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2024 Volume 43 Issue 10
2024, 43(10): 100321
doi: 10.1016/j.cjsc.2024.100321
Abstract:
In summary, the integrated conductivity and hydrophilic gradient imprinted gradient zinc anode can effectively inhibit side reactions and regulate zinc deposition behavior, thus achieving long-term cycling under high current/capacity. When multiple materials are composited for use as zinc anode coatings, different structural designs may have a dramatic effect on the electrochemical performance, even though the components are the same. The gradient imprinted design and related analysis method can be applied to other zinc anode coating materials, which will contribute to the design of future AZIBs. Moreover, at high current density/capacity, other metal-anode secondary batteries (e.g., lithium-ion batteries, sodium-ion batteries, aluminum-ion batteries, etc.) almost always suffer from serious dendrite problems, and thereby this work can also provide new research inspiration.
In summary, the integrated conductivity and hydrophilic gradient imprinted gradient zinc anode can effectively inhibit side reactions and regulate zinc deposition behavior, thus achieving long-term cycling under high current/capacity. When multiple materials are composited for use as zinc anode coatings, different structural designs may have a dramatic effect on the electrochemical performance, even though the components are the same. The gradient imprinted design and related analysis method can be applied to other zinc anode coating materials, which will contribute to the design of future AZIBs. Moreover, at high current density/capacity, other metal-anode secondary batteries (e.g., lithium-ion batteries, sodium-ion batteries, aluminum-ion batteries, etc.) almost always suffer from serious dendrite problems, and thereby this work can also provide new research inspiration.
2024, 43(10): 100322
doi: 10.1016/j.cjsc.2024.100322
Abstract:
This study reports for the first time the synthesis of homogeneous high-order metalla[4]catenane through coordination driven self-assembly strategy, and the complicated topology could be transformed into corresponding organometallic macrocyclic compound accompanied by a decrease in concentration in methanol solution. Besides, the strong interlayer π…π stacking interaction and non-classical hydrogen bonding play a crucial role in the formation and stability of metalla[4]catenane structure, which contributes to a deeper understanding of the driving forces behind the formation of molecular metalla catenanes and also has important theoretical and practical significance for promoting the development of this research system. These findings will further motivate researchers to explore the construction of mechanically interlocked supramolecular topological complexes.
This study reports for the first time the synthesis of homogeneous high-order metalla[4]catenane through coordination driven self-assembly strategy, and the complicated topology could be transformed into corresponding organometallic macrocyclic compound accompanied by a decrease in concentration in methanol solution. Besides, the strong interlayer π…π stacking interaction and non-classical hydrogen bonding play a crucial role in the formation and stability of metalla[4]catenane structure, which contributes to a deeper understanding of the driving forces behind the formation of molecular metalla catenanes and also has important theoretical and practical significance for promoting the development of this research system. These findings will further motivate researchers to explore the construction of mechanically interlocked supramolecular topological complexes.
2024, 43(10): 100325
doi: 10.1016/j.cjsc.2024.100325
Abstract:
In summary, the booming development of c-MOFs brings opportunities for the development of new electromagnetic functional materials and devices, and the design and customization of MOF structural units, overall topology modulation, and the construction of three-dimensional structures based on the understanding of electromagnetic properties and energy conversion provide new insights for further investigation of the EMW absorption mechanism and enhancement of dielectric properties. However, conductive MOFs also face challenges such as few available types, poor impedance matching, and narrow absorption bandwidth. Furthermore, in practical potential applications, conductive MOF can also be made into MOF films for stealth coatings for military equipment and EMW protection for civilian use.
In summary, the booming development of c-MOFs brings opportunities for the development of new electromagnetic functional materials and devices, and the design and customization of MOF structural units, overall topology modulation, and the construction of three-dimensional structures based on the understanding of electromagnetic properties and energy conversion provide new insights for further investigation of the EMW absorption mechanism and enhancement of dielectric properties. However, conductive MOFs also face challenges such as few available types, poor impedance matching, and narrow absorption bandwidth. Furthermore, in practical potential applications, conductive MOF can also be made into MOF films for stealth coatings for military equipment and EMW protection for civilian use.
2024, 43(10): 100329
doi: 10.1016/j.cjsc.2024.100329
Abstract:
In the future, the nanoconfined water monolayer concept may also work for the aligning assembly of heterostructures of other types of 2D materials. Indeed, the confinement engineering has provided a universal guideline for designing catalysts, membranes and chemical reactions. First, the synergy of chemical and spatial confinement elevated the secondary battery performances by innovative microstructures and properties. Second, the confinement effect may enhance the supercapacitor performances by the load of redox-active nanowires between MXene nanosheets. Third, the Marangoni effect results in the confinement of carbon nanotubes at MXene interfaces, which compose a fast-response humidity sensor. More interesting behaviors could be expected after improving the in-plane alignment of the heterostructures of 2D materials, which may exhibit enhanced magnetic and half-metallic properties as well as enhanced proton and spin-transport performances.
In the future, the nanoconfined water monolayer concept may also work for the aligning assembly of heterostructures of other types of 2D materials. Indeed, the confinement engineering has provided a universal guideline for designing catalysts, membranes and chemical reactions. First, the synergy of chemical and spatial confinement elevated the secondary battery performances by innovative microstructures and properties. Second, the confinement effect may enhance the supercapacitor performances by the load of redox-active nanowires between MXene nanosheets. Third, the Marangoni effect results in the confinement of carbon nanotubes at MXene interfaces, which compose a fast-response humidity sensor. More interesting behaviors could be expected after improving the in-plane alignment of the heterostructures of 2D materials, which may exhibit enhanced magnetic and half-metallic properties as well as enhanced proton and spin-transport performances.
2024, 43(10): 100330
doi: 10.1016/j.cjsc.2024.100330
Abstract:
In conclusion, Xiong et al. developed a HEA/SrTiO3 catalyst for efficient photothermal methane dry reforming. This work proposes a unique carbon exchange mechanism based on in-depth spectroscopic techniques, providing a new perspective on overcoming stability and selectivity issues in the DRM process. The work would be expected to inspire the development of efficient DRM catalysts under mild conditions.
In conclusion, Xiong et al. developed a HEA/SrTiO3 catalyst for efficient photothermal methane dry reforming. This work proposes a unique carbon exchange mechanism based on in-depth spectroscopic techniques, providing a new perspective on overcoming stability and selectivity issues in the DRM process. The work would be expected to inspire the development of efficient DRM catalysts under mild conditions.
2024, 43(10): 100331
doi: 10.1016/j.cjsc.2024.100331
Abstract:
In summary, this work establishes a correlation between OVs and bound exciton luminescence by single-particle spectroscopy. It confirms that the PL emission of m-BiVO4 originates from the defect state. Additionally, the study achieves visual imaging of the spatial distribution of oxygen defects by PL lifetime imaging maps. Furthermore, single-particle spectroscopy can be used to monitor charge transfer during photocatalysis in situ, indicating that the generation of OVs at specific crystal facets facilitates efficient charge transfer between electrons and reactants. This work provides an imaging technique to accurately monitor the spatial distribution of defects in single-crystal materials, and a method for spatial high-resolution real-time monitoring of multiphase catalytic reactions, aiming to provide an in-depth understanding of the relationship between the structure-activity of materials.
In summary, this work establishes a correlation between OVs and bound exciton luminescence by single-particle spectroscopy. It confirms that the PL emission of m-BiVO4 originates from the defect state. Additionally, the study achieves visual imaging of the spatial distribution of oxygen defects by PL lifetime imaging maps. Furthermore, single-particle spectroscopy can be used to monitor charge transfer during photocatalysis in situ, indicating that the generation of OVs at specific crystal facets facilitates efficient charge transfer between electrons and reactants. This work provides an imaging technique to accurately monitor the spatial distribution of defects in single-crystal materials, and a method for spatial high-resolution real-time monitoring of multiphase catalytic reactions, aiming to provide an in-depth understanding of the relationship between the structure-activity of materials.
2024, 43(10): 100344
doi: 10.1016/j.cjsc.2024.100344
Abstract:
In summary, the increasing interest in separating lanthanides and actinides for the purposes of spent nuclear fuel reprocessing has spurred renewed research efforts in this domain recently. Although the higher oxidation states of Am have been recognized for several decades, the development of separation techniques based on the control of Am oxidation state remains less advanced. The key challenge in spent fuel reprocessing lies in achieving complete oxidation and long-term stabilization of high-valence Am under practical conditions. This necessitates addressing the complexities of real-world spent fuel reprocessing scenarios (high acidity and radiation level) and minimizing the generation of secondary waste. In this perspective, we outline the most recent advances in lanthanide and actinide separation following redox-based protocols. High Am/Ln separation factors have been achieved in these works via judicious synergy between proper selection of chemical oxidants and stabilization of Am(V)/Am(VI) via complexation or ion sieving. Ongoing efforts to develop oxidation strategies and separation technologies hold the potential to yield an advanced process suitable for application within the nuclear industry. In addition, separation strategies based on oxidation state control holds promise for addressing the even more challenging task of Am/Cm separation in advanced nuclear fuel cycle.
In summary, the increasing interest in separating lanthanides and actinides for the purposes of spent nuclear fuel reprocessing has spurred renewed research efforts in this domain recently. Although the higher oxidation states of Am have been recognized for several decades, the development of separation techniques based on the control of Am oxidation state remains less advanced. The key challenge in spent fuel reprocessing lies in achieving complete oxidation and long-term stabilization of high-valence Am under practical conditions. This necessitates addressing the complexities of real-world spent fuel reprocessing scenarios (high acidity and radiation level) and minimizing the generation of secondary waste. In this perspective, we outline the most recent advances in lanthanide and actinide separation following redox-based protocols. High Am/Ln separation factors have been achieved in these works via judicious synergy between proper selection of chemical oxidants and stabilization of Am(V)/Am(VI) via complexation or ion sieving. Ongoing efforts to develop oxidation strategies and separation technologies hold the potential to yield an advanced process suitable for application within the nuclear industry. In addition, separation strategies based on oxidation state control holds promise for addressing the even more challenging task of Am/Cm separation in advanced nuclear fuel cycle.
2024, 43(10): 100390
doi: 10.1016/j.cjsc.2024.100390
Abstract:
Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery (ASSLB). Homogeneous and fast lithium-ion (Li+) interfacial transport of cathode is the overriding premise for high capability of ASSLBs. However, the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material (CAM)/sulfide solid electrolyte (SSE) interfacial issues result in high interfacial impedance, decreasing the Li+ transfer kinetics. In this review, we outline the Li+ transport properties of CAMs and SSEs, followed by a discussion of their interfacial electro-chemo-mechanical issues. Commentary is also provided on the solutions to the multiple-scale interfacial Li+ transport failure. Furthermore, the underlying interdependent mechanisms between electrodes are summarized and overviewed. Finally, we suggest future paths to better comprehend and promote the interfacial Li+ transport in ASSLBs. This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.
Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery (ASSLB). Homogeneous and fast lithium-ion (Li+) interfacial transport of cathode is the overriding premise for high capability of ASSLBs. However, the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material (CAM)/sulfide solid electrolyte (SSE) interfacial issues result in high interfacial impedance, decreasing the Li+ transfer kinetics. In this review, we outline the Li+ transport properties of CAMs and SSEs, followed by a discussion of their interfacial electro-chemo-mechanical issues. Commentary is also provided on the solutions to the multiple-scale interfacial Li+ transport failure. Furthermore, the underlying interdependent mechanisms between electrodes are summarized and overviewed. Finally, we suggest future paths to better comprehend and promote the interfacial Li+ transport in ASSLBs. This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.
2024, 43(10): 100393
doi: 10.1016/j.cjsc.2024.100393
Abstract:
Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.
Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.
2024, 43(10): 100394
doi: 10.1016/j.cjsc.2024.100394
Abstract:
The identical molecular size and similar physical properties of carbon dioxide (CO2) and acetylene (C2H2) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO2 and C2H2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO2 and C2H2, realizing the inverse separation of zeolite from selective adsorption of C2H2 to selective adsorption of CO2. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C2H2 between the cages while ensuring the transfer of CO2, increasing their diffusion differences in pore channels and leading to the CO2/C2H2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO2 distribution in K-5A-β is significantly higher than that of C2H2. Dynamic breakthrough experiments verify the excellent performance of material in practical CO2/C2H2 separation, for CO2/C2H2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C2H2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO2 and C2H2.
The identical molecular size and similar physical properties of carbon dioxide (CO2) and acetylene (C2H2) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO2 and C2H2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO2 and C2H2, realizing the inverse separation of zeolite from selective adsorption of C2H2 to selective adsorption of CO2. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C2H2 between the cages while ensuring the transfer of CO2, increasing their diffusion differences in pore channels and leading to the CO2/C2H2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO2 distribution in K-5A-β is significantly higher than that of C2H2. Dynamic breakthrough experiments verify the excellent performance of material in practical CO2/C2H2 separation, for CO2/C2H2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C2H2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO2 and C2H2.
2024, 43(10): 100395
doi: 10.1016/j.cjsc.2024.100395
Abstract:
Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr3 (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.
Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr3 (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.
2024, 43(10): 100397
doi: 10.1016/j.cjsc.2024.100397
Abstract:
As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13- framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m·K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.
As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13- framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m·K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.
2024, 43(10): 100410
doi: 10.1016/j.cjsc.2024.100410
Abstract:
Photoluminescence (PL) has been increasingly applied in anticounterfeiting and encryption as counterfeiting becomes more prevalent. However, common luminescent encryption techniques are based on static PL measurements and are easy to counterfeit. In this work, we have developed a thermal vapor deposition (TVD) approach using melem as the unique starting material to synthesize highly homogeneous carbon nitride (CN) thin films featuring unique dynamic PL switching properties. After being irradiated by a white LED, the blue PL intensity of the CN film increases significantly and then fades in darkness, demonstrating excellent recyclability. Experimental results prove that CN films contain cyano groups in the structure, and density functional theory (DFT) calculations indicate that the integration of cyano groups results in traps within the bandgap of CN, suggesting that the dynamic PL switching effect is essentially associated with the fullness of the trap states. We have therefore developed an advanced luminescent device for the secure transmission of encrypted information through controlled illumination. It can be easily read with a portable UV (365 nm) lamp and effectively erased using the white LED, thereby preventing information leakage and showing great potential for many applications.
Photoluminescence (PL) has been increasingly applied in anticounterfeiting and encryption as counterfeiting becomes more prevalent. However, common luminescent encryption techniques are based on static PL measurements and are easy to counterfeit. In this work, we have developed a thermal vapor deposition (TVD) approach using melem as the unique starting material to synthesize highly homogeneous carbon nitride (CN) thin films featuring unique dynamic PL switching properties. After being irradiated by a white LED, the blue PL intensity of the CN film increases significantly and then fades in darkness, demonstrating excellent recyclability. Experimental results prove that CN films contain cyano groups in the structure, and density functional theory (DFT) calculations indicate that the integration of cyano groups results in traps within the bandgap of CN, suggesting that the dynamic PL switching effect is essentially associated with the fullness of the trap states. We have therefore developed an advanced luminescent device for the secure transmission of encrypted information through controlled illumination. It can be easily read with a portable UV (365 nm) lamp and effectively erased using the white LED, thereby preventing information leakage and showing great potential for many applications.
2024, 43(10): 100411
doi: 10.1016/j.cjsc.2024.100411
Abstract:
The ligand effects have been extensively investigated in Au and Ag nanoclusters, while corresponding research efforts focusing on Cu nanoclusters remain relatively insufficient. Such a scarcity could primarily be attributed to the inherent instability of Cu nanoclusters relative to their Au/Ag analogues. In this work, we report the controllable preparation and structural determination of a hydride-containing Cu28 nanocluster with a chemical formula of Cu28H10(SPhpOMe)18(DPPOE)3. The combination of Cu28H10(SPhpOMe)18(DPPOE)3 and previously reported Cu28H10(SPhoMe)18(TPP)3 constructs a structure-correlated cluster pair with comparable structures and properties. Accordingly, the ligand effects in directing the geometric structures and physicochemical properties (including optical absorptions and catalytic activities towards the selected hydrogenation) of copper nanoclusters were analyzed. Overall, this work presents a structure-correlated Cu28 pair that enables the atomic-level understanding of ligand effects on the structures and properties of metal nanoclusters.
The ligand effects have been extensively investigated in Au and Ag nanoclusters, while corresponding research efforts focusing on Cu nanoclusters remain relatively insufficient. Such a scarcity could primarily be attributed to the inherent instability of Cu nanoclusters relative to their Au/Ag analogues. In this work, we report the controllable preparation and structural determination of a hydride-containing Cu28 nanocluster with a chemical formula of Cu28H10(SPhpOMe)18(DPPOE)3. The combination of Cu28H10(SPhpOMe)18(DPPOE)3 and previously reported Cu28H10(SPhoMe)18(TPP)3 constructs a structure-correlated cluster pair with comparable structures and properties. Accordingly, the ligand effects in directing the geometric structures and physicochemical properties (including optical absorptions and catalytic activities towards the selected hydrogenation) of copper nanoclusters were analyzed. Overall, this work presents a structure-correlated Cu28 pair that enables the atomic-level understanding of ligand effects on the structures and properties of metal nanoclusters.
