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2021 Volume 32 Issue 11
2021, 32(11): 3265-3276
doi: 10.1016/j.cclet.2021.03.083
Abstract:
The efficient utilization of solar energy through photocatalysis is ideal for solving environmental issues and the development sustainable future. BiOBr-based semiconductors possess unique narrowed bandgaps and layered structures, thereby widely studied as photocatalysts for environmental remediation. However, a little has been focused on the comprehensive reviewing of BiOBr despite its extensive and promising applications. In this review, the state-of-the-art developments of BiOBr-based photocatalysts for environmental remediation are summarized. Particular focus is paid to the synthetic strategies for the control of the resulting morphologies, as well as efficient modification strategies for improving the photocatalytic activities. These include boosting the bulk phase by charge separation, enhancing the spatial charge separation, and engineering the surface states. The environmental uses of BiOBr-based photocatalysts are also reviewed in terms of purification of pollutants and CO2 reduction. Finally, future challenges and opportunities of BiOBr-based materials in photocatalysis are discussed. Overall, this review provides a good basis for future exploration of high-efficiency solar-driven photocatalysts for environmental sustainability.
The efficient utilization of solar energy through photocatalysis is ideal for solving environmental issues and the development sustainable future. BiOBr-based semiconductors possess unique narrowed bandgaps and layered structures, thereby widely studied as photocatalysts for environmental remediation. However, a little has been focused on the comprehensive reviewing of BiOBr despite its extensive and promising applications. In this review, the state-of-the-art developments of BiOBr-based photocatalysts for environmental remediation are summarized. Particular focus is paid to the synthetic strategies for the control of the resulting morphologies, as well as efficient modification strategies for improving the photocatalytic activities. These include boosting the bulk phase by charge separation, enhancing the spatial charge separation, and engineering the surface states. The environmental uses of BiOBr-based photocatalysts are also reviewed in terms of purification of pollutants and CO2 reduction. Finally, future challenges and opportunities of BiOBr-based materials in photocatalysis are discussed. Overall, this review provides a good basis for future exploration of high-efficiency solar-driven photocatalysts for environmental sustainability.
2021, 32(11): 3277-3287
doi: 10.1016/j.cclet.2021.04.049
Abstract:
Air batteries are promising energy storage technologies that have gained continuous attraction due to their high energy densities. At present, investigations on anodes of air batteries are usually focused on various metals such as Li, Zn, Al. In contrast, the semiconductor anodes like Si and Ge are less investigated. Si-air battery possesses a high theoretical energy density and Ge-air battery has a high actual power density and ideal safety. Besides anodes, air cathodes where oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are also the key components in air batteries. To further promote the discharging performance and facilitate energy conversion/storage, semiconductor materials have been introduced in electrochemical cells like Li-O2 and Zn-air batteries. This review briefly summarizes semiconductor materials utilized in various air batteries, including the progress of Si-air and Ge-air batteries and recent advances in semiconductor cathodes catalysts. Finally, the remaining challenges and further perspective are discussed.
Air batteries are promising energy storage technologies that have gained continuous attraction due to their high energy densities. At present, investigations on anodes of air batteries are usually focused on various metals such as Li, Zn, Al. In contrast, the semiconductor anodes like Si and Ge are less investigated. Si-air battery possesses a high theoretical energy density and Ge-air battery has a high actual power density and ideal safety. Besides anodes, air cathodes where oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are also the key components in air batteries. To further promote the discharging performance and facilitate energy conversion/storage, semiconductor materials have been introduced in electrochemical cells like Li-O2 and Zn-air batteries. This review briefly summarizes semiconductor materials utilized in various air batteries, including the progress of Si-air and Ge-air batteries and recent advances in semiconductor cathodes catalysts. Finally, the remaining challenges and further perspective are discussed.
2021, 32(11): 3288-3297
doi: 10.1016/j.cclet.2021.04.053
Abstract:
Heterogeneous nanostructures that are defined as a hybrid structure consisting of two or more nanoscale domains with distinct chemical compositions or physical characteristics have attracted intense efforts in recent years. In this review, we focus on the introduction of a number of heterogeneous nanostructures derived using core-shell Ag-Pt nanoparticles as starting materials, including hollow, dimeric and composite structures and also highlight their application in catalyzing electrochemical reactions, e.g., methanol oxidation reaction and oxygen reduction reaction. This review not only shows the capability of core-shell Ag-Pt nanoparticles in producing various heterogeneous nanostructures as starting templates, but also highlights the structural design or electronic interaction that endows the heterogeneous nanostructures with enhanced catalytic properties either in methanol oxidation or in oxygen reduction. Further, we also make some perspectives for more heterogeneous nanostructures that may be prepared by using core-shell Ag-Pt particles or their derivatives so as to offer the readers the opportunities and challenges in this field.
Heterogeneous nanostructures that are defined as a hybrid structure consisting of two or more nanoscale domains with distinct chemical compositions or physical characteristics have attracted intense efforts in recent years. In this review, we focus on the introduction of a number of heterogeneous nanostructures derived using core-shell Ag-Pt nanoparticles as starting materials, including hollow, dimeric and composite structures and also highlight their application in catalyzing electrochemical reactions, e.g., methanol oxidation reaction and oxygen reduction reaction. This review not only shows the capability of core-shell Ag-Pt nanoparticles in producing various heterogeneous nanostructures as starting templates, but also highlights the structural design or electronic interaction that endows the heterogeneous nanostructures with enhanced catalytic properties either in methanol oxidation or in oxygen reduction. Further, we also make some perspectives for more heterogeneous nanostructures that may be prepared by using core-shell Ag-Pt particles or their derivatives so as to offer the readers the opportunities and challenges in this field.
2021, 32(11): 3298-3306
doi: 10.1016/j.cclet.2021.02.035
Abstract:
As an emerging thermal-driven membrane technology, membrane distillation (MD) has attracted immense attention for desalination and water purification. The membranes for MD generally have hydrophobic or superhydrophobic properties to enable vapor permeation without liquid passage (e.g., wetting). However, conventional MD membranes cannot undergo long term stable operations due to gradual wetting in practical applications where the feed solution often contains multiple low-surface tension contaminants (e.g., oil). Recently, omniphobic membranes repelling all sorts of liquids and typically having ultralow surface energy and re-entrant structures have been developed for robust MD to mitigate wetting and fouling. In this paper, we aim to provide a comprehensive review of recent progress on omniphobic membranes. Fundamentals, desirable properties, advantages and applications of omniphobic membranes are discussed. We also summarize the research efforts and methods to engineer omniphobic membranes. Finally, the challenges and future research directions on omniphobic membranes are discussed.
As an emerging thermal-driven membrane technology, membrane distillation (MD) has attracted immense attention for desalination and water purification. The membranes for MD generally have hydrophobic or superhydrophobic properties to enable vapor permeation without liquid passage (e.g., wetting). However, conventional MD membranes cannot undergo long term stable operations due to gradual wetting in practical applications where the feed solution often contains multiple low-surface tension contaminants (e.g., oil). Recently, omniphobic membranes repelling all sorts of liquids and typically having ultralow surface energy and re-entrant structures have been developed for robust MD to mitigate wetting and fouling. In this paper, we aim to provide a comprehensive review of recent progress on omniphobic membranes. Fundamentals, desirable properties, advantages and applications of omniphobic membranes are discussed. We also summarize the research efforts and methods to engineer omniphobic membranes. Finally, the challenges and future research directions on omniphobic membranes are discussed.
2021, 32(11): 3307-3321
doi: 10.1016/j.cclet.2021.04.001
Abstract:
Metal-organic framework nanosheets (MONs) as the emerging materials have been attracting great interest because the nanosheets possess a range of fascinating attributes including high surface areas and sufficient accessible active sites, and their nanoscale thicknesses are favorable for mass diffusion and transfer of substrates and products with respect to bulk metal-organic frameworks (MOFs). This review first summarizes the synthetic methods of various MONs from top-down and bottom-up methods as well as their diverse composites with different components. Then, the catalytic applications of MON based nanocatalysts are discussed and the relationships among the composition, structure and catalytic performances are revealed. Finally, the challenges and future outlook about the synthesis of diverse MONs and their composites for heterogeneous catalysis are prospected.
Metal-organic framework nanosheets (MONs) as the emerging materials have been attracting great interest because the nanosheets possess a range of fascinating attributes including high surface areas and sufficient accessible active sites, and their nanoscale thicknesses are favorable for mass diffusion and transfer of substrates and products with respect to bulk metal-organic frameworks (MOFs). This review first summarizes the synthetic methods of various MONs from top-down and bottom-up methods as well as their diverse composites with different components. Then, the catalytic applications of MON based nanocatalysts are discussed and the relationships among the composition, structure and catalytic performances are revealed. Finally, the challenges and future outlook about the synthesis of diverse MONs and their composites for heterogeneous catalysis are prospected.
2021, 32(11): 3322-3330
doi: 10.1016/j.cclet.2021.04.046
Abstract:
Pillar[5]arenes, designed and prepared by Ogoshi et al. in 2008 initially, refer to fifth classical macrocyclics. Among a wide range of pillar[5]arenes, rim-differentiated pillar[5]arenes containing five identical substituents on one rim and five different identical groups on the other rims are considered the most noteworthy type of pillar[5]arenes. As compared with the perfunctionalized pillar[5]arene, the self-assembly properties of rim-differentiated pillar[5]arenes have more varieties. On the other hand, in comparison with other types of pillar[5]arenes, the rim-differentiated pillar[5]arenes exhibit a more rigid symmetrical structure. In the present review, the synthetic methods, host-guest interactions, self-assembly properties and applications of rim-differentiated pillar[5]arenes are summarized. Hopefully, this review will be conducive to researchers in macrocyclic supramolecular chemistry.
Pillar[5]arenes, designed and prepared by Ogoshi et al. in 2008 initially, refer to fifth classical macrocyclics. Among a wide range of pillar[5]arenes, rim-differentiated pillar[5]arenes containing five identical substituents on one rim and five different identical groups on the other rims are considered the most noteworthy type of pillar[5]arenes. As compared with the perfunctionalized pillar[5]arene, the self-assembly properties of rim-differentiated pillar[5]arenes have more varieties. On the other hand, in comparison with other types of pillar[5]arenes, the rim-differentiated pillar[5]arenes exhibit a more rigid symmetrical structure. In the present review, the synthetic methods, host-guest interactions, self-assembly properties and applications of rim-differentiated pillar[5]arenes are summarized. Hopefully, this review will be conducive to researchers in macrocyclic supramolecular chemistry.
2021, 32(11): 3331-3341
doi: 10.1016/j.cclet.2021.05.004
Abstract:
Triphenylamine (TPA) derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis, organic semiconductors, magnetic materials, etc., mainly because of their excellent redox activity. The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials, especially in relation to their electronic properties. Considering the instability of parent TPA radical cation, many efforts have been devoted to the development of stable TPA radical cations and related materials. Among them, TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals, thus endow them with outstanding redox behaviors, multiple resonance structures, and wide application in various optoelectronic devices. In this review, we give a brief introduction of organic radicals and the documented stable TPA radicals. Subsequently, a number of TPA radical cation-based macrocycles are comprehensively surveyed. It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles, but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.
Triphenylamine (TPA) derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis, organic semiconductors, magnetic materials, etc., mainly because of their excellent redox activity. The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials, especially in relation to their electronic properties. Considering the instability of parent TPA radical cation, many efforts have been devoted to the development of stable TPA radical cations and related materials. Among them, TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals, thus endow them with outstanding redox behaviors, multiple resonance structures, and wide application in various optoelectronic devices. In this review, we give a brief introduction of organic radicals and the documented stable TPA radicals. Subsequently, a number of TPA radical cation-based macrocycles are comprehensively surveyed. It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles, but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.
2021, 32(11): 3342-3354
doi: 10.1016/j.cclet.2021.05.042
Abstract:
Thirteen new fluorine-containing drugs, which have been granted approval by the US Food and Drug Administration (FDA) in 2020, are profiled in this review. Therapeutic areas of these new fluorinated pharmaceuticals include medicines and diagnostic agents for Cushing's disease, neurofibromatosis, migraine, Alzheimer's disease, myelodysplastic syndromes, hereditary angioedema attacks, and various cancers. Molecules of these approved drugs feature aromatic fluorine (Ar-F) (11 compounds), aromatic Ar-CF3 (1), aliphatic CHF (1) and CF2 (1) groups. For each compound, we provide a spectrum of biological activity, medicinal chemistry discovery, and synthetic approaches.
Thirteen new fluorine-containing drugs, which have been granted approval by the US Food and Drug Administration (FDA) in 2020, are profiled in this review. Therapeutic areas of these new fluorinated pharmaceuticals include medicines and diagnostic agents for Cushing's disease, neurofibromatosis, migraine, Alzheimer's disease, myelodysplastic syndromes, hereditary angioedema attacks, and various cancers. Molecules of these approved drugs feature aromatic fluorine (Ar-F) (11 compounds), aromatic Ar-CF3 (1), aliphatic CHF (1) and CF2 (1) groups. For each compound, we provide a spectrum of biological activity, medicinal chemistry discovery, and synthetic approaches.
2021, 32(11): 3355-3358
doi: 10.1016/j.cclet.2021.03.063
Abstract:
Designing non-noble metal electrocatalysts toward alkaline hydrogen evolution reaction (HER) with high performance at a large current density is urgent. Herein, a CoO/CoP heterostructure catalyst (termed POZ) was designed by a phosphating strategy. The strong electron transfer on the interface of CoO/CoP was experimentally and theoretically proven. POZ showed a low overpotential of 236 mV at 400 mA/cm2, which was 249 mV lower than non-phosphated sample. It also exhibited a remarkable solar-to-hydrogen conversion efficiency of 10.5%. In this work, the construction of CoO/CoP interface realized by a simple phosphating strategy could provide an important reference to boost the HER performance on those materials not merely metal oxides.
Designing non-noble metal electrocatalysts toward alkaline hydrogen evolution reaction (HER) with high performance at a large current density is urgent. Herein, a CoO/CoP heterostructure catalyst (termed POZ) was designed by a phosphating strategy. The strong electron transfer on the interface of CoO/CoP was experimentally and theoretically proven. POZ showed a low overpotential of 236 mV at 400 mA/cm2, which was 249 mV lower than non-phosphated sample. It also exhibited a remarkable solar-to-hydrogen conversion efficiency of 10.5%. In this work, the construction of CoO/CoP interface realized by a simple phosphating strategy could provide an important reference to boost the HER performance on those materials not merely metal oxides.
2021, 32(11): 3359-3363
doi: 10.1016/j.cclet.2021.04.004
Abstract:
The electrode/electrlyte interface is of great signifance to photoelectrochemical (PEC) water oxidation as the reaction mainly occur here. Herein, we focus on the effect of supercapactance of the electrode/electrlyte interface on the performance of PEC. It is discovered that the supercapacitor on the interface is crucial because it links the charge transport and solution ion adsorption on its two sides. In this study, we demonstrate an approach to promote the performance of TiO2 nanowire array (TiO2 NWs) photoanode in photoelectrochemical cells (PECs) by increasing its supercapacitance. A 2−5 nm carbon layer was coated and the interface supercapacitance increases by about 150 times. This enhances the separation rate of electron-hole pairs by collecting more holes. Meanwhile, it also promotes the water oxidation rate by adsorbing more OH− on its surface. As a result, the photocurrent density of C-TiO2 NWs was about 8 times higher than that of its carbon-free counterpart. This approach of increasing the supercapacitance of photoanodes would be attractive for enhancement of the efficiency of PECs and this work demonstrate the importance of supercapacitance of the interface for PECs.
The electrode/electrlyte interface is of great signifance to photoelectrochemical (PEC) water oxidation as the reaction mainly occur here. Herein, we focus on the effect of supercapactance of the electrode/electrlyte interface on the performance of PEC. It is discovered that the supercapacitor on the interface is crucial because it links the charge transport and solution ion adsorption on its two sides. In this study, we demonstrate an approach to promote the performance of TiO2 nanowire array (TiO2 NWs) photoanode in photoelectrochemical cells (PECs) by increasing its supercapacitance. A 2−5 nm carbon layer was coated and the interface supercapacitance increases by about 150 times. This enhances the separation rate of electron-hole pairs by collecting more holes. Meanwhile, it also promotes the water oxidation rate by adsorbing more OH− on its surface. As a result, the photocurrent density of C-TiO2 NWs was about 8 times higher than that of its carbon-free counterpart. This approach of increasing the supercapacitance of photoanodes would be attractive for enhancement of the efficiency of PECs and this work demonstrate the importance of supercapacitance of the interface for PECs.
2021, 32(11): 3364-3367
doi: 10.1016/j.cclet.2021.04.005
Abstract:
High responsivity and sensitivity play essential roles in the development of organic field-effect transistors (OFETs)-based biosensors with regard to biological detections, particularly for disease diagnosis. Nonetheless, how to design a biosensor which improves these two outstanding properties while achieving low cost, easy processing, and time saving is a daunting challenge. Herein, a novel biosensor based on OFET with copolymer thin film, whose surface is illuminated with a suitable light beam is reported. This film can be used as both an organic semiconductor material and as a photoelectric active material. Due to amplification of signals as a result of the film's strong response to light, the biosensor possesses higher responsivity and sensitivity compared to dark condition and even realizes a maximum responsivity of up to 103 for alpha-fetoprotein (AFP) detection. The simple combination of light and transistor builds a bridge between photoelectric effect and biological system. In addition, the emergence of more excellent photoelectric active materials is expected to pave a way for ultrasensitive bio-chemical diagnostic tools.
High responsivity and sensitivity play essential roles in the development of organic field-effect transistors (OFETs)-based biosensors with regard to biological detections, particularly for disease diagnosis. Nonetheless, how to design a biosensor which improves these two outstanding properties while achieving low cost, easy processing, and time saving is a daunting challenge. Herein, a novel biosensor based on OFET with copolymer thin film, whose surface is illuminated with a suitable light beam is reported. This film can be used as both an organic semiconductor material and as a photoelectric active material. Due to amplification of signals as a result of the film's strong response to light, the biosensor possesses higher responsivity and sensitivity compared to dark condition and even realizes a maximum responsivity of up to 103 for alpha-fetoprotein (AFP) detection. The simple combination of light and transistor builds a bridge between photoelectric effect and biological system. In addition, the emergence of more excellent photoelectric active materials is expected to pave a way for ultrasensitive bio-chemical diagnostic tools.
2021, 32(11): 3368-3371
doi: 10.1016/j.cclet.2021.04.010
Abstract:
Dopamine (DA) is easy to be oxidized and polymerizes to form polydopamine (pDA) in alkaline conditions, while the synthesis is usually time-consuming (48 h). Herein, the polymerization of DA is completed with 4 h under the catalysis of acid phosphatase (ACP). The high efficiency makes the detection of DA feasibility based on the self-polymerization of DA. In this assay, pDA is grown in situ on the surface of covalent organic frameworks (COFs), and then the fluorescence of COFs is quenched significantly. The linear range of DA is achieved from 0.5–50 μmol/L with a detection limit of 0.16 μmol/L. The detection of DA is not interfered with uric acid, ascorbic acid, and some phenolic compounds, because these substances cannot polymerize in the presence of ACP. Moreover, benefiting from the good sensitivity and selectivity, DA has been successfully determined by this strategy in human urine samples with satisfactory recoveries.
Dopamine (DA) is easy to be oxidized and polymerizes to form polydopamine (pDA) in alkaline conditions, while the synthesis is usually time-consuming (48 h). Herein, the polymerization of DA is completed with 4 h under the catalysis of acid phosphatase (ACP). The high efficiency makes the detection of DA feasibility based on the self-polymerization of DA. In this assay, pDA is grown in situ on the surface of covalent organic frameworks (COFs), and then the fluorescence of COFs is quenched significantly. The linear range of DA is achieved from 0.5–50 μmol/L with a detection limit of 0.16 μmol/L. The detection of DA is not interfered with uric acid, ascorbic acid, and some phenolic compounds, because these substances cannot polymerize in the presence of ACP. Moreover, benefiting from the good sensitivity and selectivity, DA has been successfully determined by this strategy in human urine samples with satisfactory recoveries.
2021, 32(11): 3372-3376
doi: 10.1016/j.cclet.2021.04.009
Abstract:
This work presents a novel strategy for engineering a GC stationary phase with high selectivity, inertness and thermal stability by introducing the 3D π-rich TP moieties to the terminals of a polar chain polymer. Herein, we provide the first example, i.e., a new TP-terminated polycaprolactone polymer (TPP) as the stationary phase for GC analyses. As demonstrated, the TPP column achieved distinctly improved inertness to fatty acids and aldehydes, and dramatically enhanced thermal stability (about 100 ℃ higher) over the PCL column. Also, the TPP column exhibited high resolving capability towards the positional isomers of phenols, anilines and alkylated/halobenzenes and showed good potential in detecting minor impurities in chemical products. Importantly, the proposed strategy is facile, feasible and generally applicable to analogous polymers.
This work presents a novel strategy for engineering a GC stationary phase with high selectivity, inertness and thermal stability by introducing the 3D π-rich TP moieties to the terminals of a polar chain polymer. Herein, we provide the first example, i.e., a new TP-terminated polycaprolactone polymer (TPP) as the stationary phase for GC analyses. As demonstrated, the TPP column achieved distinctly improved inertness to fatty acids and aldehydes, and dramatically enhanced thermal stability (about 100 ℃ higher) over the PCL column. Also, the TPP column exhibited high resolving capability towards the positional isomers of phenols, anilines and alkylated/halobenzenes and showed good potential in detecting minor impurities in chemical products. Importantly, the proposed strategy is facile, feasible and generally applicable to analogous polymers.
2021, 32(11): 3377-3381
doi: 10.1016/j.cclet.2021.04.028
Abstract:
H2O2 has been widely applied in the fields of chemical synthesis, medical sterilization, pollutant removal, etc., due to its strong oxidizing property and the avoidable secondary pollution. Despite of the enhanced performance for H2O2 generation over g-C3N4 semiconductors through promoting the separation of photo-generated charge carriers, the effect of migration orientation of charge carriers is still ambiguous. For this emotion, surface modification of g-C3N4 was employed to adjust the migration orientation of charge carriers, in order to investigate systematically its effect on the performance of H2O2 generation. It was found that ultrathin g-C3N4 (UCN) modified by boron nitride (BN), as an effective hole-attract agent, demonstrated a significantly enhanced performance. Particularly, for the optimum UCN/BN-40% catalyst, 4.0-fold higher yield of H2O2 was obtained in comparison with the pristine UCN. As comparison, UCN modified by carbon dust demonstrated a completely opposite tendency. The remarkably improved performance over UCN/BN was ascribed to the fact that more photo-generated electrons were remained inside of triazine structure of g-C3N4, leading to the formation of larger amount of 1, 4-endoxide. It is anticipated that our work could provide new insights for the design of photocatalyst with significantly improved performance for H2O2 generation.
H2O2 has been widely applied in the fields of chemical synthesis, medical sterilization, pollutant removal, etc., due to its strong oxidizing property and the avoidable secondary pollution. Despite of the enhanced performance for H2O2 generation over g-C3N4 semiconductors through promoting the separation of photo-generated charge carriers, the effect of migration orientation of charge carriers is still ambiguous. For this emotion, surface modification of g-C3N4 was employed to adjust the migration orientation of charge carriers, in order to investigate systematically its effect on the performance of H2O2 generation. It was found that ultrathin g-C3N4 (UCN) modified by boron nitride (BN), as an effective hole-attract agent, demonstrated a significantly enhanced performance. Particularly, for the optimum UCN/BN-40% catalyst, 4.0-fold higher yield of H2O2 was obtained in comparison with the pristine UCN. As comparison, UCN modified by carbon dust demonstrated a completely opposite tendency. The remarkably improved performance over UCN/BN was ascribed to the fact that more photo-generated electrons were remained inside of triazine structure of g-C3N4, leading to the formation of larger amount of 1, 4-endoxide. It is anticipated that our work could provide new insights for the design of photocatalyst with significantly improved performance for H2O2 generation.
2021, 32(11): 3382-3386
doi: 10.1016/j.cclet.2021.04.027
Abstract:
The existence of many anions in wastewater reduces the removal efficiency of phosphate by adsorbents under realistic conditions. Facing this challenge, the study reports on an insistent and stable composite adsorbent of molybdate complexes Fe-(MoOx) embedded in a macroporous anion exchange resin (D-201). [Fe(MoOx)]-D-201 shows 93.7% adsorption capacity (28.3 mg/g) for phosphate even when the molar concentration of coexisting ions is 5 times higher than phosphate. The capacity of adsorbent is maintained more than 84.2% after five regeneration cycles to remove phosphate in the wastewater containing coexisting ions. The ability of highly selective removal of phosphate is maintained during the regeneration cycles explained by the change of the binding of molybdate clusters with phosphate, which is due to the different structures of molybdate clusters depending on various pH. In general, this work puts forward a new idea for the development of phosphorus removal adsorbents for the treatment of wastewater containing coexisting ions.
The existence of many anions in wastewater reduces the removal efficiency of phosphate by adsorbents under realistic conditions. Facing this challenge, the study reports on an insistent and stable composite adsorbent of molybdate complexes Fe-(MoOx) embedded in a macroporous anion exchange resin (D-201). [Fe(MoOx)]-D-201 shows 93.7% adsorption capacity (28.3 mg/g) for phosphate even when the molar concentration of coexisting ions is 5 times higher than phosphate. The capacity of adsorbent is maintained more than 84.2% after five regeneration cycles to remove phosphate in the wastewater containing coexisting ions. The ability of highly selective removal of phosphate is maintained during the regeneration cycles explained by the change of the binding of molybdate clusters with phosphate, which is due to the different structures of molybdate clusters depending on various pH. In general, this work puts forward a new idea for the development of phosphorus removal adsorbents for the treatment of wastewater containing coexisting ions.
2021, 32(11): 3387-3392
doi: 10.1016/j.cclet.2021.04.050
Abstract:
Hydrogen peroxide (H2O2) disproportionation, iron precipitation, and narrow pH range are the drawbacks of traditional Fenton process. To surmount these barriers, we proposed a ferric ion (Fe3+)-ascorbic acid (AA) complex catalyzed calcium peroxide (CaO2) Fenton-like system to remove organic dyes in water. This collaborative Fe3+/AA/CaO2 system presented an obvious improvement in the methyl orange (MO) decolorization, and also effectively eliminated other dyes. Response surface method was employed to optimize the running parameters for this coupling process. Under the optimized arguments (2.76 mmol/L Fe3+, 0.68 mmol/L AA, and 4 mmol/L CaO2), the MO removal achieved 98.90% after 15 min at pH 6.50, which was close to the computed outcome of 99.30%. Furthermore, this Fenton-like system could perform well in a wide range of pH (3-11), and enhance the H2O2 decomposition and Fe ions recycle. The scavenger experiment result indicated that hydroxyl radical, superoxide anion free radical, and singlet oxygen were acted on the dye elimination. Moreover, electron spin resonance analysis corroborated that the existences of these active species in the Fe3+/AA/CaO2 system. This study could advance the development of Fenton-like technique in organic effluent disposal.
Hydrogen peroxide (H2O2) disproportionation, iron precipitation, and narrow pH range are the drawbacks of traditional Fenton process. To surmount these barriers, we proposed a ferric ion (Fe3+)-ascorbic acid (AA) complex catalyzed calcium peroxide (CaO2) Fenton-like system to remove organic dyes in water. This collaborative Fe3+/AA/CaO2 system presented an obvious improvement in the methyl orange (MO) decolorization, and also effectively eliminated other dyes. Response surface method was employed to optimize the running parameters for this coupling process. Under the optimized arguments (2.76 mmol/L Fe3+, 0.68 mmol/L AA, and 4 mmol/L CaO2), the MO removal achieved 98.90% after 15 min at pH 6.50, which was close to the computed outcome of 99.30%. Furthermore, this Fenton-like system could perform well in a wide range of pH (3-11), and enhance the H2O2 decomposition and Fe ions recycle. The scavenger experiment result indicated that hydroxyl radical, superoxide anion free radical, and singlet oxygen were acted on the dye elimination. Moreover, electron spin resonance analysis corroborated that the existences of these active species in the Fe3+/AA/CaO2 system. This study could advance the development of Fenton-like technique in organic effluent disposal.
2021, 32(11): 3393-3397
doi: 10.1016/j.cclet.2021.05.066
Abstract:
With the ever-growing demand of clean water for the healthy world, water purification has become an urgent global issue. Singlet oxygen (1O2) as unique non-radical derivative of oxygen, possessing unoccupied π* orbital and exhibiting high selectivity towards electron-rich organic pollutants. Nevertheless, most of the approaches suffer from low-efficiency or biotoxicity, which severely restrict their potential applications. Therefore, in this work, we propose a general strategy via photoelectrocatalytic for selectively reducing oxygen to 1O2 with designed carbon bridged carbon nitride (CBCN). This work highlights the important role of synergistic photo-electro-catalytic effect for selectively generating the 1O2 via oxygen reduction pathway, which can be a promising way especially for degrading electron-rich pollutants.
With the ever-growing demand of clean water for the healthy world, water purification has become an urgent global issue. Singlet oxygen (1O2) as unique non-radical derivative of oxygen, possessing unoccupied π* orbital and exhibiting high selectivity towards electron-rich organic pollutants. Nevertheless, most of the approaches suffer from low-efficiency or biotoxicity, which severely restrict their potential applications. Therefore, in this work, we propose a general strategy via photoelectrocatalytic for selectively reducing oxygen to 1O2 with designed carbon bridged carbon nitride (CBCN). This work highlights the important role of synergistic photo-electro-catalytic effect for selectively generating the 1O2 via oxygen reduction pathway, which can be a promising way especially for degrading electron-rich pollutants.
2021, 32(11): 3398-3401
doi: 10.1016/j.cclet.2021.04.052
Abstract:
A hydrophobic carbon dots (Glc-OCDs) derived from octadecylamine and glucose were successfully synthesized for the first time and then grafted onto the porous silica surface by the "Nano-on-Micro" strategy, which was served as a new stationary phase (Sil-Glc-OCDs) for reversed-phase liquid chromatography. The structure of this stationary phase was carefully verified by laser scanning confocal microscope, Fourier transform infrared spectrometry, elemental analysis, contact angle measurement, etc. Several analytes including seven polycyclic aromatic hydrocarbons, eight alkylbenzenes, eight phenols and seven sulfonamides can be well separated on this stationary phase. Better separation performance for certain analytes over commercial C18 column was obtained. Interestingly, this stationary phase exhibited excellent chromatographic selectivity in the separation of the isomers of tert‑butylbenzene, sec‑butylbenzene, isobutylbenzene and n-butylbenzene. In addition, this new Sil-Glc-OCDs column was also applied for detection of calycosin-7-glucoside, ononin, calycosin, formononetin, genistein and isorhamnetin in the extract of Radix Astragali, which were found that the concentration was 0.15 g/L, 0.088 g/L, 0.14 g/L, 0.086 g/L, 0.18 g/L and 0.29 g/L, respectively. We believe that this CDs-grafted silica materials are promising for chromatographic separation.
A hydrophobic carbon dots (Glc-OCDs) derived from octadecylamine and glucose were successfully synthesized for the first time and then grafted onto the porous silica surface by the "Nano-on-Micro" strategy, which was served as a new stationary phase (Sil-Glc-OCDs) for reversed-phase liquid chromatography. The structure of this stationary phase was carefully verified by laser scanning confocal microscope, Fourier transform infrared spectrometry, elemental analysis, contact angle measurement, etc. Several analytes including seven polycyclic aromatic hydrocarbons, eight alkylbenzenes, eight phenols and seven sulfonamides can be well separated on this stationary phase. Better separation performance for certain analytes over commercial C18 column was obtained. Interestingly, this stationary phase exhibited excellent chromatographic selectivity in the separation of the isomers of tert‑butylbenzene, sec‑butylbenzene, isobutylbenzene and n-butylbenzene. In addition, this new Sil-Glc-OCDs column was also applied for detection of calycosin-7-glucoside, ononin, calycosin, formononetin, genistein and isorhamnetin in the extract of Radix Astragali, which were found that the concentration was 0.15 g/L, 0.088 g/L, 0.14 g/L, 0.086 g/L, 0.18 g/L and 0.29 g/L, respectively. We believe that this CDs-grafted silica materials are promising for chromatographic separation.
2021, 32(11): 3402-3409
doi: 10.1016/j.cclet.2021.04.061
Abstract:
The effects of different species and concentrations' signal molecules on aerobic activated sludge system were investigated through batch experiments. Results showed that the fastest NH4+-N oxidization rate and the most extracellular polymeric substances (EPS) secretion were obtained by adding 5 nmol/L N-hexanoyl-l-homoserine lactone (C6-HSL) into the aerobic activated sludge. Further study investigated the correlation among N-acyl-homoserine lactones-mediated quorum sensing (AHLs-mediated QS), nutrient removal performances and microbial communities with the long-term addition of 5 nmol/L C6-HSL. It was found that C6-HSL-manipulation could enhance the stability and optimize the decontamination performance of aerobic granular sludge (AGS) system. Microbial compositions considerably shifted with long-term C6-HSL-manipulation. Exogenous C6-HSL-manipulation inhibited quorum quenching-related (QQ-related) activities and enhanced QS-related activities during the stable period. The proposed C6-HSL-manipulation might be a potential technology to inhibit the growth of harmful bacteria in AGS, which could provide a theoretical foundation for the realization of more stable biological wastewater treatments.
The effects of different species and concentrations' signal molecules on aerobic activated sludge system were investigated through batch experiments. Results showed that the fastest NH4+-N oxidization rate and the most extracellular polymeric substances (EPS) secretion were obtained by adding 5 nmol/L N-hexanoyl-l-homoserine lactone (C6-HSL) into the aerobic activated sludge. Further study investigated the correlation among N-acyl-homoserine lactones-mediated quorum sensing (AHLs-mediated QS), nutrient removal performances and microbial communities with the long-term addition of 5 nmol/L C6-HSL. It was found that C6-HSL-manipulation could enhance the stability and optimize the decontamination performance of aerobic granular sludge (AGS) system. Microbial compositions considerably shifted with long-term C6-HSL-manipulation. Exogenous C6-HSL-manipulation inhibited quorum quenching-related (QQ-related) activities and enhanced QS-related activities during the stable period. The proposed C6-HSL-manipulation might be a potential technology to inhibit the growth of harmful bacteria in AGS, which could provide a theoretical foundation for the realization of more stable biological wastewater treatments.
2021, 32(11): 3410-3415
doi: 10.1016/j.cclet.2021.04.057
Abstract:
It is still a challenge to eliminate efficiently fluoride ion from groundwater, especially to design and synthesis an adsorbent possessing high adsorption capacity, recyclability and wide pH application conditions. Herein we present millimeter-sized sulfate-type zirconium alginate hydrogel beads with 3D network structure (AHB@Zr-SO42−) that exhibited a maximum adsorption capacity of 101.3 mg/g with wide pH applicability (pH 3−9). This material have ~2.5 times higher adsorption capacity than that of pure zirconium alginate hydrogel beads (AHB@Zr) and it was ascribed to ion exchange between SO42− and F− on the surface of AHB@Zr-SO42−, which was verified via ion chromatography measurement coupled with X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectrometer (FTIR Spectrometer) analysis. Density functional theory (DFT) calculations indicated that the ion exchange process between SO42− and F− in AHB@Zr-SO42− was energetically favorable than OH− and F− in AHB@Zr. In addition, 310 bed volumes (BV) of effluent was realized via column adsorption of groundwater containing fluoride on AHB@Zr-SO42− and indicated that it is a promising candidate for mitigating the problem of fluoride-containing groundwater.
It is still a challenge to eliminate efficiently fluoride ion from groundwater, especially to design and synthesis an adsorbent possessing high adsorption capacity, recyclability and wide pH application conditions. Herein we present millimeter-sized sulfate-type zirconium alginate hydrogel beads with 3D network structure (AHB@Zr-SO42−) that exhibited a maximum adsorption capacity of 101.3 mg/g with wide pH applicability (pH 3−9). This material have ~2.5 times higher adsorption capacity than that of pure zirconium alginate hydrogel beads (AHB@Zr) and it was ascribed to ion exchange between SO42− and F− on the surface of AHB@Zr-SO42−, which was verified via ion chromatography measurement coupled with X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectrometer (FTIR Spectrometer) analysis. Density functional theory (DFT) calculations indicated that the ion exchange process between SO42− and F− in AHB@Zr-SO42− was energetically favorable than OH− and F− in AHB@Zr. In addition, 310 bed volumes (BV) of effluent was realized via column adsorption of groundwater containing fluoride on AHB@Zr-SO42− and indicated that it is a promising candidate for mitigating the problem of fluoride-containing groundwater.
2021, 32(11): 3416-3420
doi: 10.1016/j.cclet.2021.05.002
Abstract:
Tracking the movement of droplets in digital microfluidics is essential to improve its control stability and obtain dynamic information for its applications such as point-of-care testing, environment monitoring and chemical synthesis. Herein, an intelligent, accurate and fast droplet tracking method based on machine vision is developed for applications of digital microfluidics. To continuously recognize the transparent droplets in real-time and avoid the interferes from background patterns or inhomogeneous illumination, we introduced the correlation filter tracker, enabling online learning of the multi-features of the droplets in Fourier domain. Results show the proposed droplet tracking method could accurately locate the droplets. We also demonstrated the capacity of the proposed method for estimation of the droplet velocity as faster as 20 mm/s, and its application in online monitoring the Griess reaction for both colorimetric assay of nitrite and study of reaction kinetics.
Tracking the movement of droplets in digital microfluidics is essential to improve its control stability and obtain dynamic information for its applications such as point-of-care testing, environment monitoring and chemical synthesis. Herein, an intelligent, accurate and fast droplet tracking method based on machine vision is developed for applications of digital microfluidics. To continuously recognize the transparent droplets in real-time and avoid the interferes from background patterns or inhomogeneous illumination, we introduced the correlation filter tracker, enabling online learning of the multi-features of the droplets in Fourier domain. Results show the proposed droplet tracking method could accurately locate the droplets. We also demonstrated the capacity of the proposed method for estimation of the droplet velocity as faster as 20 mm/s, and its application in online monitoring the Griess reaction for both colorimetric assay of nitrite and study of reaction kinetics.
2021, 32(11): 3421-3425
doi: 10.1016/j.cclet.2021.05.019
Abstract:
In this work, a very simple dual-readout lateral flow test strip (LFTS) platform was developed for sensitive detection of alkaline phosphatase (ALP) based on a portable device. In this assay, quantum dots (QDs) conjugated with bovine serum albumin (QDs-BSA) were chosen as fluorescence signal labels. In the absence of ALP, MnO2 nanosheets aggregate on the test line and exhibit an obvious brown color, which can be observed by naked eyes to realize semi-qualitative analysis. Meanwhile, fluorescence intensity of QDs-BSA can also be effectively quenched by MnO2 nanosheets due to inner-filter effect. Correspondingly, in the presence of ALP, ALP can catalyze the hydrolysis of ascorbic acid 2-phosphate (AAP) to generate L-ascorbic acid (AA), which can reduce MnO2 into Mn2+, accompanying with the obvious fluorescence recovery of the QDs. By simply monitoring the change of colorimetric and fluorescent signal on the test line, trace amount of ALP can be quantitatively detected. Under the optimal conditions, measurable evaluation of ALP was reached in a linear range from 1 U/L to 20 U/L with a detection limit of 0.7 U/L based on fluorescence signal. Furthermore, this colorimetric/fluorescent dual-readout assay was successfully applied to monitor ALP in human serum samples, showing its great potential as a point of care biosensor for clinical diagnosis.
In this work, a very simple dual-readout lateral flow test strip (LFTS) platform was developed for sensitive detection of alkaline phosphatase (ALP) based on a portable device. In this assay, quantum dots (QDs) conjugated with bovine serum albumin (QDs-BSA) were chosen as fluorescence signal labels. In the absence of ALP, MnO2 nanosheets aggregate on the test line and exhibit an obvious brown color, which can be observed by naked eyes to realize semi-qualitative analysis. Meanwhile, fluorescence intensity of QDs-BSA can also be effectively quenched by MnO2 nanosheets due to inner-filter effect. Correspondingly, in the presence of ALP, ALP can catalyze the hydrolysis of ascorbic acid 2-phosphate (AAP) to generate L-ascorbic acid (AA), which can reduce MnO2 into Mn2+, accompanying with the obvious fluorescence recovery of the QDs. By simply monitoring the change of colorimetric and fluorescent signal on the test line, trace amount of ALP can be quantitatively detected. Under the optimal conditions, measurable evaluation of ALP was reached in a linear range from 1 U/L to 20 U/L with a detection limit of 0.7 U/L based on fluorescence signal. Furthermore, this colorimetric/fluorescent dual-readout assay was successfully applied to monitor ALP in human serum samples, showing its great potential as a point of care biosensor for clinical diagnosis.
2021, 32(11): 3426-3430
doi: 10.1016/j.cclet.2021.05.020
Abstract:
5-Methylcytosine (5mC) is the most important epigenetic modification in mammals. The active DNA demethylation could be achieved through the ten-eleven translocation (TET) protein-mediated oxidization of 5mC with the generation of 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC) and 5-carboxylcytosine (5caC). It has been known that 5mC, 5hmC and 5fC play critical roles in modulating gene expression. However, unlike the 5mC, 5hmC, and 5fC, the functions of 5caC are still underexplored. Investigation of the functions of 5caC relies on the accurate quantification and localization analysis of 5caC in DNA. In the current study, we developed a method by chemical conversion in conjugation with ligation-based real-time quantitative PCR (qPCR) for the site-specific quantification of 5caC in DNA. This method depends on the selective conversion of 5caC to form dihydrouracil (DHU) by pyridine borane treatment. DHU behaves like thymine and pairs with adenine (DHU-A). Thus, the chemical conversion by pyridine borane leads to the transformation of base paring from 5caC-G to DHU-A, which is utilized to achieve the site-specific detection and quantification of 5caC in DNA. As a proof-of-concept, the developed method was successfully applied in the site-specific quantification of 5caC in synthesized DNA spiked in complex biological samples. The method is rapid, straightforward and cost-effective, and shows promising in promoting the investigation of the functional roles of 5caC in future study.
5-Methylcytosine (5mC) is the most important epigenetic modification in mammals. The active DNA demethylation could be achieved through the ten-eleven translocation (TET) protein-mediated oxidization of 5mC with the generation of 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC) and 5-carboxylcytosine (5caC). It has been known that 5mC, 5hmC and 5fC play critical roles in modulating gene expression. However, unlike the 5mC, 5hmC, and 5fC, the functions of 5caC are still underexplored. Investigation of the functions of 5caC relies on the accurate quantification and localization analysis of 5caC in DNA. In the current study, we developed a method by chemical conversion in conjugation with ligation-based real-time quantitative PCR (qPCR) for the site-specific quantification of 5caC in DNA. This method depends on the selective conversion of 5caC to form dihydrouracil (DHU) by pyridine borane treatment. DHU behaves like thymine and pairs with adenine (DHU-A). Thus, the chemical conversion by pyridine borane leads to the transformation of base paring from 5caC-G to DHU-A, which is utilized to achieve the site-specific detection and quantification of 5caC in DNA. As a proof-of-concept, the developed method was successfully applied in the site-specific quantification of 5caC in synthesized DNA spiked in complex biological samples. The method is rapid, straightforward and cost-effective, and shows promising in promoting the investigation of the functional roles of 5caC in future study.
2021, 32(11): 3431-3434
doi: 10.1016/j.cclet.2021.05.022
Abstract:
A facile approach was successfully employed to prepare Fe2O3/Co3O4 nanosheet arrays on nickel foams (Fe2O3/Co3O4@NF), which owned such advantages as narrow band gap energies and high separation rate of photoexcited electron-hole pairs. The combination of Fe2O3 and Co3O4 dramatically enhanced the photocatalytic activity towards sulfamethoxazole (SMZ) degradation, with the highest catalytic efficiency of k = 0.0538 min−1, which was much higher than that of Fe2O3@NF (0.0098 min−1) and Co3O4@NF (0.0094 min−1). The introduction of Ni foam could not only act as the support to anchor photocatalyst, but also work as the electron mediator to promote the transition of electron-hole pairs. Reactive species trapping experiments combined with electron paramagnetic resonance analysis confirmed ·O2− was primarily responsible for SMZ degradation. Furthermore, Fe2O3/Co3O4@NF was effective and almost unaffected by inorganic cations and anions in aqueous solution. This study could provide a facile and promising path for the construction of self-supported metal oxide-based heterojunction with high efficiency and strong stability.
A facile approach was successfully employed to prepare Fe2O3/Co3O4 nanosheet arrays on nickel foams (Fe2O3/Co3O4@NF), which owned such advantages as narrow band gap energies and high separation rate of photoexcited electron-hole pairs. The combination of Fe2O3 and Co3O4 dramatically enhanced the photocatalytic activity towards sulfamethoxazole (SMZ) degradation, with the highest catalytic efficiency of k = 0.0538 min−1, which was much higher than that of Fe2O3@NF (0.0098 min−1) and Co3O4@NF (0.0094 min−1). The introduction of Ni foam could not only act as the support to anchor photocatalyst, but also work as the electron mediator to promote the transition of electron-hole pairs. Reactive species trapping experiments combined with electron paramagnetic resonance analysis confirmed ·O2− was primarily responsible for SMZ degradation. Furthermore, Fe2O3/Co3O4@NF was effective and almost unaffected by inorganic cations and anions in aqueous solution. This study could provide a facile and promising path for the construction of self-supported metal oxide-based heterojunction with high efficiency and strong stability.
2021, 32(11): 3435-3439
doi: 10.1016/j.cclet.2021.05.029
Abstract:
A facile hydrothermal method was applied to gain stably and highly efficient CuO-CeO2 (denoted as Cu1Ce2) catalyst for toluene oxidation. The changes of surface and inter properties on Cu1Ce2 were investigated comparing with pure CeO2 and pure CuO. The formation of Cu-Ce interface promotes the electron transfer between Cu and Ce through Cu2+ + Ce3+ ↔ Cu+ + Ce4+ and leads to high redox properties and mobility of oxygen species. Thus, the Cu1Ce2 catalyst makes up the shortcoming of CeO2 and CuO and achieved high catalytic performance with T50 = 234 ℃ and T99 = 250 ℃ (the temperature at which 50% and 90% C7H8 conversion is obtained, respectively) for toluene oxidation. Different reaction steps and intermediates for toluene oxidation over Cu1Ce2, CeO2 and CuO were detected by in situ DRIFTS, the fast benzyl species conversion and preferential transformation of benzoates into carbonates through C=C breaking over Cu1Ce2 should accelerate the reaction.
A facile hydrothermal method was applied to gain stably and highly efficient CuO-CeO2 (denoted as Cu1Ce2) catalyst for toluene oxidation. The changes of surface and inter properties on Cu1Ce2 were investigated comparing with pure CeO2 and pure CuO. The formation of Cu-Ce interface promotes the electron transfer between Cu and Ce through Cu2+ + Ce3+ ↔ Cu+ + Ce4+ and leads to high redox properties and mobility of oxygen species. Thus, the Cu1Ce2 catalyst makes up the shortcoming of CeO2 and CuO and achieved high catalytic performance with T50 = 234 ℃ and T99 = 250 ℃ (the temperature at which 50% and 90% C7H8 conversion is obtained, respectively) for toluene oxidation. Different reaction steps and intermediates for toluene oxidation over Cu1Ce2, CeO2 and CuO were detected by in situ DRIFTS, the fast benzyl species conversion and preferential transformation of benzoates into carbonates through C=C breaking over Cu1Ce2 should accelerate the reaction.
2021, 32(11): 3440-3445
doi: 10.1016/j.cclet.2021.05.067
Abstract:
Hydrogen fuel cells are among the promising energy sources worldwide, which could accomplish cyclic production of energy and avoid the emission of green-house or contaminative byproducts. However, sulfur compounds (SCs) even at trace level (nmol/mol) are usually involved in cell construction and further H2 production, which would cause degradation of the catalysts and shorten the lifetime of the fuel cells. Moreover, the highly reactive SCs could cause varied species and concentrations of them in complex matrices, so online rather than offline analysis of SCs in H2 would be preferred. In this context, we developed a new system combining online cryogenic preconcentration of nine SCs and subsequent determination by GC-SCD (sulfur chemiluminescent detector), with the correlation coefficients of the calibration curves higher than 0.999, calculated limits of detection no higher than 0.050 nmol/mol, analytical time around 30 min per sample, and satisfactory precision and accuracy (RSD < 5% and SD < 15%). The analytical performance was much better than or at least comparable to the previously reported and the developed system was successfully applied for real sample analysis.
Hydrogen fuel cells are among the promising energy sources worldwide, which could accomplish cyclic production of energy and avoid the emission of green-house or contaminative byproducts. However, sulfur compounds (SCs) even at trace level (nmol/mol) are usually involved in cell construction and further H2 production, which would cause degradation of the catalysts and shorten the lifetime of the fuel cells. Moreover, the highly reactive SCs could cause varied species and concentrations of them in complex matrices, so online rather than offline analysis of SCs in H2 would be preferred. In this context, we developed a new system combining online cryogenic preconcentration of nine SCs and subsequent determination by GC-SCD (sulfur chemiluminescent detector), with the correlation coefficients of the calibration curves higher than 0.999, calculated limits of detection no higher than 0.050 nmol/mol, analytical time around 30 min per sample, and satisfactory precision and accuracy (RSD < 5% and SD < 15%). The analytical performance was much better than or at least comparable to the previously reported and the developed system was successfully applied for real sample analysis.
2021, 32(11): 3446-3449
doi: 10.1016/j.cclet.2021.05.034
Abstract:
Single-cell imaging, a powerful analytical method to study single-cell behavior, such as gene expression and protein profiling, provides an essential basis for modern medical diagnosis. The coding and localization function of microfluidic chips has been developed and applied in living single-cell imaging in recent years. Simultaneously, chip-based living single-cell imaging is also limited by complicated trapping steps, low cell utilization, and difficult high-resolution imaging. To solve these problems, an ultra-thin temperature-controllable microwell array chip (UTCMA chip) was designed to develop a living single-cell workstation in this study for continuous on-chip culture and real-time high-resolution imaging of living single cells. The chip-based on ultra-thin ITO glass is highly matched with an inverted microscope (or confocal microscope) with a high magnification objective (100 × oil lens), and the temperature of the chip can be controlled by combining it with a home-made temperature control device. High-throughput single-cell patterning is realized in one step when the microwell array on the chip uses hydrophilic glass as the substrate and hydrophobic SU-8 photoresist as the wall. The cell utilization rate, single-cell capture rate, and microwell occupancy rate are all close to 100% in the microwell array. This method will be useful in rare single-cell research, extending its application in the biological and medical-related fields, such as early diagnosis of disease, personalized therapy, and research-based on single-cell analysis.
Single-cell imaging, a powerful analytical method to study single-cell behavior, such as gene expression and protein profiling, provides an essential basis for modern medical diagnosis. The coding and localization function of microfluidic chips has been developed and applied in living single-cell imaging in recent years. Simultaneously, chip-based living single-cell imaging is also limited by complicated trapping steps, low cell utilization, and difficult high-resolution imaging. To solve these problems, an ultra-thin temperature-controllable microwell array chip (UTCMA chip) was designed to develop a living single-cell workstation in this study for continuous on-chip culture and real-time high-resolution imaging of living single cells. The chip-based on ultra-thin ITO glass is highly matched with an inverted microscope (or confocal microscope) with a high magnification objective (100 × oil lens), and the temperature of the chip can be controlled by combining it with a home-made temperature control device. High-throughput single-cell patterning is realized in one step when the microwell array on the chip uses hydrophilic glass as the substrate and hydrophobic SU-8 photoresist as the wall. The cell utilization rate, single-cell capture rate, and microwell occupancy rate are all close to 100% in the microwell array. This method will be useful in rare single-cell research, extending its application in the biological and medical-related fields, such as early diagnosis of disease, personalized therapy, and research-based on single-cell analysis.
2021, 32(11): 3450-3456
doi: 10.1016/j.cclet.2021.05.040
Abstract:
Bandgap engineering through single-atom site binding on semiconducting photocatalyst can boost the intrinsic activity, selectivity, carrier separation, and electron transport. Here, we report a mixed-valence Ag(0) and Ag(Ⅰ) single atoms co-decorated semiconducting chalcopyrite quantum dots (Ag/CuFeS2 QDs) photocatalyst. It demonstrates efficient photocatalytic performances for specific organic dye (rhodamine B, denoted as RhB) as well as inorganic dye (Cr(Ⅵ)) removal in water under natural sunlight irradiation. The RhB degradation and Cr(Ⅵ) removal efficiencies by Ag/CuFeS2 QDs were 3.55 and 6.75 times higher than those of the naked CuFeS2 QDs at their optimal pH conditions, respectively. Besides, in a mixture of RhB and Cr(Ⅵ) solution under neutral condition, the removal ratio has been elevated from 30.2% to 79.4% for Cr(Ⅵ), and from 95.2% to 97.3% for RhB degradation by using Ag/CuFeS2 QDs after 2 h sunlight illumination. The intrinsic mechanism for the photocatalytic performance improvement is attributed to the narrow bandgap of the single-atomic Ag(Ⅰ) anchored CuFeS2 QDs, which engineers the electronic structure as well as expands the optical light response range. Significantly, the highly active Ag(0)/CuFeS2 and Ag(Ⅰ)/CuFeS2 effectively improve the separation efficiency of the carriers, thus enhancing the photocatalytic performances. This work presents a highly efficient single atom/QDs photocatalyst, constructed through bandgap engineering via mixed-valence single noble metal atoms binding on semiconducting QDs. It paves the way for developing high-efficiency single-atom photocatalysts for complex pollutions removal in dyeing wastewater environment.
Bandgap engineering through single-atom site binding on semiconducting photocatalyst can boost the intrinsic activity, selectivity, carrier separation, and electron transport. Here, we report a mixed-valence Ag(0) and Ag(Ⅰ) single atoms co-decorated semiconducting chalcopyrite quantum dots (Ag/CuFeS2 QDs) photocatalyst. It demonstrates efficient photocatalytic performances for specific organic dye (rhodamine B, denoted as RhB) as well as inorganic dye (Cr(Ⅵ)) removal in water under natural sunlight irradiation. The RhB degradation and Cr(Ⅵ) removal efficiencies by Ag/CuFeS2 QDs were 3.55 and 6.75 times higher than those of the naked CuFeS2 QDs at their optimal pH conditions, respectively. Besides, in a mixture of RhB and Cr(Ⅵ) solution under neutral condition, the removal ratio has been elevated from 30.2% to 79.4% for Cr(Ⅵ), and from 95.2% to 97.3% for RhB degradation by using Ag/CuFeS2 QDs after 2 h sunlight illumination. The intrinsic mechanism for the photocatalytic performance improvement is attributed to the narrow bandgap of the single-atomic Ag(Ⅰ) anchored CuFeS2 QDs, which engineers the electronic structure as well as expands the optical light response range. Significantly, the highly active Ag(0)/CuFeS2 and Ag(Ⅰ)/CuFeS2 effectively improve the separation efficiency of the carriers, thus enhancing the photocatalytic performances. This work presents a highly efficient single atom/QDs photocatalyst, constructed through bandgap engineering via mixed-valence single noble metal atoms binding on semiconducting QDs. It paves the way for developing high-efficiency single-atom photocatalysts for complex pollutions removal in dyeing wastewater environment.
2021, 32(11): 3457-3462
doi: 10.1016/j.cclet.2021.05.074
Abstract:
The rapid degradation of organic pollutants, process monitoring and online controlling to obtain advanced products and decreased by-products are great and challenging tasks in environmental treatments. Herein, an accelerated plasma degradation in milliseconds was achieved by combining electrospray-based acceleration and plasma-based degradation. Taking the degradation of chloroaniline as an example, 97% of the degradation can be achieved in milliseconds. The velocity distribution of droplets was determined to be 40–50 m/s after being degraded for 0.30 ms, which exhibited different degradation behaviors in different milliseconds. Simultaneously, by virtue of the real-time and on-line detection ability of ambient mass spectrometry, intermediates, by-products and advanced products were monitored. Therefore, degradation mechanisms for different degradation times were proposed, which would provide theoretical guidance on obtaining efficient and green degradation. The fabrication, examining and understanding of accelerated plasma degradation not only enlarged application of accelerated reactions, but also promoted green and efficient degradation for environmental treatments.
The rapid degradation of organic pollutants, process monitoring and online controlling to obtain advanced products and decreased by-products are great and challenging tasks in environmental treatments. Herein, an accelerated plasma degradation in milliseconds was achieved by combining electrospray-based acceleration and plasma-based degradation. Taking the degradation of chloroaniline as an example, 97% of the degradation can be achieved in milliseconds. The velocity distribution of droplets was determined to be 40–50 m/s after being degraded for 0.30 ms, which exhibited different degradation behaviors in different milliseconds. Simultaneously, by virtue of the real-time and on-line detection ability of ambient mass spectrometry, intermediates, by-products and advanced products were monitored. Therefore, degradation mechanisms for different degradation times were proposed, which would provide theoretical guidance on obtaining efficient and green degradation. The fabrication, examining and understanding of accelerated plasma degradation not only enlarged application of accelerated reactions, but also promoted green and efficient degradation for environmental treatments.
2021, 32(11): 3463-3468
doi: 10.1016/j.cclet.2021.05.039
Abstract:
Ultrabroad spectral absorption is required for semiconductor photocatalysts utilized for solar-to-chemical energy conversion. The light response range can be extended by element doping, but the photocatalytic performance is generally not enhanced correspondingly. Here we present a solid alkali activation strategy to synthesize near-infrared (NIR) light-activated carbon-doped polymeric carbon nitride (A-cPCN) by combining the copolymerization of melamine and 1, 3, 5-trimesic acid. The prepared A-cPCN is highly crystalline with a narrowed bandgap and enhanced efficiency in the separation of photogenerated electrons and holes. Under irradiation with NIR light (780 nm ≥ λ ≥ 700 nm), A-cPCN shows an excellent photocatalytic activity for H2 generation from water with rate of 165 µmol g−1 h−1, and the photo-redox activity for H2O2 production (109 µmol g−1 h−1) from H2O and O2, whereas no observed photocatalytic activity over pure PCN. The NIR photocatalytic activity is due to carbon doping, which leads to the formation of an interband level, and the alkali activation that achieved shrinking the transfer distance of photocarriers. The current synergistic strategy may open insights to fabricate other carbon-nitrogen-based photocatalysts for enhanced solar energy capture and conversion.
Ultrabroad spectral absorption is required for semiconductor photocatalysts utilized for solar-to-chemical energy conversion. The light response range can be extended by element doping, but the photocatalytic performance is generally not enhanced correspondingly. Here we present a solid alkali activation strategy to synthesize near-infrared (NIR) light-activated carbon-doped polymeric carbon nitride (A-cPCN) by combining the copolymerization of melamine and 1, 3, 5-trimesic acid. The prepared A-cPCN is highly crystalline with a narrowed bandgap and enhanced efficiency in the separation of photogenerated electrons and holes. Under irradiation with NIR light (780 nm ≥ λ ≥ 700 nm), A-cPCN shows an excellent photocatalytic activity for H2 generation from water with rate of 165 µmol g−1 h−1, and the photo-redox activity for H2O2 production (109 µmol g−1 h−1) from H2O and O2, whereas no observed photocatalytic activity over pure PCN. The NIR photocatalytic activity is due to carbon doping, which leads to the formation of an interband level, and the alkali activation that achieved shrinking the transfer distance of photocarriers. The current synergistic strategy may open insights to fabricate other carbon-nitrogen-based photocatalysts for enhanced solar energy capture and conversion.
2021, 32(11): 3469-3473
doi: 10.1016/j.cclet.2021.05.064
Abstract:
The development of the preparation strategy for high-quality and large-size graphene via eco-friendly routes is still a challenging issue. Herein, we have successfully developed a novel route to chemically exfoliate natural graphite into high-quality and large-size graphene in a binary-peroxidant system. This system is composed of urea peroxide (CO(NH2)2·H2O2) and hydrogen peroxide (H2O2), where CO(NH2)2·H2O2 is used in preparing graphene for the first time. Benefiting from the complete decomposition of CO(NH2)2·H2O2 and H2O2 into gaseous species under microwave (MW) irradiation, no water-washing and effluent-treatment are needed in this chemical exfoliation procedure, thus the preparation of graphene in an eco-friendly way is realized. The resultant graphene behaves a large-size, high-quality and few-layer feature with a yield of ~100%. Then 4 µm-thick ultrathin graphene paper fabricated from the as-exfoliated graphene is used as an electromagnetic interference (EMI) shielding material. And its absolute effectiveness of EMI shielding (SSE/t) is up to 34, 176.9 dB cm2/g, which is, to the best of our knowledge, among the highest values so far reported for typical EMI shielding materials. The EMI shielding performance demonstrates a great application potential of graphene paper in meeting the ever-increasingly EMI shielding demands in miniaturized electronic devices.
The development of the preparation strategy for high-quality and large-size graphene via eco-friendly routes is still a challenging issue. Herein, we have successfully developed a novel route to chemically exfoliate natural graphite into high-quality and large-size graphene in a binary-peroxidant system. This system is composed of urea peroxide (CO(NH2)2·H2O2) and hydrogen peroxide (H2O2), where CO(NH2)2·H2O2 is used in preparing graphene for the first time. Benefiting from the complete decomposition of CO(NH2)2·H2O2 and H2O2 into gaseous species under microwave (MW) irradiation, no water-washing and effluent-treatment are needed in this chemical exfoliation procedure, thus the preparation of graphene in an eco-friendly way is realized. The resultant graphene behaves a large-size, high-quality and few-layer feature with a yield of ~100%. Then 4 µm-thick ultrathin graphene paper fabricated from the as-exfoliated graphene is used as an electromagnetic interference (EMI) shielding material. And its absolute effectiveness of EMI shielding (SSE/t) is up to 34, 176.9 dB cm2/g, which is, to the best of our knowledge, among the highest values so far reported for typical EMI shielding materials. The EMI shielding performance demonstrates a great application potential of graphene paper in meeting the ever-increasingly EMI shielding demands in miniaturized electronic devices.
2021, 32(11): 3474-3478
doi: 10.1016/j.cclet.2021.04.056
Abstract:
Exosomal miRNAs, as potential biomarkers in liquid biopsy for cancer early diagnosis, have aroused widespread concern. Herein, an electrochemical biosensor based on DNA "nano-bridge" was designed and applied to detect exosomal microRNA-21 (miR-21) derived from breast cancer cells. In brief, the target miR-21 can specifically open the hairpin probe 1(HP1) labeled on the gold electrode (GE) surface through strand displacement reaction. Thus the exposed loop region of HP1 can act as an initiator sequence to activate the hybridization chain reaction (HCR) between two kinetically trapped hairpin probes: HP2 immobilized on the GE surface and biotin labeled HP3 in solution. Cascade HCR leads to the formation of DNA "nano-bridge" tethered to the GE surface with a great deal of "piers". Upon addition of avidin-modified horseradish peroxidase (HRP), numerous HRP were bound to the formed "nano-bridge" through biotin-avidin interaction to arouse tremendous current signal. In theory, only a single miR-21 is able to trigger the continuous HCR between HP2 and HP3 until all of the HP2 are exhausted. Therefore the proposed biosensor achieved ultrahigh sensitivity toward miR-21 with the detection limit down to 168 amol/L, as well as little cross-hybridization even at the single-base-mismatched level. Successful attempts were also made in the detection of exosomal miR-21 obtained from the MCF-7 of breast cancer cell line. To our knowledge, this is the first attempt to built horizontal DNA nano-structure on the electrode surface for exosomal miRNAs detection. In a word, the high sensitivity, selectivity, low cost make the proposed method hold great potential application for early point-of-care (POC) diagnostics of cancer.
Exosomal miRNAs, as potential biomarkers in liquid biopsy for cancer early diagnosis, have aroused widespread concern. Herein, an electrochemical biosensor based on DNA "nano-bridge" was designed and applied to detect exosomal microRNA-21 (miR-21) derived from breast cancer cells. In brief, the target miR-21 can specifically open the hairpin probe 1(HP1) labeled on the gold electrode (GE) surface through strand displacement reaction. Thus the exposed loop region of HP1 can act as an initiator sequence to activate the hybridization chain reaction (HCR) between two kinetically trapped hairpin probes: HP2 immobilized on the GE surface and biotin labeled HP3 in solution. Cascade HCR leads to the formation of DNA "nano-bridge" tethered to the GE surface with a great deal of "piers". Upon addition of avidin-modified horseradish peroxidase (HRP), numerous HRP were bound to the formed "nano-bridge" through biotin-avidin interaction to arouse tremendous current signal. In theory, only a single miR-21 is able to trigger the continuous HCR between HP2 and HP3 until all of the HP2 are exhausted. Therefore the proposed biosensor achieved ultrahigh sensitivity toward miR-21 with the detection limit down to 168 amol/L, as well as little cross-hybridization even at the single-base-mismatched level. Successful attempts were also made in the detection of exosomal miR-21 obtained from the MCF-7 of breast cancer cell line. To our knowledge, this is the first attempt to built horizontal DNA nano-structure on the electrode surface for exosomal miRNAs detection. In a word, the high sensitivity, selectivity, low cost make the proposed method hold great potential application for early point-of-care (POC) diagnostics of cancer.
2021, 32(11): 3479-3482
doi: 10.1016/j.cclet.2021.05.057
Abstract:
Recent studies have shown that CTP may act as a ligand to regulate the activity of its target proteins in many biological processes. However, proteome-wide identification of CTP-binding proteins remains challenging. Here, we employed a biotinylated CTP affinity probe coupled with stable isotope labeling by amino acids in cell culture (SILAC)-based quantitative proteomics approach to capture, identify and quantify CTP-binding proteins in human cells. By performing two types of competitive SILAC experiments with high vs. low concentrations of CTP probe (100 vs. 10 µmol/L) or with CTP probe in the presence of free CTP, we identified 90 potential CTP-binding proteins which are involved in a variety of biological processes, including protein folding, nucleotide binding and cell-cell adhesion. Together, we developed a chemical proteomic method for uncovering the CTP-binding proteins in human cells, which could be widely applicable for profiling CTP-binding proteins in other biological samples.
Recent studies have shown that CTP may act as a ligand to regulate the activity of its target proteins in many biological processes. However, proteome-wide identification of CTP-binding proteins remains challenging. Here, we employed a biotinylated CTP affinity probe coupled with stable isotope labeling by amino acids in cell culture (SILAC)-based quantitative proteomics approach to capture, identify and quantify CTP-binding proteins in human cells. By performing two types of competitive SILAC experiments with high vs. low concentrations of CTP probe (100 vs. 10 µmol/L) or with CTP probe in the presence of free CTP, we identified 90 potential CTP-binding proteins which are involved in a variety of biological processes, including protein folding, nucleotide binding and cell-cell adhesion. Together, we developed a chemical proteomic method for uncovering the CTP-binding proteins in human cells, which could be widely applicable for profiling CTP-binding proteins in other biological samples.
2021, 32(11): 3483-3486
doi: 10.1016/j.cclet.2021.05.068
Abstract:
Nanodiamond (ND) polarizer can be used for dynamic nuclear polarization (DNP), owing to unpaired electrons provided by surface defects. However, 1H enhancement via Overhauser DNP (ODNP) using ND in-situ liquid has been found much smaller than traditional radicals. Herein, we study the surface properties of ND using electron spin resonance (ESR) and Raman methods firstly. Then the enhancement of 1H ODNP is explored using ND as polarizer with different nanoparticle sizes and concentrations at home-built 0.06 T DNP spectrometer. The surface of ND with the size of 30 nm is further modification via high temperature air oxidized and the enhancement was measured. The results show that nanoparticle sizes and Raman peak intensity ratio of sp2/sp3 hybridization are approximate negative correlation and positive correlation to enhancement, respectively. Furthermore, there is no significant enhancement in the oxidation group, and a −22.5-fold 1H ODNP enhancement is achieved in-situ liquid at room temperature, which demonstrate the ND can be used as an efficient enhancer. We expect ND to play a greater role in biomedical research, especially for multimodal imaging with improving the performance of ND surface.
Nanodiamond (ND) polarizer can be used for dynamic nuclear polarization (DNP), owing to unpaired electrons provided by surface defects. However, 1H enhancement via Overhauser DNP (ODNP) using ND in-situ liquid has been found much smaller than traditional radicals. Herein, we study the surface properties of ND using electron spin resonance (ESR) and Raman methods firstly. Then the enhancement of 1H ODNP is explored using ND as polarizer with different nanoparticle sizes and concentrations at home-built 0.06 T DNP spectrometer. The surface of ND with the size of 30 nm is further modification via high temperature air oxidized and the enhancement was measured. The results show that nanoparticle sizes and Raman peak intensity ratio of sp2/sp3 hybridization are approximate negative correlation and positive correlation to enhancement, respectively. Furthermore, there is no significant enhancement in the oxidation group, and a −22.5-fold 1H ODNP enhancement is achieved in-situ liquid at room temperature, which demonstrate the ND can be used as an efficient enhancer. We expect ND to play a greater role in biomedical research, especially for multimodal imaging with improving the performance of ND surface.
2021, 32(11): 3487-3490
doi: 10.1016/j.cclet.2021.04.036
Abstract:
The development of multifunctional theranostic nano-agents is an important resolution for personalized treatment of cancer. In this work, we synthesized a new kind of gadolinium boride nanoparticles (GBN) by a microwave-assisted chemical etching method, and discovered their optical characteristics including fluorescence imaging and near-infrared (NIR) photothermal conversion capability. Bright greenishyellow fluorescence enabled for intracellular localization, while effective NIR-photothermal conversion supported photothermal therapy (PTT). In vitro and in vivo results indicated that GBN exhibited a superior antitumor performance and high biocompatibility. This study demonstrated a promising multifunctional theranostic nanoplatform for cancer treatment.
The development of multifunctional theranostic nano-agents is an important resolution for personalized treatment of cancer. In this work, we synthesized a new kind of gadolinium boride nanoparticles (GBN) by a microwave-assisted chemical etching method, and discovered their optical characteristics including fluorescence imaging and near-infrared (NIR) photothermal conversion capability. Bright greenishyellow fluorescence enabled for intracellular localization, while effective NIR-photothermal conversion supported photothermal therapy (PTT). In vitro and in vivo results indicated that GBN exhibited a superior antitumor performance and high biocompatibility. This study demonstrated a promising multifunctional theranostic nanoplatform for cancer treatment.
2021, 32(11): 3491-3495
doi: 10.1016/j.cclet.2021.03.066
Abstract:
Modifying electrochemical surface area (ECSA) and surface chemistry are promising approaches to enhance the capacities of oxygen cathodes for lithium-oxygen (Li-O2) batteries. Although various chemical approaches have been successfully used to tune the cathode surface, versatile physical techniques including plasma etching etc. could be more effortless and effective than arduous chemical treatments. Herein, for the first time, we propose a facile oxygen plasma treatment to simultaneously etch and modify the surface of Co3O4 nanosheet arrays (NAs) cathode for Li-O2 batteries. The oxygen plasma not only etches Co3O4 nanosheets to enhance the ECSA but also lowers the oxygen vacancy concentration to enable a Co3+-rich surface. In addition, the NA architecture enables the full exposure of oxygen vacancies and surface Co3+ that function as the catalytically active sites. Thus, the synergistic effects of enhanced ECSA, modest oxygen vacancy and high surface Co3+ achieve a significantly enhanced reversible capacity of 3.45 mAh/cm2 for Co3O4 NAs. This work not only develops a promising high-capacity cathode for Li-O2 batteries, but also provides a facile physical method to simultaneously tune the nanostructure and surface chemistry of energy storage materials.
Modifying electrochemical surface area (ECSA) and surface chemistry are promising approaches to enhance the capacities of oxygen cathodes for lithium-oxygen (Li-O2) batteries. Although various chemical approaches have been successfully used to tune the cathode surface, versatile physical techniques including plasma etching etc. could be more effortless and effective than arduous chemical treatments. Herein, for the first time, we propose a facile oxygen plasma treatment to simultaneously etch and modify the surface of Co3O4 nanosheet arrays (NAs) cathode for Li-O2 batteries. The oxygen plasma not only etches Co3O4 nanosheets to enhance the ECSA but also lowers the oxygen vacancy concentration to enable a Co3+-rich surface. In addition, the NA architecture enables the full exposure of oxygen vacancies and surface Co3+ that function as the catalytically active sites. Thus, the synergistic effects of enhanced ECSA, modest oxygen vacancy and high surface Co3+ achieve a significantly enhanced reversible capacity of 3.45 mAh/cm2 for Co3O4 NAs. This work not only develops a promising high-capacity cathode for Li-O2 batteries, but also provides a facile physical method to simultaneously tune the nanostructure and surface chemistry of energy storage materials.
2021, 32(11): 3496-3500
doi: 10.1016/j.cclet.2021.03.069
Abstract:
The rapid development of next-generation flexible electronics stimulates the growing demand for flexible and wearable power sources with high energy density. Li metal capacitor (LMC), combining with a Li metal anode and an activated carbon cathode, exhibits extremely high energy density and high power density due to the unique energy storage mechanism, thus showing great potential for powering wearable electronic devices. Herein, a flexible LMC based on an in situ prepared PETEA-based gel polymer electrolyte (GPE) was reported for the first time. Owing to the high ionic conductivity of PETEA-based GPE (5.75 × 10-3 S/cm at 20 ℃), the assembled flexible LMC delivers a high capacitance of 210 F/g at 0.1 A/g within the voltage range from 1.5 V to 4.3 V vs. Li/Li+, a high energy density of 474 Wh/kg at 0.1 A/g and a high power density of 29 kW/kg at 10 A/g. More importantly, PETEA-based GPE endows the LMC with excellent flexibility and safety, which could work normally under abuse tests, such as bending, nail penetration and cutting. The in situ prepared PETEA-based GPE simplifies the fabrication process, avoids the risk of leakage and inhibits the growth of Li dendrite, making LMC a promising flexible energy storage device for the flexible electronic field.
The rapid development of next-generation flexible electronics stimulates the growing demand for flexible and wearable power sources with high energy density. Li metal capacitor (LMC), combining with a Li metal anode and an activated carbon cathode, exhibits extremely high energy density and high power density due to the unique energy storage mechanism, thus showing great potential for powering wearable electronic devices. Herein, a flexible LMC based on an in situ prepared PETEA-based gel polymer electrolyte (GPE) was reported for the first time. Owing to the high ionic conductivity of PETEA-based GPE (5.75 × 10-3 S/cm at 20 ℃), the assembled flexible LMC delivers a high capacitance of 210 F/g at 0.1 A/g within the voltage range from 1.5 V to 4.3 V vs. Li/Li+, a high energy density of 474 Wh/kg at 0.1 A/g and a high power density of 29 kW/kg at 10 A/g. More importantly, PETEA-based GPE endows the LMC with excellent flexibility and safety, which could work normally under abuse tests, such as bending, nail penetration and cutting. The in situ prepared PETEA-based GPE simplifies the fabrication process, avoids the risk of leakage and inhibits the growth of Li dendrite, making LMC a promising flexible energy storage device for the flexible electronic field.
2021, 32(11): 3501-3504
doi: 10.1016/j.cclet.2021.03.077
Abstract:
Recently, widespread attention has been devoted to the typical layered BiOCl or BiOBr because of the suitable nanostructure and band structure. However, owing to the fast carrier recombination, the photocatalytic performance of BiOX materials is not so satisfactory. Loading 1T phase WS2 nanosheets (NSs) onto Bi5O7Br NSs can improve the photocatalytic N2 fixation activity. Among these, the obtained 1T-WS2@Bi5O7Br composites with optimum 5% 1T-WS2 NSs display a significantly improved photocatalytic N2 fixation rate (8.43 mmol L-1h-1g-1), 2.51 times higher than pure Bi5O7Br (3.36 mmol L-1h-1g-1). And the outstanding stability of 1T-WS2@Bi5O7Br-5 composites is also achieved. Exactly, the photoexcited electrons from Bi5O7Br NSs are quickly transferred to conductive 1T phase WS2 as electron acceptors, which can promote the separation of carriers. In addition, 1T-WS2 NSs can provide abundant active sites on the basal and edge planes, which can promote the efficiency of photocatalytic N2 fixation. This work offers a novel solution to improve the photocatalytic performance of Bi5O7Br NSs.
Recently, widespread attention has been devoted to the typical layered BiOCl or BiOBr because of the suitable nanostructure and band structure. However, owing to the fast carrier recombination, the photocatalytic performance of BiOX materials is not so satisfactory. Loading 1T phase WS2 nanosheets (NSs) onto Bi5O7Br NSs can improve the photocatalytic N2 fixation activity. Among these, the obtained 1T-WS2@Bi5O7Br composites with optimum 5% 1T-WS2 NSs display a significantly improved photocatalytic N2 fixation rate (8.43 mmol L-1h-1g-1), 2.51 times higher than pure Bi5O7Br (3.36 mmol L-1h-1g-1). And the outstanding stability of 1T-WS2@Bi5O7Br-5 composites is also achieved. Exactly, the photoexcited electrons from Bi5O7Br NSs are quickly transferred to conductive 1T phase WS2 as electron acceptors, which can promote the separation of carriers. In addition, 1T-WS2 NSs can provide abundant active sites on the basal and edge planes, which can promote the efficiency of photocatalytic N2 fixation. This work offers a novel solution to improve the photocatalytic performance of Bi5O7Br NSs.
2021, 32(11): 3505-3508
doi: 10.1016/j.cclet.2021.04.007
Abstract:
The conversion of CO2 under mild condition is of great importance because these reactions involving CO2 can not only produce value-added chemicals from abundant and inexpensive CO2 feedstock but also close the carbon cycle. However, the chemical inertness of CO2 requires the development of high-performance catalysts. Herein, Ag nanoparticles/MIL-100(Fe) composites were synthesized by simple impregnation-reduction method and employed as catalysts for the photothermal carboxylation of terminal alkynes with CO2. MIL-100(Fe) could stabilize Ag nanoparticles and prevent them from aggregation during catalytic process. Taking the advantages of photothermal effects and catalytic activities of both Ag nanoparticles and MIL-100(Fe), various aromatic alkynes could be converted to corresponding carboxylic acid products (86%–92% yields) with 1 atm CO2 at room temperature under visible light irradiation when using Ag nanoparticles/MIL-100(Fe) as photothermal catalysts. The catalysts also showed good recyclability with almost no loss of catalytic activity for three consecutive runs. More importantly, the catalytic performance of Ag nanoparticles/MIL-100(Fe) under visible light irradiation at room temperature was comparable to that upon heating, showing that the light source could replace conventional heating method to drive the reaction. This work provided a promising strategy of utilizing solar energy for achieving efficient CO2 conversion to value-added chemicals under mild condition.
The conversion of CO2 under mild condition is of great importance because these reactions involving CO2 can not only produce value-added chemicals from abundant and inexpensive CO2 feedstock but also close the carbon cycle. However, the chemical inertness of CO2 requires the development of high-performance catalysts. Herein, Ag nanoparticles/MIL-100(Fe) composites were synthesized by simple impregnation-reduction method and employed as catalysts for the photothermal carboxylation of terminal alkynes with CO2. MIL-100(Fe) could stabilize Ag nanoparticles and prevent them from aggregation during catalytic process. Taking the advantages of photothermal effects and catalytic activities of both Ag nanoparticles and MIL-100(Fe), various aromatic alkynes could be converted to corresponding carboxylic acid products (86%–92% yields) with 1 atm CO2 at room temperature under visible light irradiation when using Ag nanoparticles/MIL-100(Fe) as photothermal catalysts. The catalysts also showed good recyclability with almost no loss of catalytic activity for three consecutive runs. More importantly, the catalytic performance of Ag nanoparticles/MIL-100(Fe) under visible light irradiation at room temperature was comparable to that upon heating, showing that the light source could replace conventional heating method to drive the reaction. This work provided a promising strategy of utilizing solar energy for achieving efficient CO2 conversion to value-added chemicals under mild condition.
2021, 32(11): 3509-3513
doi: 10.1016/j.cclet.2021.03.007
Abstract:
At present, frequent outbreaks of bacteria and viruses have seriously affected people's normal lives. Therefore, the study of broad-spectrum antibacterial nanocomposites is very promising. However, most antibacterial materials have some disadvantages, such as single bactericidal mechanisms and unrepeatable use. Based on the current situation, a kind of nanocomposite with three structures of graphene oxide (GO), quaternary ammonium salt (QAs) and N-halamine was prepared, which showed synergistic effect to improve antibacterial activity and combined with a variety of sterilization mechanisms. Meanwhile, GO can provide richer ways of sterilization and high specific surface area, which is conducive to the grafting of quaternarized N-halamine. The advantages of physical sterilization of GO, charge adsorption of QAs, reuse of N-halamine and efficient sterilization are fully utilized. The results showed that the quaternarized N-halamine-grafted GO was obtained successfully. GO grafted with quaternarized N-halamine polymer showed strong speedy bactericidal activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) (99%). It had good storage and regeneration properties.
At present, frequent outbreaks of bacteria and viruses have seriously affected people's normal lives. Therefore, the study of broad-spectrum antibacterial nanocomposites is very promising. However, most antibacterial materials have some disadvantages, such as single bactericidal mechanisms and unrepeatable use. Based on the current situation, a kind of nanocomposite with three structures of graphene oxide (GO), quaternary ammonium salt (QAs) and N-halamine was prepared, which showed synergistic effect to improve antibacterial activity and combined with a variety of sterilization mechanisms. Meanwhile, GO can provide richer ways of sterilization and high specific surface area, which is conducive to the grafting of quaternarized N-halamine. The advantages of physical sterilization of GO, charge adsorption of QAs, reuse of N-halamine and efficient sterilization are fully utilized. The results showed that the quaternarized N-halamine-grafted GO was obtained successfully. GO grafted with quaternarized N-halamine polymer showed strong speedy bactericidal activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) (99%). It had good storage and regeneration properties.
2021, 32(11): 3514-3517
doi: 10.1016/j.cclet.2021.04.037
Abstract:
The perfluoroalkylsulfonylation (CF3SO2, C2F5SO2 and CHF2SO2) in the enaminone CH bonds has been developed simply via the promotion of molecular iodine by using stable and cheap sodium perfluoroalkyl sulfinates as coupling partners. The stereoselective synthesis of E-configurated α-perfluoroalkylsulfonyl enaminones has been realized via unprecedented CH bond elaboration and CC double bond configuration inversion by free radical process.
The perfluoroalkylsulfonylation (CF3SO2, C2F5SO2 and CHF2SO2) in the enaminone CH bonds has been developed simply via the promotion of molecular iodine by using stable and cheap sodium perfluoroalkyl sulfinates as coupling partners. The stereoselective synthesis of E-configurated α-perfluoroalkylsulfonyl enaminones has been realized via unprecedented CH bond elaboration and CC double bond configuration inversion by free radical process.
2021, 32(11): 3518-3521
doi: 10.1016/j.cclet.2021.04.058
Abstract:
A new strategy is developed for the synthesis of 1-aminoisoquinoline derivatives. This Rh(Ⅲ)-catalyzed [4 + 2] annulation reaction employs benzamidines as efficient directing groups and the vinylene carbonate as an acetylene surrogate. Additionally, the reaction features broad substrate scopes and good yields, only producing carbonate anion as byproduct.
A new strategy is developed for the synthesis of 1-aminoisoquinoline derivatives. This Rh(Ⅲ)-catalyzed [4 + 2] annulation reaction employs benzamidines as efficient directing groups and the vinylene carbonate as an acetylene surrogate. Additionally, the reaction features broad substrate scopes and good yields, only producing carbonate anion as byproduct.
2021, 32(11): 3522-3525
doi: 10.1016/j.cclet.2021.04.060
Abstract:
The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization, followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry. Herein, a Schiff-base condensation method performed at room temperature was used to control the formation of [1 + 1] and [2 + 2] macrocycles. In pure MeOH, the isomer [1 + 1] macrocycles were synthesized and organic particles such as dendritic, rods, and solid microspheres were directly precipitated from the reaction solution. The [1 + 1] macrocycles can be efficiently converted into their corresponding [2 + 2] macrocycles accompanied by the tunable morphology of the organic particles when n-hexane was added to the MeOH solution. Further studies showed that these organic particles have potential application toward the selective removal of Cd2+ ions with different adsorption ability in MeOH solution.
The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization, followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry. Herein, a Schiff-base condensation method performed at room temperature was used to control the formation of [1 + 1] and [2 + 2] macrocycles. In pure MeOH, the isomer [1 + 1] macrocycles were synthesized and organic particles such as dendritic, rods, and solid microspheres were directly precipitated from the reaction solution. The [1 + 1] macrocycles can be efficiently converted into their corresponding [2 + 2] macrocycles accompanied by the tunable morphology of the organic particles when n-hexane was added to the MeOH solution. Further studies showed that these organic particles have potential application toward the selective removal of Cd2+ ions with different adsorption ability in MeOH solution.
2021, 32(11): 3526-3530
doi: 10.1016/j.cclet.2021.05.003
Abstract:
An efficient approach to functionalized 4, 6-disubstituted-and 4, 6, 6-trisubstituted-1, 3-oxazinan-2-ones skeleton has been developed through the reaction of semicyclic N, O-acetals 4a and 4b with 1, 1- disubstituted ethylenes 5 or 8. As a result of such a [4 + 2] cycloaddition process, 4, 6, 6-trisubstituted- 1, 3-oxazinan-2-ones 6aa, 6af-6au, 7ba, 7bf-7bw and 6, 6-spiro containing 1, 3-oxazinan-2-ones 9ad, 9ae, 10ba-10bg were obtained in 36%-96% yields and with moderate to excellent diastereoselectivities. In addition, the synthesis of (±)-norallosedamine 12 could be conveniently achieved from the cycloadduct 7bf.
An efficient approach to functionalized 4, 6-disubstituted-and 4, 6, 6-trisubstituted-1, 3-oxazinan-2-ones skeleton has been developed through the reaction of semicyclic N, O-acetals 4a and 4b with 1, 1- disubstituted ethylenes 5 or 8. As a result of such a [4 + 2] cycloaddition process, 4, 6, 6-trisubstituted- 1, 3-oxazinan-2-ones 6aa, 6af-6au, 7ba, 7bf-7bw and 6, 6-spiro containing 1, 3-oxazinan-2-ones 9ad, 9ae, 10ba-10bg were obtained in 36%-96% yields and with moderate to excellent diastereoselectivities. In addition, the synthesis of (±)-norallosedamine 12 could be conveniently achieved from the cycloadduct 7bf.
2021, 32(11): 3531-3534
doi: 10.1016/j.cclet.2021.05.006
Abstract:
Functional dicyclophanes with various substituents (e.g., NO2, Br, OCH3 and OH) were synthesized via one-pot SN2 reaction. Dicyclophanes can form nanospheres via the head-to-tail self-assembly between the cavities and the TPE units to exhibit aggregation-induced emission (AIE) in aqueous solution. These AIE-active nanospheres with cationic feature exhibited selective recognition with fluorescence response for anionic ATP via electrostatic interactions and hydrophobic effects in water.
Functional dicyclophanes with various substituents (e.g., NO2, Br, OCH3 and OH) were synthesized via one-pot SN2 reaction. Dicyclophanes can form nanospheres via the head-to-tail self-assembly between the cavities and the TPE units to exhibit aggregation-induced emission (AIE) in aqueous solution. These AIE-active nanospheres with cationic feature exhibited selective recognition with fluorescence response for anionic ATP via electrostatic interactions and hydrophobic effects in water.
2021, 32(11): 3535-3538
doi: 10.1016/j.cclet.2021.05.007
Abstract:
A photoinduced reaction of potassium alkyltrifluoroborates, sulfur dioxide, and para-quinone methides under visible light irradiation at room temperature is developed, giving rise to diarylmethyl alkylsulfones in moderate to good yields. This reaction works well under photocatalysis with a broad substrate scope by using DABCO·(SO2)2 as the source of sulfur dioxide. Mechanistic study shows that this transformation is initiated by alkyl radicals generated in situ from potassium alkyltrifluoroborates in the presence of photocatalyst. The subsequent insertion of sulfur dioxide and radical 1, 6-addition of para-quinone methides with alkylsulfonyl radical intermediates afford the corresponding diarylmethyl alkylsulfones.
A photoinduced reaction of potassium alkyltrifluoroborates, sulfur dioxide, and para-quinone methides under visible light irradiation at room temperature is developed, giving rise to diarylmethyl alkylsulfones in moderate to good yields. This reaction works well under photocatalysis with a broad substrate scope by using DABCO·(SO2)2 as the source of sulfur dioxide. Mechanistic study shows that this transformation is initiated by alkyl radicals generated in situ from potassium alkyltrifluoroborates in the presence of photocatalyst. The subsequent insertion of sulfur dioxide and radical 1, 6-addition of para-quinone methides with alkylsulfonyl radical intermediates afford the corresponding diarylmethyl alkylsulfones.
2021, 32(11): 3539-3543
doi: 10.1016/j.cclet.2021.05.045
Abstract:
The mixture of p-(methoxy)calix[n]arenes (n = 6, 7 or 8) was prepared in one step from p-methoxyphenol under basic conditions, and their fully methylated derivatives p-(dimethyloxy)calix[n]arenes (n = 6, 7 or 8) were also prepared and purified by column chromatography to indentify their structures. In this process, the single crystal of p-(dimethyloxy)calix[7]arene was obtained and its structure was confirmed. The proportion ofp-(methoxy)calix[6]-, [7]- and [8]-arenes in the mixture obtained from the reaction was investigated under different reaction conditions, and p-(methoxy)calix[6]- and [8]-arenes could be separated from the mixture by solvent extraction. In addition, the host-guest interaction of p-(dimethyloxy)calix[6]arene with methyl-4, 4′-bipyridinium hexafluorophosphate in organic solvents was investigated.
The mixture of p-(methoxy)calix[n]arenes (n = 6, 7 or 8) was prepared in one step from p-methoxyphenol under basic conditions, and their fully methylated derivatives p-(dimethyloxy)calix[n]arenes (n = 6, 7 or 8) were also prepared and purified by column chromatography to indentify their structures. In this process, the single crystal of p-(dimethyloxy)calix[7]arene was obtained and its structure was confirmed. The proportion ofp-(methoxy)calix[6]-, [7]- and [8]-arenes in the mixture obtained from the reaction was investigated under different reaction conditions, and p-(methoxy)calix[6]- and [8]-arenes could be separated from the mixture by solvent extraction. In addition, the host-guest interaction of p-(dimethyloxy)calix[6]arene with methyl-4, 4′-bipyridinium hexafluorophosphate in organic solvents was investigated.
2021, 32(11): 3544-3547
doi: 10.1016/j.cclet.2021.05.069
Abstract:
A condition-controlled strategy for selectively synthesis of 2-acylbenzothiazoles and bibenzo[b][1, 4]thiazines from aryl methyl ketones and disulfanediyldianilines was realized using I2/DMSO or I2/MeCN systems, respectively. The desired products were synthesized in only 15 min with moderate to excellent yields (50%-90%) under microwave-assisted, metal-free conditions. The strategy provides a great advantage for selective synthetic applications in the efficient synthesis of benzothiazoles and bibenzothiazines heterocycle compounds.
A condition-controlled strategy for selectively synthesis of 2-acylbenzothiazoles and bibenzo[b][1, 4]thiazines from aryl methyl ketones and disulfanediyldianilines was realized using I2/DMSO or I2/MeCN systems, respectively. The desired products were synthesized in only 15 min with moderate to excellent yields (50%-90%) under microwave-assisted, metal-free conditions. The strategy provides a great advantage for selective synthetic applications in the efficient synthesis of benzothiazoles and bibenzothiazines heterocycle compounds.
2021, 32(11): 3548-3552
doi: 10.1016/j.cclet.2021.01.050
Abstract:
Solid oxide fuel cells (SOFCs) can directly convert renewable biogas into electricity with high efficiency at high temperature, however the long-term stability of SOFCs is significantly affected by the carbon deposition on the anode during cell operation. Herein, we report a novel carbon removal approach by high temperature infrared light driven photocatalytic oxidation. Upon the comparison of electrochemical performance of Ni-YSZ anode and TiO2 modified Ni-YSZ anode in the state-of-the-art single cell (Ni-YSZ/YSZ/LSCM), the modified anodes exhibit markedly improved peak powder density with simulated biogas fuel (70% CH4+ 30% CO2) at 850 ℃ with less coking after 40 h operation. The high activity and carbon deposition resistance of the modified anode is possibly attributed to thein situ generated hydroxyl radical from the reduced TiOx powder under high temperature infrared light excitation, which is supported by detailed analysis of microstructural information of anodes and the powder-based thermo-photocatalytic experiments.
Solid oxide fuel cells (SOFCs) can directly convert renewable biogas into electricity with high efficiency at high temperature, however the long-term stability of SOFCs is significantly affected by the carbon deposition on the anode during cell operation. Herein, we report a novel carbon removal approach by high temperature infrared light driven photocatalytic oxidation. Upon the comparison of electrochemical performance of Ni-YSZ anode and TiO2 modified Ni-YSZ anode in the state-of-the-art single cell (Ni-YSZ/YSZ/LSCM), the modified anodes exhibit markedly improved peak powder density with simulated biogas fuel (70% CH4+ 30% CO2) at 850 ℃ with less coking after 40 h operation. The high activity and carbon deposition resistance of the modified anode is possibly attributed to thein situ generated hydroxyl radical from the reduced TiOx powder under high temperature infrared light excitation, which is supported by detailed analysis of microstructural information of anodes and the powder-based thermo-photocatalytic experiments.
2021, 32(11): 3553-3557
doi: 10.1016/j.cclet.2021.02.034
Abstract:
Although transition metal phospho-sulfides deliver outstanding electrochemical performance, complex preparation methods hindered their further development. Herein, we report a facile one-step electrodeposition approach to deposit interconnected nanowalls-like nickel cobalt phospho-sulfide (Ni-Co-P-S) nanosheets onto the surface of carbon cloth. The thin Ni-Co-P-S nanosheets with multi-components and synergetic effects delivered rich active sites, further enhancing reversible capacitance. Therefore, the as-prepared Ni-Co-P-S electrode materials exhibit excellent electrochemical performance in a three-electrode system, showcasing a high specific capacitance of 2744 F/g at 4 A/g. The full supercapacitors based on Ni-Co-P-S as positive electrode and active carbon as negative electrode showcase a high specific capacitance of 110.9 F/g at 1 A/g, impressive energy density of 39.4 Wh/kg at a power density of 797.5 W/kg in terms of excellent cycling stability (91.87% retention after 10, 000 cycles). This simple electrode position strategy for synthesizing Ni-Co-P-S can be extended to prepare electrode materials for various sustainable electrochemical energy storage/conversion technologies.
Although transition metal phospho-sulfides deliver outstanding electrochemical performance, complex preparation methods hindered their further development. Herein, we report a facile one-step electrodeposition approach to deposit interconnected nanowalls-like nickel cobalt phospho-sulfide (Ni-Co-P-S) nanosheets onto the surface of carbon cloth. The thin Ni-Co-P-S nanosheets with multi-components and synergetic effects delivered rich active sites, further enhancing reversible capacitance. Therefore, the as-prepared Ni-Co-P-S electrode materials exhibit excellent electrochemical performance in a three-electrode system, showcasing a high specific capacitance of 2744 F/g at 4 A/g. The full supercapacitors based on Ni-Co-P-S as positive electrode and active carbon as negative electrode showcase a high specific capacitance of 110.9 F/g at 1 A/g, impressive energy density of 39.4 Wh/kg at a power density of 797.5 W/kg in terms of excellent cycling stability (91.87% retention after 10, 000 cycles). This simple electrode position strategy for synthesizing Ni-Co-P-S can be extended to prepare electrode materials for various sustainable electrochemical energy storage/conversion technologies.
X-site doping in ABX3 triggers phase transition and higher Tc of the dielectric switch in perovskite
2021, 32(11): 3558-3561
doi: 10.1016/j.cclet.2021.02.040
Abstract:
Material stability is always the key factor for applied materials especially the working environment that requires higher temperature sensitivity or temperature fluctuation range. In which, the stimulus-response perovskite materials are just sensitive to stability to ensure the accuracy and stability of the signals, in the applied devices of batteries and memory storage devices and so on. However, it is still a tremendous challenge to improve the stability of perovskite materials, and maintain reliability in the devices. Here, a novel ABX2X'1 (X-site doping in an ABX3) compound [CEMP]-[CdBr2(SCN)] (1, CEMP = 1-(2-chloro-ethyl)-1-methyl-piperidine) with remarkable high-temperature reversible dielectric switching behavior was proposed. The strategy of [SCN]− doping in perovskite for improving the stability was successfully achieved. Meanwhile, the steric hindrance is increased while the energy barrier is also increased by replacing hydrogen with flexible groups, which leads to a high-temperature reversible phase transition. The new finding provides a new direction to enrich new applications and design ideas of perovskite materials. Especially the X-site strategy of doping or substitution in the ABX3, it will promote ingenious and perfect experimental results in material synthesis and performance improvement by chemistry disciplines.
Material stability is always the key factor for applied materials especially the working environment that requires higher temperature sensitivity or temperature fluctuation range. In which, the stimulus-response perovskite materials are just sensitive to stability to ensure the accuracy and stability of the signals, in the applied devices of batteries and memory storage devices and so on. However, it is still a tremendous challenge to improve the stability of perovskite materials, and maintain reliability in the devices. Here, a novel ABX2X'1 (X-site doping in an ABX3) compound [CEMP]-[CdBr2(SCN)] (1, CEMP = 1-(2-chloro-ethyl)-1-methyl-piperidine) with remarkable high-temperature reversible dielectric switching behavior was proposed. The strategy of [SCN]− doping in perovskite for improving the stability was successfully achieved. Meanwhile, the steric hindrance is increased while the energy barrier is also increased by replacing hydrogen with flexible groups, which leads to a high-temperature reversible phase transition. The new finding provides a new direction to enrich new applications and design ideas of perovskite materials. Especially the X-site strategy of doping or substitution in the ABX3, it will promote ingenious and perfect experimental results in material synthesis and performance improvement by chemistry disciplines.
2021, 32(11): 3562-3565
doi: 10.1016/j.cclet.2021.02.063
Abstract:
Hydrogen isotope separation is a challenging task due to their similar properties. Herein, based on the chemical affinity quantum sieve (CAQS) effect, the D2/H2 separation performance of M2(m-dobdc) (M = Co, Ni, Mg, Mn; m-dobdc4− = 4,6-dioxido-1,3-benzenedicarboxylate), a series of honeycomb-shaped MOFs with high stability and abundant open metal sites, are studied by gases sorption and breakthrough experiments, in which two critical factors, gas uptake and adsorption enthalpy, are taken into consideration. Among these MOFs, Co2(m-dobdc) exhibits the longest D2 retention time of 180 min/g (H2/D2/Ne: 1/1/98) at 77 K because of its second-highest adsorption enthalpy (10.7 kJ/mol for H2 and 11.8 kJ/mol for D2) and the best sorption capacity (5.22 mmol/g for H2 and 5.49 mmol/g for D2) under low pressure of 1 kPa and 77 K), which make it a promising material for industrial hydrogen isotope separation. Moreover, the results indicate that H2 and D2 capacities under low pressure (about 1 kPa) dominate the final D2/H2 separation property of MOFs.
Hydrogen isotope separation is a challenging task due to their similar properties. Herein, based on the chemical affinity quantum sieve (CAQS) effect, the D2/H2 separation performance of M2(m-dobdc) (M = Co, Ni, Mg, Mn; m-dobdc4− = 4,6-dioxido-1,3-benzenedicarboxylate), a series of honeycomb-shaped MOFs with high stability and abundant open metal sites, are studied by gases sorption and breakthrough experiments, in which two critical factors, gas uptake and adsorption enthalpy, are taken into consideration. Among these MOFs, Co2(m-dobdc) exhibits the longest D2 retention time of 180 min/g (H2/D2/Ne: 1/1/98) at 77 K because of its second-highest adsorption enthalpy (10.7 kJ/mol for H2 and 11.8 kJ/mol for D2) and the best sorption capacity (5.22 mmol/g for H2 and 5.49 mmol/g for D2) under low pressure of 1 kPa and 77 K), which make it a promising material for industrial hydrogen isotope separation. Moreover, the results indicate that H2 and D2 capacities under low pressure (about 1 kPa) dominate the final D2/H2 separation property of MOFs.
2021, 32(11): 3566-3569
doi: 10.1016/j.cclet.2021.02.066
Abstract:
In this work, two aza-BODIPY derivatives, 3,5-diphenyl-1,7-di(p-dodecyloxyphenyl)-aza-BODIPY (CJF) and 3,5-di(p-bromophenyl-1,7-di(p-dodecyloxyphenyl)-aza-BODIPY (2Br-CJF) acted as model molecules to form the self-assembly monolayers on the solid-liquid interface. With the utilizing of scanning tunnelling microscope (STM), we demonstrated that intermolecular Br…F—BF interactions existed in 2Br-CJF self-assembly structure and played an important role in strengthening the stability of 2Br-CJF self-assembly structure. This result is supported by density functional theory (DFT) calculation.
In this work, two aza-BODIPY derivatives, 3,5-diphenyl-1,7-di(p-dodecyloxyphenyl)-aza-BODIPY (CJF) and 3,5-di(p-bromophenyl-1,7-di(p-dodecyloxyphenyl)-aza-BODIPY (2Br-CJF) acted as model molecules to form the self-assembly monolayers on the solid-liquid interface. With the utilizing of scanning tunnelling microscope (STM), we demonstrated that intermolecular Br…F—BF interactions existed in 2Br-CJF self-assembly structure and played an important role in strengthening the stability of 2Br-CJF self-assembly structure. This result is supported by density functional theory (DFT) calculation.
2021, 32(11): 3570-3574
doi: 10.1016/j.cclet.2021.03.005
Abstract:
Na3V2(PO4)3 is a very prospective sodium-ion batteries (SIBs) electrode material owing to its NASICON structure and high reversible capacity. Conversely, on account of its intrinsic poor electronic conductivity, Na3V2(PO4)3 electrode materials confront with some significant limitations like poor cycle and rate performance which inhibit their practical applications in the energy fields. Herein, a simple two-step method has been implemented for the successful preparation of carbon-coated Na3V2(PO4)3 materials. As synthesized sample shows a remarkable electrochemical performance of 124.1 mAh/g at 0.1 C (1 C = 117.6 mA/g), retaining 78.5 mAh/g under a high rate of 200 C and a long cycle-performance (retaining 80.7 mAh/g even after 10000 cycles at 20 C), outperforming the most advanced cathode materials as reported in literatures.
Na3V2(PO4)3 is a very prospective sodium-ion batteries (SIBs) electrode material owing to its NASICON structure and high reversible capacity. Conversely, on account of its intrinsic poor electronic conductivity, Na3V2(PO4)3 electrode materials confront with some significant limitations like poor cycle and rate performance which inhibit their practical applications in the energy fields. Herein, a simple two-step method has been implemented for the successful preparation of carbon-coated Na3V2(PO4)3 materials. As synthesized sample shows a remarkable electrochemical performance of 124.1 mAh/g at 0.1 C (1 C = 117.6 mA/g), retaining 78.5 mAh/g under a high rate of 200 C and a long cycle-performance (retaining 80.7 mAh/g even after 10000 cycles at 20 C), outperforming the most advanced cathode materials as reported in literatures.
2021, 32(11): 3575-3578
doi: 10.1016/j.cclet.2021.03.025
Abstract:
The trade-off between the electrochemical performance and mechanical strength is still a challenge for Ti3C2Tx free-standing electrode. Herein, a facile approach was proposed to fabricate a Microfibrillated cellulose@Ti3C2Tx (MFC@Ti3C2Tx) self-assembled microgel film by means of hydrogen bonding linkage. Benefiting from the rich hydroxyl groups on the MFC, the Ti3C2Tx nanosheets coated on the MFC in a time scale of minutes (within 1 min) instead of hours. The ultralong 1D frame of MFC effectively mitigated the re-aggregation of Ti3C2Tx nanosheet. The fluffy MFC@Ti3C2Tx film structure and the constructed 1D/2D conducting Ti3C2Tx pathways in horizontal and vertical directions endowed the fast ion transport of the electrolytes and the improved accessibility to the Ti3C2Tx surface. As a result, the freestanding MFC@Ti3C2Tx microgel film delivered a high specific capacitance of 451 F/g. And the rate performance was increased to 71% from the 64% of that of pristine Ti3C2Tx film. Furthermore, the tensile strength of MFC@Ti3C2Tx film was also promoted to 46.3 MPa, 3 folds of that of the pristine Ti3C2Tx film, due to the high strength of MFC and the hydrogen bonding effect.
The trade-off between the electrochemical performance and mechanical strength is still a challenge for Ti3C2Tx free-standing electrode. Herein, a facile approach was proposed to fabricate a Microfibrillated cellulose@Ti3C2Tx (MFC@Ti3C2Tx) self-assembled microgel film by means of hydrogen bonding linkage. Benefiting from the rich hydroxyl groups on the MFC, the Ti3C2Tx nanosheets coated on the MFC in a time scale of minutes (within 1 min) instead of hours. The ultralong 1D frame of MFC effectively mitigated the re-aggregation of Ti3C2Tx nanosheet. The fluffy MFC@Ti3C2Tx film structure and the constructed 1D/2D conducting Ti3C2Tx pathways in horizontal and vertical directions endowed the fast ion transport of the electrolytes and the improved accessibility to the Ti3C2Tx surface. As a result, the freestanding MFC@Ti3C2Tx microgel film delivered a high specific capacitance of 451 F/g. And the rate performance was increased to 71% from the 64% of that of pristine Ti3C2Tx film. Furthermore, the tensile strength of MFC@Ti3C2Tx film was also promoted to 46.3 MPa, 3 folds of that of the pristine Ti3C2Tx film, due to the high strength of MFC and the hydrogen bonding effect.
2021, 32(11): 3579-3583
doi: 10.1016/j.cclet.2021.03.040
Abstract:
Surface oxidized iron-nickel nanorods coupling with reduced graphene architectures (FeNi-O-rGA) are successfully constructed via hydrothermal, freeze-drying, and thermal activation approaches. The hierarchical structure can provide lots of pathways for fast ion diffusion and charge transfer, and expose abundant catalytic sites. Meanwhile, the activity of FeNi-O-rGA is boosted by the optimized metal-oxygen bond strength in FeNi3 alloys. Partial oxidized FeNi nanorods are strongly coupled with rGA by the formation of metal-O-C bonds, which can impede the aggregation of FeNi3 alloys and increase the utilization of active sites. The special structure and partially oxidized FeNi nanorods for FeNi-O-rGA can result in excellent OER activity and catalytic stability. Only 215 mV of overpotential is required to drive the current density of 10 mA/cm2 as well as the Tafel slope of 50.9 mV/dec in 1 mol/L KOH. The change of surface chemistry of FeNi-O-rGA is confirmed by XPS after the OER test, which indicates the highly catalytic stability of FeNi-O-rGA due to the formation of intermediate metal oxyhydroxide.
Surface oxidized iron-nickel nanorods coupling with reduced graphene architectures (FeNi-O-rGA) are successfully constructed via hydrothermal, freeze-drying, and thermal activation approaches. The hierarchical structure can provide lots of pathways for fast ion diffusion and charge transfer, and expose abundant catalytic sites. Meanwhile, the activity of FeNi-O-rGA is boosted by the optimized metal-oxygen bond strength in FeNi3 alloys. Partial oxidized FeNi nanorods are strongly coupled with rGA by the formation of metal-O-C bonds, which can impede the aggregation of FeNi3 alloys and increase the utilization of active sites. The special structure and partially oxidized FeNi nanorods for FeNi-O-rGA can result in excellent OER activity and catalytic stability. Only 215 mV of overpotential is required to drive the current density of 10 mA/cm2 as well as the Tafel slope of 50.9 mV/dec in 1 mol/L KOH. The change of surface chemistry of FeNi-O-rGA is confirmed by XPS after the OER test, which indicates the highly catalytic stability of FeNi-O-rGA due to the formation of intermediate metal oxyhydroxide.
2021, 32(11): 3584-3590
doi: 10.1016/j.cclet.2021.03.058
Abstract:
The angle dependence of photonic crystals (PCs) dramatically limits their practical applications in the colorimetrical sensing of humidity and volatile organic compound (VOC) vapors. In addition, it is challenging for inverse opal PCs to colorimetrically distinguish between vapors with similar refractive indices. Different from the mechanism of PC-based sensors, here, we report an angle-independent polyacrylamide (PAAm) organogel structural color film based on the mechanisms of retroreflection, total internal reflection (TIR) and interference with a shape similar to a single-sided "egg waffle". During the process of responding to humidity and VOC vapors, the color of the film remains angle-independent in the normal angle range of 0° to 45° under coaxial illumination and observation conditions. At the same time, the film can colorimetrically distinguish between vapors with similar refractive indices, such as methanol and ethanol, which is mainly due to the differences in their polarity and solubility parameters. The film shows good stability, reversibility and selectivity when exposed to vapors. A colorimetric sensor with a new response mechanism is proposed and has the potential to effectively distinguish between vapors with similar refractive indices. Furthermore, this responsive retroreflective structural color film (RRSCF) provides a universal strategy to develop targeted angle-independent structural color sensors by selecting optimized materials.
The angle dependence of photonic crystals (PCs) dramatically limits their practical applications in the colorimetrical sensing of humidity and volatile organic compound (VOC) vapors. In addition, it is challenging for inverse opal PCs to colorimetrically distinguish between vapors with similar refractive indices. Different from the mechanism of PC-based sensors, here, we report an angle-independent polyacrylamide (PAAm) organogel structural color film based on the mechanisms of retroreflection, total internal reflection (TIR) and interference with a shape similar to a single-sided "egg waffle". During the process of responding to humidity and VOC vapors, the color of the film remains angle-independent in the normal angle range of 0° to 45° under coaxial illumination and observation conditions. At the same time, the film can colorimetrically distinguish between vapors with similar refractive indices, such as methanol and ethanol, which is mainly due to the differences in their polarity and solubility parameters. The film shows good stability, reversibility and selectivity when exposed to vapors. A colorimetric sensor with a new response mechanism is proposed and has the potential to effectively distinguish between vapors with similar refractive indices. Furthermore, this responsive retroreflective structural color film (RRSCF) provides a universal strategy to develop targeted angle-independent structural color sensors by selecting optimized materials.
2021, 32(11): 3591-3595
doi: 10.1016/j.cclet.2021.03.053
Abstract:
Crystalline engineering and heterostructure have attracted much attention as effective strategies to improve the electrocatalytic activity for hydrogen evolution reaction (HER). In this study, a new heterostructure catalyst (Ru/RuS2@N-rGO) with low crystallinity was fabricated by a simple and low-temperature method for HER in alkaline solution, applying the Na2SO4 as S source and polypyrrole as N source. Optimizing through the controllable crystalline engineering and composition ratio of Ru and RuS2, the Ru/RuS2@N-rGO heterocatalyst at the calcining 500 ℃ revealed highly efficient HER activity with overpotential 18 mV at a current density 10 mA/cm2 and remarkable stability for 24 h in 1.0 mol/L KOH. This work provides a facile and effective method in designing advanced electrocatalysts for HER in the alkaline electrolytes by synergistically structural and component modulations.
Crystalline engineering and heterostructure have attracted much attention as effective strategies to improve the electrocatalytic activity for hydrogen evolution reaction (HER). In this study, a new heterostructure catalyst (Ru/RuS2@N-rGO) with low crystallinity was fabricated by a simple and low-temperature method for HER in alkaline solution, applying the Na2SO4 as S source and polypyrrole as N source. Optimizing through the controllable crystalline engineering and composition ratio of Ru and RuS2, the Ru/RuS2@N-rGO heterocatalyst at the calcining 500 ℃ revealed highly efficient HER activity with overpotential 18 mV at a current density 10 mA/cm2 and remarkable stability for 24 h in 1.0 mol/L KOH. This work provides a facile and effective method in designing advanced electrocatalysts for HER in the alkaline electrolytes by synergistically structural and component modulations.
2021, 32(11): 3596-3600
doi: 10.1016/j.cclet.2021.03.062
Abstract:
In this paper, a hydrothermal approach is utilized for the first time in integrating graphene oxide (GO), acetic acid (HAc) and nickel foam to prepare hydrogenated graphene (HG). There are two primary aims of this study: one is to ascertain the structure of the as-prepared HG, and the other one is to investigate the ferromagnetism of the HG. Under hydrothermal conditions, GO was reduced and hydrogenated by HAc, while the nickel foam served as a catalyst. This work provides a novel and facile route for the synthesis of hydrogenated graphene, which may lead to the application of hydrogenated graphene in spin electronic devices.
In this paper, a hydrothermal approach is utilized for the first time in integrating graphene oxide (GO), acetic acid (HAc) and nickel foam to prepare hydrogenated graphene (HG). There are two primary aims of this study: one is to ascertain the structure of the as-prepared HG, and the other one is to investigate the ferromagnetism of the HG. Under hydrothermal conditions, GO was reduced and hydrogenated by HAc, while the nickel foam served as a catalyst. This work provides a novel and facile route for the synthesis of hydrogenated graphene, which may lead to the application of hydrogenated graphene in spin electronic devices.
2021, 32(11): 3601-3606
doi: 10.1016/j.cclet.2021.04.002
Abstract:
Potassium-ion batteries (KIBs) have become the most promising alternative to lithium-ion batteries for large-scale energy storage system due to their abundance and low cost. However, previous reports focused on the intercalation-type cathode materials usually showed an inferior capacity, together with a poor cyclic life caused by the repetitive intercalation of large-size K-ions, which hinders their practical application. Here, we combine the strategies of carbon coating, template etching and hydrothermal selenization to prepare yolk-shelled FeSe2@N-doped carbon nanoboxes (FeSe2@C NBs), where the inner highly-crystalline FeSe2 clusters are completely surrounded by the self-supported carbon shell. The integrated and highly conductive carbon shell not only provides a fast electron/ion diffusion channel, but also prevents the agglomeration of FeSe2 clusters. When evaluated as a conversion-type cathode material for KIBs, the FeSe2@C NBs electrode delivers a relatively high specific capacity of 257 mAh/g at 100 mA/g and potential platform of about 1.6 V, which endow a high energy density of about 411 Wh/kg. Most importantly, by designing a robust host with large internal void space to accommodate the volumetric variation of the inner FeSe2 clusters, the battery based on FeSe2@C NBs exhibits ultra-long cycle stability. Specifically, even after 700 cycles at 100 mA/g, a capacity of 221 mAh/g along with an average fading rate of only 0.02% can be retained, which achieves the optimal balance of high specific capacity and long-cycle stability.
Potassium-ion batteries (KIBs) have become the most promising alternative to lithium-ion batteries for large-scale energy storage system due to their abundance and low cost. However, previous reports focused on the intercalation-type cathode materials usually showed an inferior capacity, together with a poor cyclic life caused by the repetitive intercalation of large-size K-ions, which hinders their practical application. Here, we combine the strategies of carbon coating, template etching and hydrothermal selenization to prepare yolk-shelled FeSe2@N-doped carbon nanoboxes (FeSe2@C NBs), where the inner highly-crystalline FeSe2 clusters are completely surrounded by the self-supported carbon shell. The integrated and highly conductive carbon shell not only provides a fast electron/ion diffusion channel, but also prevents the agglomeration of FeSe2 clusters. When evaluated as a conversion-type cathode material for KIBs, the FeSe2@C NBs electrode delivers a relatively high specific capacity of 257 mAh/g at 100 mA/g and potential platform of about 1.6 V, which endow a high energy density of about 411 Wh/kg. Most importantly, by designing a robust host with large internal void space to accommodate the volumetric variation of the inner FeSe2 clusters, the battery based on FeSe2@C NBs exhibits ultra-long cycle stability. Specifically, even after 700 cycles at 100 mA/g, a capacity of 221 mAh/g along with an average fading rate of only 0.02% can be retained, which achieves the optimal balance of high specific capacity and long-cycle stability.
2021, 32(11): 3607-3612
doi: 10.1016/j.cclet.2021.04.011
Abstract:
Mixed metal sulfides have been widely used as anode material of sodium-ion batteries (SIBs) because of their excellent conductivity and sodium ion storage performance. Herein, ReS2@NiS2 heterostructures have been triumphantly designed and prepared through anchoring ReS2 nanosheet arrays on the surface of NiS2 hollow nanosphere. Specifically, the carbon nanospheres was used as hard template to synthesize NiS2 hollow spheres as the substrate and then the ultrathin two-dimensional ReS2 nanosheet arrays were uniformly grown on the surface of NiS2. The internal hollow property provides sufficient space to relieve the volume expansion, and the outer two-dimensional nanosheet realizes the rapid electron transport and insertion/extraction of Na+. Owing to the great improvement of the transport kinetics of Na+, NiS2@ReS2 heterostructure electrode can achieve a high specific capacity of 400 mAh/g at the high current density of 1 A/g and still maintain a stable cycle stability even after 220 cycles. This hard template method not only paves a new way for the design and construct binary metal sulfide heterostructure electrode materials with outstanding electrochemical performance for Na+ batteries but also open up the potential applications of anode materials of SIBs.
Mixed metal sulfides have been widely used as anode material of sodium-ion batteries (SIBs) because of their excellent conductivity and sodium ion storage performance. Herein, ReS2@NiS2 heterostructures have been triumphantly designed and prepared through anchoring ReS2 nanosheet arrays on the surface of NiS2 hollow nanosphere. Specifically, the carbon nanospheres was used as hard template to synthesize NiS2 hollow spheres as the substrate and then the ultrathin two-dimensional ReS2 nanosheet arrays were uniformly grown on the surface of NiS2. The internal hollow property provides sufficient space to relieve the volume expansion, and the outer two-dimensional nanosheet realizes the rapid electron transport and insertion/extraction of Na+. Owing to the great improvement of the transport kinetics of Na+, NiS2@ReS2 heterostructure electrode can achieve a high specific capacity of 400 mAh/g at the high current density of 1 A/g and still maintain a stable cycle stability even after 220 cycles. This hard template method not only paves a new way for the design and construct binary metal sulfide heterostructure electrode materials with outstanding electrochemical performance for Na+ batteries but also open up the potential applications of anode materials of SIBs.
2021, 32(11): 3613-3618
doi: 10.1016/j.cclet.2021.04.012
Abstract:
Spatial isolation of different functional sites at the nanoscale in multifunctional catalysts for steering reaction sequence and paths remains a major challenge. Herein, we reported the spatial separation of dual-site Au and RuO2 on the nanosurface of TiO2 (Au/TiO2/RuO2) through the strong metal-support interaction (SMSI) and the lattice matching (LM) for robust photocatalytic hydrogen evolution. The SMSI between Au and TiO2 induced the encapsulation of Au nanoparticles by an impermeable TiOx overlayer, which can function as a physical separation barrier to the permeation of the second precursor. The LM between RuO2 and rutile-TiO2 can increase the stability of RuO2/TiO2 interface and thus prevent the aggregation of dual-site Au and RuO2 in the calcination process of removing TiOx overlayer of Au. The photocatalytic hydrogen production is used as a model reaction to evaluate the performance of spatially separated dual-site Au/TiO2/RuO2 catalysts. The rate of hydrogen production of the Au/TiO2/RuO2 is as high as 84 μmol h−1g−1 under solar light irradiation without sacrificial agents, which is 2.5 times higher than the reference Au/TiO2 and non-separated Au/RuO2/TiO2 samples. Systematic characterizations verify that the spatially separated dual-site Au and RuO2 on the nanosurface of TiO2 can effectively separate the photo-generated carriers and lower the height of the Schottky barrier, respectively, under UV and visible light irradiation. This study provides new inspiration for the precise construction of different sites in multifunctional catalysts.
Spatial isolation of different functional sites at the nanoscale in multifunctional catalysts for steering reaction sequence and paths remains a major challenge. Herein, we reported the spatial separation of dual-site Au and RuO2 on the nanosurface of TiO2 (Au/TiO2/RuO2) through the strong metal-support interaction (SMSI) and the lattice matching (LM) for robust photocatalytic hydrogen evolution. The SMSI between Au and TiO2 induced the encapsulation of Au nanoparticles by an impermeable TiOx overlayer, which can function as a physical separation barrier to the permeation of the second precursor. The LM between RuO2 and rutile-TiO2 can increase the stability of RuO2/TiO2 interface and thus prevent the aggregation of dual-site Au and RuO2 in the calcination process of removing TiOx overlayer of Au. The photocatalytic hydrogen production is used as a model reaction to evaluate the performance of spatially separated dual-site Au/TiO2/RuO2 catalysts. The rate of hydrogen production of the Au/TiO2/RuO2 is as high as 84 μmol h−1g−1 under solar light irradiation without sacrificial agents, which is 2.5 times higher than the reference Au/TiO2 and non-separated Au/RuO2/TiO2 samples. Systematic characterizations verify that the spatially separated dual-site Au and RuO2 on the nanosurface of TiO2 can effectively separate the photo-generated carriers and lower the height of the Schottky barrier, respectively, under UV and visible light irradiation. This study provides new inspiration for the precise construction of different sites in multifunctional catalysts.
2021, 32(11): 3619-3622
doi: 10.1016/j.cclet.2021.06.062
Abstract:
In this work, hollow Fe2O3/Co3O4 microcubes have been successfully synthesized through a hydrothermal method followed by an annealing process using metal-organic framework of Prussian blue as a soft template. The morphologies, microstructures, surface area and element compositions have been carefully characterized by a series of techniques. Meanwhile, compared with that of pure Fe2O3 and Co3O4, the gas sensor based on the hollow microcubes exhibits enhanced sensing performances towards acetone, e.g., a higher response of 21.2 and a shorter response time of 5 s towards 20 ppm acetone at a relatively low working temperature of 200 ℃. Moreover, the hollow microcubes-based gas sensor still shows perfect long-term stability, excellent repeatability and the ability of sub-ppm level detection, which provides a possibility for its application in real life. The enhanced gas sensing performances can be attributed to the hollow structure with a high surface area and the formed p-n heterojunctions within the microcubes.
In this work, hollow Fe2O3/Co3O4 microcubes have been successfully synthesized through a hydrothermal method followed by an annealing process using metal-organic framework of Prussian blue as a soft template. The morphologies, microstructures, surface area and element compositions have been carefully characterized by a series of techniques. Meanwhile, compared with that of pure Fe2O3 and Co3O4, the gas sensor based on the hollow microcubes exhibits enhanced sensing performances towards acetone, e.g., a higher response of 21.2 and a shorter response time of 5 s towards 20 ppm acetone at a relatively low working temperature of 200 ℃. Moreover, the hollow microcubes-based gas sensor still shows perfect long-term stability, excellent repeatability and the ability of sub-ppm level detection, which provides a possibility for its application in real life. The enhanced gas sensing performances can be attributed to the hollow structure with a high surface area and the formed p-n heterojunctions within the microcubes.
2021, 32(11): 3623-3626
doi: 10.1016/j.cclet.2021.04.015
Abstract:
Whilst most bioorthogonal reactions focus on targeting binding-site cysteine residues, proximity-induced reactivity effect ensures that reaction also occurs at nucleophilic lysine residues. We report one example here that the propargylated-sulfonium center undergoes a nucleophilic reaction with lysine residue via proximity-induced conjugation. This propargylated-sulfonium tethered peptide resulting from a facile propargylation of thiolethers, enables amino-yne reaction at the selected lysine on MDM4 protein. This strategy represents a viable approach of lysine-targeted covalent inhibition in proximity.
Whilst most bioorthogonal reactions focus on targeting binding-site cysteine residues, proximity-induced reactivity effect ensures that reaction also occurs at nucleophilic lysine residues. We report one example here that the propargylated-sulfonium center undergoes a nucleophilic reaction with lysine residue via proximity-induced conjugation. This propargylated-sulfonium tethered peptide resulting from a facile propargylation of thiolethers, enables amino-yne reaction at the selected lysine on MDM4 protein. This strategy represents a viable approach of lysine-targeted covalent inhibition in proximity.
2021, 32(11): 3627-3631
doi: 10.1016/j.cclet.2021.04.016
Abstract:
Herein, a rapid alkenylation of quinoxalin-2(1H)-ones enabled by a combination of Mannich-type reaction and solar photocatalysis is demonstrated. A wide range of functional groups are compatible, affording the corresponding products in moderate-to-good yields. Control experiments illustrate that the in situ generated 1O2 plays a central role in this reaction. This green and efficient strategy provides a practical solution for the synthesis of potentially bioactive compounds that containing a 3, 4-dihydroquinoxalin-2(1H)-one structure.
Herein, a rapid alkenylation of quinoxalin-2(1H)-ones enabled by a combination of Mannich-type reaction and solar photocatalysis is demonstrated. A wide range of functional groups are compatible, affording the corresponding products in moderate-to-good yields. Control experiments illustrate that the in situ generated 1O2 plays a central role in this reaction. This green and efficient strategy provides a practical solution for the synthesis of potentially bioactive compounds that containing a 3, 4-dihydroquinoxalin-2(1H)-one structure.
2021, 32(11): 3632-3635
doi: 10.1016/j.cclet.2021.04.019
Abstract:
An efficient and practical methods for the synthesis of carbamoyl quinoline-2, 4-diones via the reaction of ortho-cyanoarylacrylamides with oxamic acids was described. This cyclic reaction could be performed efficiently under metal free conditions. Various products with functional groups could be obtained with moderate to high yields via radical mechanism.
An efficient and practical methods for the synthesis of carbamoyl quinoline-2, 4-diones via the reaction of ortho-cyanoarylacrylamides with oxamic acids was described. This cyclic reaction could be performed efficiently under metal free conditions. Various products with functional groups could be obtained with moderate to high yields via radical mechanism.
2021, 32(11): 3636-3640
doi: 10.1016/j.cclet.2021.04.039
Abstract:
Zwitterionic polymer materials have been extensively studied, but zwitterionic peptides supramolecular hydrogel materials are rarely studied. In this study, the preparation of two zwitterionic hydrogels using self-assembled peptides were reported. The hydrogels could be fabricated easily by changing the temperature or enzyme catalysis in a short time. And the differences in structure and function of the zwitterion peptide hydrogels caused by the two preparation methods were also be compared. We found that the hydrogel prepared by enzyme induced self-assembly has better solubility and lower cytotoxicity than that prepared by the heating-cooling process. The result showed the enzyme induced self-assembly way to form zwitterionic peptides supramolecular hydrogel materials could have further biomedical applications.
Zwitterionic polymer materials have been extensively studied, but zwitterionic peptides supramolecular hydrogel materials are rarely studied. In this study, the preparation of two zwitterionic hydrogels using self-assembled peptides were reported. The hydrogels could be fabricated easily by changing the temperature or enzyme catalysis in a short time. And the differences in structure and function of the zwitterion peptide hydrogels caused by the two preparation methods were also be compared. We found that the hydrogel prepared by enzyme induced self-assembly has better solubility and lower cytotoxicity than that prepared by the heating-cooling process. The result showed the enzyme induced self-assembly way to form zwitterionic peptides supramolecular hydrogel materials could have further biomedical applications.
2021, 32(11): 3641-3645
doi: 10.1016/j.cclet.2021.04.035
Abstract:
Nonalcoholic fatty liver disease (NAFLD) can cause serious liver damage. Early diagnosis and effective treatment of NAFLD can greatly improve treatment rates. The initiation and development of NAFLD has been closely linked to endoplasmic reticulum (ER) stress, which might cause ER viscosity variations. Therefore, if the internal relationship between ER viscosity and NAFLD is clarified, an effective approach for early diagnosis may result. Herein, we fabricated a novel near-infrared (NIR) fluorescence imaging probe, Er-V, for monitoring ER viscosity through a molecular rotor strategy. Er-V exhibited a strong NIR fluorescence signal (at 626 nm) when the environmental viscosity hindered the rotation of the malononitrile group. Using Er-V, we successfully observed a significant enhancement in viscosity in the liver of mice with NAFLD. Therefore, this imaging method based on Er-V is expected to provide a new approach for early detection and diagnosis of NAFLD.
Nonalcoholic fatty liver disease (NAFLD) can cause serious liver damage. Early diagnosis and effective treatment of NAFLD can greatly improve treatment rates. The initiation and development of NAFLD has been closely linked to endoplasmic reticulum (ER) stress, which might cause ER viscosity variations. Therefore, if the internal relationship between ER viscosity and NAFLD is clarified, an effective approach for early diagnosis may result. Herein, we fabricated a novel near-infrared (NIR) fluorescence imaging probe, Er-V, for monitoring ER viscosity through a molecular rotor strategy. Er-V exhibited a strong NIR fluorescence signal (at 626 nm) when the environmental viscosity hindered the rotation of the malononitrile group. Using Er-V, we successfully observed a significant enhancement in viscosity in the liver of mice with NAFLD. Therefore, this imaging method based on Er-V is expected to provide a new approach for early detection and diagnosis of NAFLD.
Fluorine-defects induced solid-state red emission of carbon dots with an excellent thermosensitivity
2021, 32(11): 3646-3651
doi: 10.1016/j.cclet.2021.04.033
Abstract:
Up to date, solid-state carbon dots (CDs) with bright red fluorescence have scarcely achieved due to aggregation-caused quenching (ACQ) effect and extremely low quantum yield in deep-red to near infrared region. Here, we report a novel fluorine-defects induced solid-state red fluorescence (λem = 676 nm, the absolute fluorescence quantum yields is 4.17%) in fluorine, nitrogen and sulfur co-doped CDs (F, N, S-CDs), which is the first report of such a long wavelength emission of solid-state CDs. As a control, CDs without fluorine-doping (N, S-CDs) show no fluorescence in solid-state, and the fluorescence quantum yield/emission wavelength of N, S-CDs in solution-state are also lower/shorter than that of F, N, S-CDs, which is mainly due to the F-induced defect traps on the surface/edge of F, N, S-CDs. Moreover, the solid-state F, N, S-CDs exhibit an interesting temperature-sensitive behavior in the range of 80-420 K, with the maximum fluorescence intensity at 120 K, unveiling its potential as the temperature-dependent fluorescent sensor and the solid-state light-emitting device adapted to multiple temperatures.
Up to date, solid-state carbon dots (CDs) with bright red fluorescence have scarcely achieved due to aggregation-caused quenching (ACQ) effect and extremely low quantum yield in deep-red to near infrared region. Here, we report a novel fluorine-defects induced solid-state red fluorescence (λem = 676 nm, the absolute fluorescence quantum yields is 4.17%) in fluorine, nitrogen and sulfur co-doped CDs (F, N, S-CDs), which is the first report of such a long wavelength emission of solid-state CDs. As a control, CDs without fluorine-doping (N, S-CDs) show no fluorescence in solid-state, and the fluorescence quantum yield/emission wavelength of N, S-CDs in solution-state are also lower/shorter than that of F, N, S-CDs, which is mainly due to the F-induced defect traps on the surface/edge of F, N, S-CDs. Moreover, the solid-state F, N, S-CDs exhibit an interesting temperature-sensitive behavior in the range of 80-420 K, with the maximum fluorescence intensity at 120 K, unveiling its potential as the temperature-dependent fluorescent sensor and the solid-state light-emitting device adapted to multiple temperatures.
2021, 32(11): 3652-3652
doi: 10.1016/j.cclet.2021.09.101
Abstract:
