Login In
2025 Volume 44 Issue 8
2025, 44(8): 100625
doi: 10.1016/j.cjsc.2025.100625
Abstract:
Metal-organic frameworks (MOFs) with new topologies and enhanced properties can be obtained by connecting metal-organic layers (MOLs) using multifunctional linkers. However, new topologies constructed by this method using linear-shaped ligands have not yet been explored. Herein, we present the design of NUT-123 by incorporating a near-linear perylene diimide (PDI) derivate, PDI–CH3–COOH, into the preselected zirconium-based MOLs. 3D electron diffraction confirms the successful construction of a novel topology in NUT-123. Furthermore, the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI–CH3–COOH. NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility, achieving 100% conversion of various organic sulfides. Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer. This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.
Metal-organic frameworks (MOFs) with new topologies and enhanced properties can be obtained by connecting metal-organic layers (MOLs) using multifunctional linkers. However, new topologies constructed by this method using linear-shaped ligands have not yet been explored. Herein, we present the design of NUT-123 by incorporating a near-linear perylene diimide (PDI) derivate, PDI–CH3–COOH, into the preselected zirconium-based MOLs. 3D electron diffraction confirms the successful construction of a novel topology in NUT-123. Furthermore, the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI–CH3–COOH. NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility, achieving 100% conversion of various organic sulfides. Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer. This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.
2025, 44(8): 100626
doi: 10.1016/j.cjsc.2025.100626
Abstract:
Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes. The method of metal coordination has emerged as a robust methodology for chirality induction in many systems. In this work, we engineered two rigid and flexible chiral organic ligands (L1 and L2) by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties. They demonstrate versatile coordination capabilities toward both 3d- and 4f-block metals, enabling modulation of luminescent characteristics with blue, green and red emissions. Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L1/L2 with Zn2+, Eu3+, and Tb3+. The coordination processes effectively rigidify molecular conformations, leading to an enhanced CPL performance. Particularly, the Tb-L2 complex displays superior lanthanide-centered emission with a fluorescence quantum yield of ∼55% and an emission dissymmetry factor glum = 5.5 × 10−3. By engineering the substitution on pillar[5]arene scaffolds, we have established a metal-coordination platform with CPL characteristics, which paves the way in the design of new metal-based luminescent materials.
Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes. The method of metal coordination has emerged as a robust methodology for chirality induction in many systems. In this work, we engineered two rigid and flexible chiral organic ligands (L1 and L2) by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties. They demonstrate versatile coordination capabilities toward both 3d- and 4f-block metals, enabling modulation of luminescent characteristics with blue, green and red emissions. Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L1/L2 with Zn2+, Eu3+, and Tb3+. The coordination processes effectively rigidify molecular conformations, leading to an enhanced CPL performance. Particularly, the Tb-L2 complex displays superior lanthanide-centered emission with a fluorescence quantum yield of ∼55% and an emission dissymmetry factor glum = 5.5 × 10−3. By engineering the substitution on pillar[5]arene scaffolds, we have established a metal-coordination platform with CPL characteristics, which paves the way in the design of new metal-based luminescent materials.
2025, 44(8): 100627
doi: 10.1016/j.cjsc.2025.100627
Abstract:
Ethylene glycol oxidation reaction (EGOR) is important to address the environmental issues caused by the increased production of polyethylene terephthalate (PET). Metal organic frameworks (MOFs) with superior stability, high specific surface area and excellent catalytic performance can convert PET into valuable products through EGOR and hydrogen evolution reaction (HER). Herein, a microbial template strategy was adopted to prepare carbon sphere-supported orthogonal nanosheet bimetallic MOF catalysts. The prepared catalyst needs only 1.42 V, 307 mV, and 1.83 V at a current density of 100 mA cm−2 for EGOR, HER, and EGOR//HER, respectively. More importantly, it can stably perform for at least 160 h at a current density of 500 mA cm−2. The high specific surface area of bimetallic MOF and the synergistic effect of yeast carbon shell increase the contact area between the intrinsic active sites and ∗OH and EG, thus improving the EGOR and HER catalytic activity and stability. This work provides a novel strategy to construct bimetallic orthogonal electrocatalysts with efficient HER//EGOR performance, which is of great significance for achieving sustainable energy conversion and environmental purification.
Ethylene glycol oxidation reaction (EGOR) is important to address the environmental issues caused by the increased production of polyethylene terephthalate (PET). Metal organic frameworks (MOFs) with superior stability, high specific surface area and excellent catalytic performance can convert PET into valuable products through EGOR and hydrogen evolution reaction (HER). Herein, a microbial template strategy was adopted to prepare carbon sphere-supported orthogonal nanosheet bimetallic MOF catalysts. The prepared catalyst needs only 1.42 V, 307 mV, and 1.83 V at a current density of 100 mA cm−2 for EGOR, HER, and EGOR//HER, respectively. More importantly, it can stably perform for at least 160 h at a current density of 500 mA cm−2. The high specific surface area of bimetallic MOF and the synergistic effect of yeast carbon shell increase the contact area between the intrinsic active sites and ∗OH and EG, thus improving the EGOR and HER catalytic activity and stability. This work provides a novel strategy to construct bimetallic orthogonal electrocatalysts with efficient HER//EGOR performance, which is of great significance for achieving sustainable energy conversion and environmental purification.
2025, 44(8): 100628
doi: 10.1016/j.cjsc.2025.100628
Abstract:
Wearable sensors represent a promising technology to monitor human health and movement, however, it is pivotal and challenging to tailor-make highly conductive hydrogels to achieve high sensitivity and environmental weatherability for application at extreme temperature conditions. Herein, the dual-conductive hydrogels consisting of ion-conductive deep eutectic solvents (DES) and electron-conductive MXene within polymer matrix have been presented. The increment of ion and electron migration path could generate substantial resistance variation and thus improves the sensitivity of hydrogels under small strain and large strain, resembling those in low and high frequency sound discrimination of auditory transduction. Additionally, the hydrogen bonding interactions among water molecules, DES and MXene as well as polymers endow the hydrogels with superior anti-freezing and water-retaining performance. The resultant hydrogel sensor achieves ultra-fast strain response time of 0.01 s and high sensitivity over 1.0 in wide strain ranges from 1% to 150%. High sensitivity, anti-freezing and water-retaining performance enable the hydrogels to monitor strain at extreme temperature conditions from −20 to 60 °C and could detect human motion in real time. This work provides a rational approach to the construction of high-sensitivity and environmental weatherable hydrogels based on the dual-conductive fillers for the development of advanced wearable sensors.
Wearable sensors represent a promising technology to monitor human health and movement, however, it is pivotal and challenging to tailor-make highly conductive hydrogels to achieve high sensitivity and environmental weatherability for application at extreme temperature conditions. Herein, the dual-conductive hydrogels consisting of ion-conductive deep eutectic solvents (DES) and electron-conductive MXene within polymer matrix have been presented. The increment of ion and electron migration path could generate substantial resistance variation and thus improves the sensitivity of hydrogels under small strain and large strain, resembling those in low and high frequency sound discrimination of auditory transduction. Additionally, the hydrogen bonding interactions among water molecules, DES and MXene as well as polymers endow the hydrogels with superior anti-freezing and water-retaining performance. The resultant hydrogel sensor achieves ultra-fast strain response time of 0.01 s and high sensitivity over 1.0 in wide strain ranges from 1% to 150%. High sensitivity, anti-freezing and water-retaining performance enable the hydrogels to monitor strain at extreme temperature conditions from −20 to 60 °C and could detect human motion in real time. This work provides a rational approach to the construction of high-sensitivity and environmental weatherable hydrogels based on the dual-conductive fillers for the development of advanced wearable sensors.
2025, 44(8): 100629
doi: 10.1016/j.cjsc.2025.100629
Abstract:
UiO-66-H MOFs can effectively catalyze the direct selective oxidation of methane (DSOM) to high value-added oxygenates under mild conditions. However, UiO-66-NH2 with benzene-1,4-dicarboxylate (NH2-BDC) ligand modifying the Zr-oxo nodes exhibits relatively inferior catalytic performance for DSOM. Here, a combination of density functional theory (DFT) calculations and experiments was employed to explore the underlying reasons for the limited catalytic activity of UiO-66-NH2. The results indicate that the methane hydroxylation performance of UiO-66-NH2 is almost unaffected by the increase of •OH concentration. This is attributed to the formation of substantial non-covalent hydrogen bonds between the oxygen atoms of oxygenic species on the Zr-oxo nodes and the hydrogen atoms of –NH2 groups, which diminishes the spin density distribution on the active sites of (•OH)m/UiO-66-NH2, leading to minimal change of the adsorption energy of CH4. Additionally, the calculated adsorption energies (Eads) of CH4 exhibit a linear relationship with the catalytic activity of UiO-66-NH2 for DSOM reaction.
UiO-66-H MOFs can effectively catalyze the direct selective oxidation of methane (DSOM) to high value-added oxygenates under mild conditions. However, UiO-66-NH2 with benzene-1,4-dicarboxylate (NH2-BDC) ligand modifying the Zr-oxo nodes exhibits relatively inferior catalytic performance for DSOM. Here, a combination of density functional theory (DFT) calculations and experiments was employed to explore the underlying reasons for the limited catalytic activity of UiO-66-NH2. The results indicate that the methane hydroxylation performance of UiO-66-NH2 is almost unaffected by the increase of •OH concentration. This is attributed to the formation of substantial non-covalent hydrogen bonds between the oxygen atoms of oxygenic species on the Zr-oxo nodes and the hydrogen atoms of –NH2 groups, which diminishes the spin density distribution on the active sites of (•OH)m/UiO-66-NH2, leading to minimal change of the adsorption energy of CH4. Additionally, the calculated adsorption energies (Eads) of CH4 exhibit a linear relationship with the catalytic activity of UiO-66-NH2 for DSOM reaction.
2025, 44(8): 100630
doi: 10.1016/j.cjsc.2025.100630
Abstract:
Solar-driven photocatalytic overall water splitting (POWS) has emerged as a sustainable pathway for hydrogen production, yet faces intrinsic challenges in developing robust catalysts that balance efficiency, stability, and cost-effectiveness. Polymeric carbon nitride (PCN) represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability. Nevertheless, limited by rapid charge recombination and insufficient oxidative capability, little success has been achieved on pristine PCN photocatalyst in POWS. In this context, recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance. Based on the fundamental principles of photocatalysis, this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems. With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems, modification strategies including crystallinity engineering, supramolecular precursor design, cocatalyst modulation, and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years. Future perspectives for PCN-based photocatalysts are proposed, aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
Solar-driven photocatalytic overall water splitting (POWS) has emerged as a sustainable pathway for hydrogen production, yet faces intrinsic challenges in developing robust catalysts that balance efficiency, stability, and cost-effectiveness. Polymeric carbon nitride (PCN) represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability. Nevertheless, limited by rapid charge recombination and insufficient oxidative capability, little success has been achieved on pristine PCN photocatalyst in POWS. In this context, recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance. Based on the fundamental principles of photocatalysis, this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems. With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems, modification strategies including crystallinity engineering, supramolecular precursor design, cocatalyst modulation, and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years. Future perspectives for PCN-based photocatalysts are proposed, aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
2025, 44(8): 100631
doi: 10.1016/j.cjsc.2025.100631
Abstract:
Transition metal oxides (TMOs) have received extensive attention for their unique physical and chemical properties. It is worth noting that Fe-based materials stand out because of their rich natural resources, low toxicity, low price and other advantages, but at the same time confront with critical challenges such as capacity attenuation and volume expansion. Here, a universal synthesis method of MO/MFe2O4 (M = Ni, Cu, Zn) nanomaterials derived from Prussian blue analogues (PBAs) is proposed based on the self-sacrificing template strategy of metal-organic frameworks (MOFs). The calcined products retain the porous structure and small particle size of PBAs, which shorten the ion transport path, provide abundant electroactive sites and void space, effectively alleviate the effect of volume expansion, and improve the reaction kinetics. These MO/MFe2O4 anode materials exhibit excellent cyclic reversibility and stability during repeated charge/discharge process, among which, NiO/NiFe2O4 shows the best electrochemical performance, retaining a superior specific capacity of 1301.7 mAh g−1 following 230 cycles at 0.1 A g−1. In addition, the lithium adsorption capacity of the materials was further explored through the calculation of density functional theory (DFT). The research perspectives and strategies reported in this paper have strong universality and offer innovative insights for the synthesis of alternative advanced materials.
Transition metal oxides (TMOs) have received extensive attention for their unique physical and chemical properties. It is worth noting that Fe-based materials stand out because of their rich natural resources, low toxicity, low price and other advantages, but at the same time confront with critical challenges such as capacity attenuation and volume expansion. Here, a universal synthesis method of MO/MFe2O4 (M = Ni, Cu, Zn) nanomaterials derived from Prussian blue analogues (PBAs) is proposed based on the self-sacrificing template strategy of metal-organic frameworks (MOFs). The calcined products retain the porous structure and small particle size of PBAs, which shorten the ion transport path, provide abundant electroactive sites and void space, effectively alleviate the effect of volume expansion, and improve the reaction kinetics. These MO/MFe2O4 anode materials exhibit excellent cyclic reversibility and stability during repeated charge/discharge process, among which, NiO/NiFe2O4 shows the best electrochemical performance, retaining a superior specific capacity of 1301.7 mAh g−1 following 230 cycles at 0.1 A g−1. In addition, the lithium adsorption capacity of the materials was further explored through the calculation of density functional theory (DFT). The research perspectives and strategies reported in this paper have strong universality and offer innovative insights for the synthesis of alternative advanced materials.
2025, 44(8): 100632
doi: 10.1016/j.cjsc.2025.100632
Abstract:
Dry reforming of methane (DRM) has gained significant attention as a promising route to convert two major greenhouse gases (CO2 and CH4) to syngas. The development of efficient catalysts is critical for the engineering applications. In this study, the CexZr1–xO2/ZSM-5 composites with different oxygen vacancy concentrations were synthesized by tuning the Ce/Zr ratio, followed by the deposition of metal Ni to island-like CexZr1–xO2 on ZSM-5, forming a variety of Ni-CexZr1–xO2/ZSM-5 catalysts, which were applied for the DRM reaction under 750 °C. Combined with various characterizations, it was found that the oxygen vacancy concentration illustrated the volcanic tendency with the decreased Ce/Zr ratio, and the interaction between metal Ni and CexZr1–xO2 exhibited a positive relationship with oxygen vacancy concentration. The enhanced between Ni and CexZr1–xO2 interaction could improve the strength and amount of Ni–O–M (M = Ce/Zr) species, making the d-band centers of catalysts closer to the Fermi energy level, which was beneficial to the CH4 and CO2 activation, along with the improved capacity to resist sintering and coking. Especially, the C1Z3 (Ni–Ce0.25Zr0.75O2/ZSM-5) catalyst with the Ce/Zr ratio of 1/3 demonstrated the optimal catalytic performance with 91.9% CH4 and 93.8% CO2 conversions within 50 h, accompanied by the best structural and catalytic stability after 100 h. In-situ DRIFTS was employed to study the reaction path and mechanism, discovering that significant amounts of strengthened Ni–O–M species were conducive to activating adsorbed CH4 and CO2, and desorbing the linear CO species.
Dry reforming of methane (DRM) has gained significant attention as a promising route to convert two major greenhouse gases (CO2 and CH4) to syngas. The development of efficient catalysts is critical for the engineering applications. In this study, the CexZr1–xO2/ZSM-5 composites with different oxygen vacancy concentrations were synthesized by tuning the Ce/Zr ratio, followed by the deposition of metal Ni to island-like CexZr1–xO2 on ZSM-5, forming a variety of Ni-CexZr1–xO2/ZSM-5 catalysts, which were applied for the DRM reaction under 750 °C. Combined with various characterizations, it was found that the oxygen vacancy concentration illustrated the volcanic tendency with the decreased Ce/Zr ratio, and the interaction between metal Ni and CexZr1–xO2 exhibited a positive relationship with oxygen vacancy concentration. The enhanced between Ni and CexZr1–xO2 interaction could improve the strength and amount of Ni–O–M (M = Ce/Zr) species, making the d-band centers of catalysts closer to the Fermi energy level, which was beneficial to the CH4 and CO2 activation, along with the improved capacity to resist sintering and coking. Especially, the C1Z3 (Ni–Ce0.25Zr0.75O2/ZSM-5) catalyst with the Ce/Zr ratio of 1/3 demonstrated the optimal catalytic performance with 91.9% CH4 and 93.8% CO2 conversions within 50 h, accompanied by the best structural and catalytic stability after 100 h. In-situ DRIFTS was employed to study the reaction path and mechanism, discovering that significant amounts of strengthened Ni–O–M species were conducive to activating adsorbed CH4 and CO2, and desorbing the linear CO species.
2025, 44(8): 100633
doi: 10.1016/j.cjsc.2025.100633
Abstract:
Plasmon-induced hot electron can transfer from noble metal to its cohesive semiconductor in their heterostructure to initiate the photocatalytic reaction upon resonance excitation. However, the co-excitation of semiconductor in the heterostructure would also lead to the inversus transfer of photo-electron from semiconductor to noble metal, which inevitably limits the use of active electrons. After co-excitation of both localized surface plasmon resonance (LSPR) of noble metal and interband transition of semiconductor, the interfacial electron transfer process strongly depends on the energy band configuration of their heterostructure. When the Au content in the AuAg alloy nanoparticles (NPs) changes from 0 to 100 at.%, the interfacial energy band configuration at AuAg NPs/TiO2 NPs in the electrospun nanofibers (NFs) shifts from Ohmic to Schottky contacts. Further investigation finds that the optimal Schottky barrier configuration in Au0.25Ag0.75/TiO2 NFs can not only boost the plasmon-induced hot electron transfer from Au0.25Ag0.75 to TiO2 NPs, but also suppresses the backflow of photo-electrons from TiO2 to Au0.25Ag0.75 NPs in NFs. Thus, upon UV-visible light irradiation, the CO2 photo-reduction activity of Au0.25Ag0.75/TiO2 NFs is ∼3 and ∼2 times higher than that of either Ag/TiO2 or Au/TiO2 NFs.
Plasmon-induced hot electron can transfer from noble metal to its cohesive semiconductor in their heterostructure to initiate the photocatalytic reaction upon resonance excitation. However, the co-excitation of semiconductor in the heterostructure would also lead to the inversus transfer of photo-electron from semiconductor to noble metal, which inevitably limits the use of active electrons. After co-excitation of both localized surface plasmon resonance (LSPR) of noble metal and interband transition of semiconductor, the interfacial electron transfer process strongly depends on the energy band configuration of their heterostructure. When the Au content in the AuAg alloy nanoparticles (NPs) changes from 0 to 100 at.%, the interfacial energy band configuration at AuAg NPs/TiO2 NPs in the electrospun nanofibers (NFs) shifts from Ohmic to Schottky contacts. Further investigation finds that the optimal Schottky barrier configuration in Au0.25Ag0.75/TiO2 NFs can not only boost the plasmon-induced hot electron transfer from Au0.25Ag0.75 to TiO2 NPs, but also suppresses the backflow of photo-electrons from TiO2 to Au0.25Ag0.75 NPs in NFs. Thus, upon UV-visible light irradiation, the CO2 photo-reduction activity of Au0.25Ag0.75/TiO2 NFs is ∼3 and ∼2 times higher than that of either Ag/TiO2 or Au/TiO2 NFs.
2025, 44(8): 100648
doi: 10.1016/j.cjsc.2025.100648
Abstract:
2025, 44(8): 100649
doi: 10.1016/j.cjsc.2025.100649
Abstract:
The reduction of N2 to NH3 is an important reaction for the industrial production of ammonia gas. Here, we theoretically studied the thermal synthesis of ammonia catalyzed by Ru1@Mo2COx single-atom catalyst, where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx. The results show that Ru1@Mo2COx exhibits excellent stability. Moreover, Ru1@Mo2COx can effectively adsorb and activate N2, owing to up to −0.87 |e| charge transfer from Ru1@Mo2COx to N2. The optimal pathway of N2-to-NH3 conversion is association pathway I, of which the rate-determining step is *NH2→*NH3 with of barrier energy of 1.26 eV. Especially, the Mo2COx center functions as an electron reservoir, donating electrons to the NxHy species, while the Ru single atom serves as a charge transfer pathway, thereby enhancing the reaction activity. This finding provides a theoretical foundation for the rational design of MXene-based single-atom catalysts for thermal catalytic NH3 synthesis.
The reduction of N2 to NH3 is an important reaction for the industrial production of ammonia gas. Here, we theoretically studied the thermal synthesis of ammonia catalyzed by Ru1@Mo2COx single-atom catalyst, where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx. The results show that Ru1@Mo2COx exhibits excellent stability. Moreover, Ru1@Mo2COx can effectively adsorb and activate N2, owing to up to −0.87 |e| charge transfer from Ru1@Mo2COx to N2. The optimal pathway of N2-to-NH3 conversion is association pathway I, of which the rate-determining step is *NH2→*NH3 with of barrier energy of 1.26 eV. Especially, the Mo2COx center functions as an electron reservoir, donating electrons to the NxHy species, while the Ru single atom serves as a charge transfer pathway, thereby enhancing the reaction activity. This finding provides a theoretical foundation for the rational design of MXene-based single-atom catalysts for thermal catalytic NH3 synthesis.
2025, 44(8): 100650
doi: 10.1016/j.cjsc.2025.100650
Abstract:
