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Chinese Journal of Structural Chemistry
Chinese Journal of Structural Chemistry
主管 : 中国科学院
刊期 : 月刊主编 : 洪茂椿
语种 : 英文主办 : 中国科学院福建物质结构研究所、中国化学会
ISSN : 0254-5861 CN : 35-1112/TQ展开 >The Chinese Journal of Structural Chemistry, founded in 1982 by Prof. Jiaxi Lu, is an international peer-reviewed journal published in English. It publishes original research works about the structure and property of matter, including but not limited to coordination chemistry, organometallic chemistry, catalysis, energy, nanomaterial, theory/computation, structural characterization, pharmacy and life science. Published monthly by Fujian Institute of Research on the Structure of Matter, CAS, in the form of Articles, Communications, Reviews, Perspectives, and News & Views. - 影响因子: 10.3
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Recent Advances of Cu-Based Materials for Electrochemical Nitrate Reduction to Ammonia
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Transition Metal Boride-Based Materials for Electrocatalytic Water Splitting
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Uncovering the Mechanism for Urea Electrochemical Synthesis by Coupling N2 and CO2 on Mo2C-MXene
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Methods to Make Conductive Covalent Organic Frameworks for Electrocatalytic Applications
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2026, 45(3): 100773
doi: 10.1016/j.cjsc.2025.100773
摘要:
Amorphous solids, which do not possess the long-range order, hold great promise in mechanical, optical, and chemical properties, etc., and have also been revealed as critical biomineralization precursors. However, fundamental questions about their three-dimensional (3D) atomic structure remain challenging due to the long-range disorder. Conventional protocols probe such molecular structures through scattering or real-space imaging. The former provides ensemble-averaged data that masks local structural deviations, while the latter is hampered by the electron-beam sensitivity of materials. Nevertheless, based on distance-sensitive heteronuclear coupling, rotational echo double resonance (REDOR), a specialized solid-state nuclear magnetic resonance (NMR) measurement, is efficient in detecting local deviations and usually nondestructive. Here, using amorphous calcium carbonate/phosphate Ca(CO3)x(PO4)2(1-x)/3 (0 < x <1, CaCPs) solids synthesized by ion cross-linking as an example, we develop a nondestructive method to reveal local deviations of amorphous ionic solids by combining REDOR, Monte Carlo (MC), and molecular dynamic (MD) simulation. Briefly, MC simulations generated atomic structures with heterogeneous medium-range spatial apportionment of ions, and MD simulations relaxed the initial configuration to rationalize short-range order. Then, theoretical REDOR decay curves of MC/MD-generated structures were compared with experimental values to check the medium-range order. We revealed that there was heterogeneous medium-range spatial apportionment of anions in CaCPs. Because solid-state NMR applies to virtually any spin-bearing material, this methodology provides an alternative route to resolve the atomic structure of amorphous solids.
Amorphous solids, which do not possess the long-range order, hold great promise in mechanical, optical, and chemical properties, etc., and have also been revealed as critical biomineralization precursors. However, fundamental questions about their three-dimensional (3D) atomic structure remain challenging due to the long-range disorder. Conventional protocols probe such molecular structures through scattering or real-space imaging. The former provides ensemble-averaged data that masks local structural deviations, while the latter is hampered by the electron-beam sensitivity of materials. Nevertheless, based on distance-sensitive heteronuclear coupling, rotational echo double resonance (REDOR), a specialized solid-state nuclear magnetic resonance (NMR) measurement, is efficient in detecting local deviations and usually nondestructive. Here, using amorphous calcium carbonate/phosphate Ca(CO3)x(PO4)2(1-x)/3 (0 < x <1, CaCPs) solids synthesized by ion cross-linking as an example, we develop a nondestructive method to reveal local deviations of amorphous ionic solids by combining REDOR, Monte Carlo (MC), and molecular dynamic (MD) simulation. Briefly, MC simulations generated atomic structures with heterogeneous medium-range spatial apportionment of ions, and MD simulations relaxed the initial configuration to rationalize short-range order. Then, theoretical REDOR decay curves of MC/MD-generated structures were compared with experimental values to check the medium-range order. We revealed that there was heterogeneous medium-range spatial apportionment of anions in CaCPs. Because solid-state NMR applies to virtually any spin-bearing material, this methodology provides an alternative route to resolve the atomic structure of amorphous solids.
2026, 45(3): 100800
doi: 10.1016/j.cjsc.2025.100800
摘要:
2026, 45(3): 100802
doi: 10.1016/j.cjsc.2025.100802
摘要:
Research on high-performance birefringent crystals with birefringence values greater than 0.3 has grown rapidly in recent years. These materials hold great promise for enabling the compactness and miniaturization of optical components that manipulate the phase and polairization of light. Crystals based on organic π-conjugated units frequently exhibit birefringence values exceeding 0.3, establishing them as effective building blocks for next-generation birefringent materials. This work highlights recent progress in the development of birefringent crystals derived from organic π-conjugated units. We emphasize the pivotal role of these functional building blocks in crystal design and materials discovery, and review representative studies that report high-performance birefringent crystals. The article concludes with a discussion of current challenges and outlines future research directions in this emerging field.
Research on high-performance birefringent crystals with birefringence values greater than 0.3 has grown rapidly in recent years. These materials hold great promise for enabling the compactness and miniaturization of optical components that manipulate the phase and polairization of light. Crystals based on organic π-conjugated units frequently exhibit birefringence values exceeding 0.3, establishing them as effective building blocks for next-generation birefringent materials. This work highlights recent progress in the development of birefringent crystals derived from organic π-conjugated units. We emphasize the pivotal role of these functional building blocks in crystal design and materials discovery, and review representative studies that report high-performance birefringent crystals. The article concludes with a discussion of current challenges and outlines future research directions in this emerging field.
2026, 45(3): 100813
doi: 10.1016/j.cjsc.2025.100813
摘要:
Organic near-infrared (NIR) fluorophores are being considered as next-gen tools for targeted imaging of HeLa cells and cervical cancer because they have less phototoxicity, less background autofluorescence, and better tissue penetration than traditional fluorophores. Through this review article, we have discussed how recent developments in rational molecular engineering have resulted in probes that are more attuned to particular tumor microenvironmental signals as viscosity, pH, reactive oxygen species, and enzyme overexpression. These probes are brighter, have larger Stokes shifts, and can be tuned through techniques like π-extension, donor-acceptor frameworks, heteroatom incorporation, and aggregation-induced emission algorithms. Potential platforms for image-guided therapy in cervical malignancies include BODIPY, carbazole, phenothiazine/phenoxazine, phenyl derivatives, and rhodamine/xanthene analogues. Early diagnosis, surgical guiding, and theranostic applications are just a few of the many uses for these platforms. Efforts within the scientific community to enhance clinical accuracy should focus on three key areas: (1) expanding the NIR-II window for fluorophore emission to improve tissue penetration and signal quality; (2) developing activatable probes specific to organelles; and (3) integrating these systems with cutting-edge optical imaging tools analysis. Nevertheless, there are still challenges to be solved, including issues with photostability, synthesis complexity, nonspecific interactions, water solubility, and gaps in the translation of results from preclinical models to human applications. These limitations must be overcome through systematic evaluation, scalable synthesis, and thorough safety profiling if organic NIR probes for imaging and treatment of cervical cancer can be quickly brought into clinical uses.
Organic near-infrared (NIR) fluorophores are being considered as next-gen tools for targeted imaging of HeLa cells and cervical cancer because they have less phototoxicity, less background autofluorescence, and better tissue penetration than traditional fluorophores. Through this review article, we have discussed how recent developments in rational molecular engineering have resulted in probes that are more attuned to particular tumor microenvironmental signals as viscosity, pH, reactive oxygen species, and enzyme overexpression. These probes are brighter, have larger Stokes shifts, and can be tuned through techniques like π-extension, donor-acceptor frameworks, heteroatom incorporation, and aggregation-induced emission algorithms. Potential platforms for image-guided therapy in cervical malignancies include BODIPY, carbazole, phenothiazine/phenoxazine, phenyl derivatives, and rhodamine/xanthene analogues. Early diagnosis, surgical guiding, and theranostic applications are just a few of the many uses for these platforms. Efforts within the scientific community to enhance clinical accuracy should focus on three key areas: (1) expanding the NIR-II window for fluorophore emission to improve tissue penetration and signal quality; (2) developing activatable probes specific to organelles; and (3) integrating these systems with cutting-edge optical imaging tools analysis. Nevertheless, there are still challenges to be solved, including issues with photostability, synthesis complexity, nonspecific interactions, water solubility, and gaps in the translation of results from preclinical models to human applications. These limitations must be overcome through systematic evaluation, scalable synthesis, and thorough safety profiling if organic NIR probes for imaging and treatment of cervical cancer can be quickly brought into clinical uses.
2026, 45(3): 100814
doi: 10.1016/j.cjsc.2025.100814
摘要:
2026, 45(3): 100828
doi: 10.1016/j.cjsc.2025.100828
摘要:
Polymeric hole transport layers (HTLs) are emerging as one of the most promising classes of hole transporting materials for inverted (p–i–n) perovskite solar cells, offering tunable molecular design, reliable film formation, and potential for scalable processing. Within this class, fluorene-based polymers stand out due to their rigid π-conjugated backbone, which imparts thermal stability and optical transparency, and the unique C9 substitution site, which enables precise control over solubility, morphology, interfacial chemistry, and energy alignment. By linking the fluorene core with alkyl, functionalised alkyl, vinylene, biphenyl/spiro, or in situ crosslinkable motifs, researchers have created a diverse family of HTLs that balance mobility, stability, and manufacturability. Recent studies show that well-engineered fluorene polymers can deliver power conversion efficiencies above 20% and retain over 90% of their initial performance after 1000 hours of operational stress. Despite advances, challenges remain, as fabrication and stability inconsistencies hinder comparison, and few fluorene-based systems combine efficiency, stability, and scalability. Bridging this gap will require systematic mapping of C9 substitution patterns to device metrics, hybrid designs that merge complementary traits, and ISOS-compliant benchmarking. This review provides a unifying framework to guide the development of next-generation fluorene-based polymeric HTLs for durable, commercially viable perovskite photovoltaics.
Polymeric hole transport layers (HTLs) are emerging as one of the most promising classes of hole transporting materials for inverted (p–i–n) perovskite solar cells, offering tunable molecular design, reliable film formation, and potential for scalable processing. Within this class, fluorene-based polymers stand out due to their rigid π-conjugated backbone, which imparts thermal stability and optical transparency, and the unique C9 substitution site, which enables precise control over solubility, morphology, interfacial chemistry, and energy alignment. By linking the fluorene core with alkyl, functionalised alkyl, vinylene, biphenyl/spiro, or in situ crosslinkable motifs, researchers have created a diverse family of HTLs that balance mobility, stability, and manufacturability. Recent studies show that well-engineered fluorene polymers can deliver power conversion efficiencies above 20% and retain over 90% of their initial performance after 1000 hours of operational stress. Despite advances, challenges remain, as fabrication and stability inconsistencies hinder comparison, and few fluorene-based systems combine efficiency, stability, and scalability. Bridging this gap will require systematic mapping of C9 substitution patterns to device metrics, hybrid designs that merge complementary traits, and ISOS-compliant benchmarking. This review provides a unifying framework to guide the development of next-generation fluorene-based polymeric HTLs for durable, commercially viable perovskite photovoltaics.
2026, 45(3): 100829
doi: 10.1016/j.cjsc.2025.100829
摘要:
It is of vital importance to effectively capture 137Cs for human health and ecological protection due to its strong radioactivity and biotoxicity. Herein, the efficient uptake of Cs+ has been achieved by a new layered gallium oxalatophosphonate {[(CH3)2NH2][CH3CH2NH3]}2[Ga4(PO4)4(H2PO4)2(C2O4)] (FJSM-NGAPC), whose structure features the anionic gallium oxalatophosphate layer of [Ga4(PO4)4(H2PO4)2(C2O4)]n4n- with [(CH3)2NH2]+ and [CH3CH2NH3]+ cations in the interlayer spaces. The maximum Cs+ adsorption capacity of FJSM-NGAPC can reach 407.81 mg/g, which surpasses that of common Cs+ scavengers. In the presence of a large excess of interfering Na+ ions, it shows high selectivity for Cs+ ions and the maximum KdCs can reach 1.36 × 104 mL/g. In particular, FJSM-NGAPC can maintain removal performance for Cs+ in the pH range from 3.07 to 10.01 with KdCs values all above 103 mL/g. Impressively, the Cs+ adsorption mechanism is clearly revealed at the molecular level by the single crystal to single crystal (SC-SC) structural transformation. This process confirms ion exchange between Cs+ and interlayer [(CH3)2NH2]+ and [CH3CH2NH3]+ cations, accompanied by strong Cs···O interactions. This work provides an efficient metal oxalatophosphate as the scavenger for radiocesium and clearly elucidates the radiocesium capture mechanism, facilitating the design of new oxalatophosphates materials for radionuclide remediation.
It is of vital importance to effectively capture 137Cs for human health and ecological protection due to its strong radioactivity and biotoxicity. Herein, the efficient uptake of Cs+ has been achieved by a new layered gallium oxalatophosphonate {[(CH3)2NH2][CH3CH2NH3]}2[Ga4(PO4)4(H2PO4)2(C2O4)] (FJSM-NGAPC), whose structure features the anionic gallium oxalatophosphate layer of [Ga4(PO4)4(H2PO4)2(C2O4)]n4n- with [(CH3)2NH2]+ and [CH3CH2NH3]+ cations in the interlayer spaces. The maximum Cs+ adsorption capacity of FJSM-NGAPC can reach 407.81 mg/g, which surpasses that of common Cs+ scavengers. In the presence of a large excess of interfering Na+ ions, it shows high selectivity for Cs+ ions and the maximum KdCs can reach 1.36 × 104 mL/g. In particular, FJSM-NGAPC can maintain removal performance for Cs+ in the pH range from 3.07 to 10.01 with KdCs values all above 103 mL/g. Impressively, the Cs+ adsorption mechanism is clearly revealed at the molecular level by the single crystal to single crystal (SC-SC) structural transformation. This process confirms ion exchange between Cs+ and interlayer [(CH3)2NH2]+ and [CH3CH2NH3]+ cations, accompanied by strong Cs···O interactions. This work provides an efficient metal oxalatophosphate as the scavenger for radiocesium and clearly elucidates the radiocesium capture mechanism, facilitating the design of new oxalatophosphates materials for radionuclide remediation.
2026, 45(3): 100830
doi: 10.1016/j.cjsc.2025.100830
摘要:
Reversible multicolor photochromic materials based on electron donor-acceptor (EDA) systems have recently attracted considerable attention due to their potential applications in displaying, ink-free erasable printing and anti-counterfeiting. However, it is extremely challenging to realize multicolor photochromism by using same EDA system. Herein, a novel EDA iodoargentate hybrid, [(2-Bz-pyH)(Ag5I6)]·MeCN (1) (2-Bz-pyH+ = N-protonated 2-benzylpyridinium, MeCN = acetonitrile), has been obtained via solvent evaporation method at room temperature. Interestingly, upon ∼ 365 nm Hg lamp irradiation, 1 and MeCN-desolvated 1 (denoted 1-H) display lattice solvent-modulated multicolor photochromic performance (pale yellow to brown for 1, yellow to reddish brown for 1-H) and fast response time (within 1 s). Additionally, 1-H was separately fumigated with DMF/DMSO/THF/DIOX vapors, and these samples also exhibit different photochromic properties under the same light conditions. Meanwhile, the new photochromic mechanism of intermolecular charge transfer composite with photolysis iodoargentate frameworks has been proposed through the combination of experimental and theoretical investigations. These results provide a new perspective for designing multicolor photochromic materials through lattice solvent-modulated same EDA system.
Reversible multicolor photochromic materials based on electron donor-acceptor (EDA) systems have recently attracted considerable attention due to their potential applications in displaying, ink-free erasable printing and anti-counterfeiting. However, it is extremely challenging to realize multicolor photochromism by using same EDA system. Herein, a novel EDA iodoargentate hybrid, [(2-Bz-pyH)(Ag5I6)]·MeCN (1) (2-Bz-pyH+ = N-protonated 2-benzylpyridinium, MeCN = acetonitrile), has been obtained via solvent evaporation method at room temperature. Interestingly, upon ∼ 365 nm Hg lamp irradiation, 1 and MeCN-desolvated 1 (denoted 1-H) display lattice solvent-modulated multicolor photochromic performance (pale yellow to brown for 1, yellow to reddish brown for 1-H) and fast response time (within 1 s). Additionally, 1-H was separately fumigated with DMF/DMSO/THF/DIOX vapors, and these samples also exhibit different photochromic properties under the same light conditions. Meanwhile, the new photochromic mechanism of intermolecular charge transfer composite with photolysis iodoargentate frameworks has been proposed through the combination of experimental and theoretical investigations. These results provide a new perspective for designing multicolor photochromic materials through lattice solvent-modulated same EDA system.
2026, 45(3): 100831
doi: 10.1016/j.cjsc.2025.100831
摘要:
The conversion of molecular dinitrogen (N2) into ammonia (NH3) is one of the most important chemical processes. The hemilabile axial bonding in the transition metal (TM) complexes with d-p, d-d and d-df interactions could provide an electron reservoir that controls the evolution of the oxidation state on the active center, which is potential to facilitate N2-to-NH3 conversion. In this perspective, the bionic nitrogen fixing process is illustrated on a molecular level, which features flexible axial bonding to regulate “electron reservoir”. The comprehensive overview summarizes the features of TM complexes with axial supporting ligand and focuses on how the axial ‘‘assistant” atom tunes the electronic properties of the metal center to facilitate dinitrogen binding, as well as proton/electron delivery in N2 reduction. To illustrate the mechanism of axial ‘‘electron reservoir” in dinitrogen fixation on different TM complexes with axial supporting ligand, the relationships of geometric parameters, the variation of electronic structure and oxidation state, the influence principles of axial bonding regulated by anchor atoms, the critical roles of peripheral ligands and the overall comprehension from orbital interaction are all involved. A preliminary view of the major challenges and future opportunities of TM dinitrogen complexes with flexible axial bonding is highlighted at the end. Through this perspective, we hope to give a comprehensive demonstration of the flexible axial bonding as “electron reservoir” in dinitrogen fixation, and shed light on the rational design for fabricating efficient catalysts in the future.
The conversion of molecular dinitrogen (N2) into ammonia (NH3) is one of the most important chemical processes. The hemilabile axial bonding in the transition metal (TM) complexes with d-p, d-d and d-df interactions could provide an electron reservoir that controls the evolution of the oxidation state on the active center, which is potential to facilitate N2-to-NH3 conversion. In this perspective, the bionic nitrogen fixing process is illustrated on a molecular level, which features flexible axial bonding to regulate “electron reservoir”. The comprehensive overview summarizes the features of TM complexes with axial supporting ligand and focuses on how the axial ‘‘assistant” atom tunes the electronic properties of the metal center to facilitate dinitrogen binding, as well as proton/electron delivery in N2 reduction. To illustrate the mechanism of axial ‘‘electron reservoir” in dinitrogen fixation on different TM complexes with axial supporting ligand, the relationships of geometric parameters, the variation of electronic structure and oxidation state, the influence principles of axial bonding regulated by anchor atoms, the critical roles of peripheral ligands and the overall comprehension from orbital interaction are all involved. A preliminary view of the major challenges and future opportunities of TM dinitrogen complexes with flexible axial bonding is highlighted at the end. Through this perspective, we hope to give a comprehensive demonstration of the flexible axial bonding as “electron reservoir” in dinitrogen fixation, and shed light on the rational design for fabricating efficient catalysts in the future.
2026, 45(3): 100832
doi: 10.1016/j.cjsc.2025.100832
摘要:
Layered BiOCl photocatalyst exhibits great promise for photocatalytic wastewater treatment in environmental remediation. However, its structural instability hinders further development toward photodegrading organic pollutants due to the photocorrosion caused by slow photocarrier separation. To address this major challenge, the constructed BiOCl-based S-scheme heterojunction is considered as one wonderful strategy which can efficiently steer photocarrier separation by the internal electric field and synergistically achieve stable surface structure. In this work, 2D/2D FeOOH/BiOCl S-scheme heterojunction by coupling FeOOH and BiOCl nanoplate was prepared via in situ photodeposition approach. Photocatalytic results indicate that the optimal 10 wt% FeOOH/BiOCl exhibits excellent photocatalytic activity and stability in tetracycline (TC) degradation, obtaining over 89.14% photodegradation efficiency with a kinetic constant of 0.024 min−1, which is 5.2 times higher than that of bare BiOCl (0.0046 min−1). Moreover, based on the results of cycle experiment and structural characterization, FeOOH-modified BiOCl still maintains nearly 80% photodegradation efficiency after cyclic reaction, significantly boosting photocarrier separation rate and improving structural stability of BiOCl crystal. The present study offers a novel strategy for stabilizing oxyhalide crystals by construction of S-scheme heterojunction, enabling effective photodegradation of organic pollutants.
Layered BiOCl photocatalyst exhibits great promise for photocatalytic wastewater treatment in environmental remediation. However, its structural instability hinders further development toward photodegrading organic pollutants due to the photocorrosion caused by slow photocarrier separation. To address this major challenge, the constructed BiOCl-based S-scheme heterojunction is considered as one wonderful strategy which can efficiently steer photocarrier separation by the internal electric field and synergistically achieve stable surface structure. In this work, 2D/2D FeOOH/BiOCl S-scheme heterojunction by coupling FeOOH and BiOCl nanoplate was prepared via in situ photodeposition approach. Photocatalytic results indicate that the optimal 10 wt% FeOOH/BiOCl exhibits excellent photocatalytic activity and stability in tetracycline (TC) degradation, obtaining over 89.14% photodegradation efficiency with a kinetic constant of 0.024 min−1, which is 5.2 times higher than that of bare BiOCl (0.0046 min−1). Moreover, based on the results of cycle experiment and structural characterization, FeOOH-modified BiOCl still maintains nearly 80% photodegradation efficiency after cyclic reaction, significantly boosting photocarrier separation rate and improving structural stability of BiOCl crystal. The present study offers a novel strategy for stabilizing oxyhalide crystals by construction of S-scheme heterojunction, enabling effective photodegradation of organic pollutants.
2026, 45(3): 100833
doi: 10.1016/j.cjsc.2025.100833
摘要:
Carrier recombination in polymer photocatalysts involves both undissociated exciton decay and charge recombination, which are the main obstacles limiting their photocatalytic activity. Achieving efficient charge generation and separation in a polymer system is a fundamental strategy for the potential success of solar energy conversion to hydrogen, but it remains a huge challenge. In this study, we propose an innovative intermolecular π–π stacking strategy to construct a π-delocalized all-polymer S-scheme heterojunction for photocatalytic hydrogen evolution. Two conjugated porous polymers (CPPs)—PyB, composed of benzo[1,2-b:4,5-b′]dithiophene (BDT) and pyrene units, and PhB, composed of BDT and benzene—were synthesized and integrated with CN nanosheets. The highly planar and π-extended structure of PyB facilitated strong interfacial π–π stacking with CN, forming an extended π-delocalized network that enhanced the internal electric field (IEF), improved charge separation, and boosted visible-light absorption. As a result, the optimized PyB/CN-20 composite achieved a remarkable hydrogen evolution rate (HER) of 23.84 mmol⋅h−1⋅g−1 under visible light, approximately 287 times higher than that of pristine CN. This work underscores the critical role of polymer planarity and π-conjugation in heterojunction efficiency, and provides new insights into the rational design of π-delocalized S-scheme systems and establishes a general strategy for developing highly efficient, metal-free photocatalysts by leveraging molecular-level structural control.
Carrier recombination in polymer photocatalysts involves both undissociated exciton decay and charge recombination, which are the main obstacles limiting their photocatalytic activity. Achieving efficient charge generation and separation in a polymer system is a fundamental strategy for the potential success of solar energy conversion to hydrogen, but it remains a huge challenge. In this study, we propose an innovative intermolecular π–π stacking strategy to construct a π-delocalized all-polymer S-scheme heterojunction for photocatalytic hydrogen evolution. Two conjugated porous polymers (CPPs)—PyB, composed of benzo[1,2-b:4,5-b′]dithiophene (BDT) and pyrene units, and PhB, composed of BDT and benzene—were synthesized and integrated with CN nanosheets. The highly planar and π-extended structure of PyB facilitated strong interfacial π–π stacking with CN, forming an extended π-delocalized network that enhanced the internal electric field (IEF), improved charge separation, and boosted visible-light absorption. As a result, the optimized PyB/CN-20 composite achieved a remarkable hydrogen evolution rate (HER) of 23.84 mmol⋅h−1⋅g−1 under visible light, approximately 287 times higher than that of pristine CN. This work underscores the critical role of polymer planarity and π-conjugation in heterojunction efficiency, and provides new insights into the rational design of π-delocalized S-scheme systems and establishes a general strategy for developing highly efficient, metal-free photocatalysts by leveraging molecular-level structural control.
2026, 45(3): 100834
doi: 10.1016/j.cjsc.2025.100834
摘要:
2026, 45(3): 100841
doi: 10.1016/j.cjsc.2025.100841
摘要:
The catalytic performance of single-atom catalysts in CO2 photoreduction can be optimized through precise modulation of the coordination structures of single-atoms. In this study, Ru single-atoms (Ru-SAs) immobilized on the Zr6O8 clusters of a porphyrinic metal–organic framework (Zn-PCN-222) were modified with sulfhydryl groups (–SH). The resulting RuS-SAs@Zn-PCN-222 exhibited high photocatalytic activity for CO2 reduction to HCOO− using ammonia borane as the H* donor, giving rise to a HCOO− production rate of 54.4 mmol·g–1·h–1 with 99.9% selectivity, which was approximately 20.1 and 4.5 times higher than that of Zn-PCN-222 and –SH-free Ru-SAs@Zn-PCN-222, respectively. Photoelectrochemical measurements demonstrated that the incorporated RuS-SAs enhanced the separation and migration of photogenerated charges in RuS-SAs@Zn-PCN-222. Further in situ experiments revealed that the RuS-SAs could accept photogenerated electrons from Zn-PCN-222 as well as electrons from the –SH groups, and then inject to inert CO2 molecules, thereby facilitating CO2 activation and its subsequent coupling with H* to form HCOO−.
The catalytic performance of single-atom catalysts in CO2 photoreduction can be optimized through precise modulation of the coordination structures of single-atoms. In this study, Ru single-atoms (Ru-SAs) immobilized on the Zr6O8 clusters of a porphyrinic metal–organic framework (Zn-PCN-222) were modified with sulfhydryl groups (–SH). The resulting RuS-SAs@Zn-PCN-222 exhibited high photocatalytic activity for CO2 reduction to HCOO− using ammonia borane as the H* donor, giving rise to a HCOO− production rate of 54.4 mmol·g–1·h–1 with 99.9% selectivity, which was approximately 20.1 and 4.5 times higher than that of Zn-PCN-222 and –SH-free Ru-SAs@Zn-PCN-222, respectively. Photoelectrochemical measurements demonstrated that the incorporated RuS-SAs enhanced the separation and migration of photogenerated charges in RuS-SAs@Zn-PCN-222. Further in situ experiments revealed that the RuS-SAs could accept photogenerated electrons from Zn-PCN-222 as well as electrons from the –SH groups, and then inject to inert CO2 molecules, thereby facilitating CO2 activation and its subsequent coupling with H* to form HCOO−.
2026, 45(3): 100842
doi: 10.1016/j.cjsc.2025.100842
摘要:
In recent years, metal-organic frameworks (MOFs) have emerged as promising materials in modifying perovskite solar cells (PSCs) due to their unique porous structures, exceptional specific surface area, tunable organic–inorganic coordination environments, and abundant modification sites. These features endowed MOFs with the ability to regulate the crystallization rate of perovskite films, promote uniform crystal growth, and passivate both surface and grain boundary defects. This review systematically categorizes the applications of MOFs in PSCs based on MOF types and their corresponding functional mechanisms, while exploring the selection criteria for MOFs with different structures from five key dimensions: pores, framework structures, functional groups, MOF composites, and MOF derivatives. Focusing on the structural design of MOFs, this review further aims to forecast the development trends of MOFs at the MOF/PSCs interface and provide guidance for the rational design and selection of MOFs for propelling next-generation photovoltaic technologies.
In recent years, metal-organic frameworks (MOFs) have emerged as promising materials in modifying perovskite solar cells (PSCs) due to their unique porous structures, exceptional specific surface area, tunable organic–inorganic coordination environments, and abundant modification sites. These features endowed MOFs with the ability to regulate the crystallization rate of perovskite films, promote uniform crystal growth, and passivate both surface and grain boundary defects. This review systematically categorizes the applications of MOFs in PSCs based on MOF types and their corresponding functional mechanisms, while exploring the selection criteria for MOFs with different structures from five key dimensions: pores, framework structures, functional groups, MOF composites, and MOF derivatives. Focusing on the structural design of MOFs, this review further aims to forecast the development trends of MOFs at the MOF/PSCs interface and provide guidance for the rational design and selection of MOFs for propelling next-generation photovoltaic technologies.
2026, 45(3): 100843
doi: 10.1016/j.cjsc.2025.100843
摘要:
Organic cage compounds, which are among the most important classes of supramolecular hosts, have been found to be capable of capturing various guests through host-guest interactions due to their inherent cavities. To date, the exploration of potential applications based on such host-guest chemistry has been a subject of intensive research. Herein, we report a highly stable sp2 carbon-conjugated porous organic cage (POC), abbreviated as sp2c-POC3, formed via the Knoevenagel reaction between tetraformyl-functionalized calix[4]resorcinarene and V-shaped diacetonitrile subunits. X-ray crystallographic analysis reveals that sp2c-POC3 is a [2+4] long lantern-shaped cage. It contains four rhombic windows with an average edge length of approximately 2.1 nm and a large cavity with a volume of approximately 782 Å3. Notably, this cage can selectively capture perchlorate (ClO4-) anions. Taking advantage of such anion trapping ability and the porous nature, a quasi-solid-state electrolyte (QSSE) based on sp2c-POC3 and incorporating LiClO4 has been rationally designed. This sp2c-POC3-based QSSE exhibits a high ionic conductivity of 2.5×10-3 S cm-1 at room temperature.
Organic cage compounds, which are among the most important classes of supramolecular hosts, have been found to be capable of capturing various guests through host-guest interactions due to their inherent cavities. To date, the exploration of potential applications based on such host-guest chemistry has been a subject of intensive research. Herein, we report a highly stable sp2 carbon-conjugated porous organic cage (POC), abbreviated as sp2c-POC3, formed via the Knoevenagel reaction between tetraformyl-functionalized calix[4]resorcinarene and V-shaped diacetonitrile subunits. X-ray crystallographic analysis reveals that sp2c-POC3 is a [2+4] long lantern-shaped cage. It contains four rhombic windows with an average edge length of approximately 2.1 nm and a large cavity with a volume of approximately 782 Å3. Notably, this cage can selectively capture perchlorate (ClO4-) anions. Taking advantage of such anion trapping ability and the porous nature, a quasi-solid-state electrolyte (QSSE) based on sp2c-POC3 and incorporating LiClO4 has been rationally designed. This sp2c-POC3-based QSSE exhibits a high ionic conductivity of 2.5×10-3 S cm-1 at room temperature.
2026, 45(3): 100844
doi: 10.1016/j.cjsc.2025.100844
摘要:
Nonlinear optical (NLO) crystals with efficient frequency conversion are essential for all-solid-state lasers, and exploring new second harmonic generation (SHG) enhancing strategy is crucial for the structure-property relationship research and application of NLO crystals. Conventional strategies focus on inducing parallel alignment of NLO active units. In this work, two new regulation means, i.e. bond polarization and flexible deformation, have been identified in rare earth carbonates REXCO3 (RE = La, Ce, Y; X = OH, F) with anionic motifs circular aligned through experimental characterization and first-principles calculations. They can promote the SHG effect in the form of electronic polarization and polyhedra distortion, respectively. Such regulation methods break the common acceptation that only carbonates aligning in a parallel pattern can effectively achieve the superposition of hyperpolarizabilities and result in considerable SHG effect. By realizing the synergistic effect of circular alignment and rare earth polyhedra, the polarizability and flexible stretching ability of the RE-O coordination bonds are effectively exerted in the designed structure, C2_La2O2CO3. This work unveils a new mechanism for SHG enhancement in rare earth carbonates and provides new insight for designing advanced NLO materials.
Nonlinear optical (NLO) crystals with efficient frequency conversion are essential for all-solid-state lasers, and exploring new second harmonic generation (SHG) enhancing strategy is crucial for the structure-property relationship research and application of NLO crystals. Conventional strategies focus on inducing parallel alignment of NLO active units. In this work, two new regulation means, i.e. bond polarization and flexible deformation, have been identified in rare earth carbonates REXCO3 (RE = La, Ce, Y; X = OH, F) with anionic motifs circular aligned through experimental characterization and first-principles calculations. They can promote the SHG effect in the form of electronic polarization and polyhedra distortion, respectively. Such regulation methods break the common acceptation that only carbonates aligning in a parallel pattern can effectively achieve the superposition of hyperpolarizabilities and result in considerable SHG effect. By realizing the synergistic effect of circular alignment and rare earth polyhedra, the polarizability and flexible stretching ability of the RE-O coordination bonds are effectively exerted in the designed structure, C2_La2O2CO3. This work unveils a new mechanism for SHG enhancement in rare earth carbonates and provides new insight for designing advanced NLO materials.
2026, 45(2): 100746
doi: 10.1016/j.cjsc.2025.100746
摘要:
2026, 45(2): 100770
doi: 10.1016/j.cjsc.2025.100770
摘要:
Nanofibers hold great promise as oxygen electrode materials in solid oxide cells (SOCs). However, conventional fabrication methods—such as slurry processing and high-temperature sintering—inevitably disrupt their delicate nano-architectures. Here, we propose an innovative self-assembly strategy mediated by current polarization to construct La0.6Sr0.4Co0.2Fe0.8O3-δ-Gd0.1Ce0.9O2-δ (LSCF-GDC) nanofiber composite film electrodes. This approach largely preserves the fibrous morphology while promoting coherent heterointerfaces, abundant active sites, and efficient electron/ion pathways. Benefiting from this tailored architecture, the electrode achieves a low polarization resistance of 0.117 Ω cm2 and a peak power density of 1.482 W cm-2 at 800 °C. Moreover, in CO2 electrolysis mode, it delivers an impressive current density of 2.30 A cm-2 at 1.8 V. These results establish nanofiber heterostructure films, enabled by current polarization assembly, as a powerful strategy to simultaneously enhance activity, durability, and mass transport, offering new opportunities for high-performance intermediate-temperature SOCs.
Nanofibers hold great promise as oxygen electrode materials in solid oxide cells (SOCs). However, conventional fabrication methods—such as slurry processing and high-temperature sintering—inevitably disrupt their delicate nano-architectures. Here, we propose an innovative self-assembly strategy mediated by current polarization to construct La0.6Sr0.4Co0.2Fe0.8O3-δ-Gd0.1Ce0.9O2-δ (LSCF-GDC) nanofiber composite film electrodes. This approach largely preserves the fibrous morphology while promoting coherent heterointerfaces, abundant active sites, and efficient electron/ion pathways. Benefiting from this tailored architecture, the electrode achieves a low polarization resistance of 0.117 Ω cm2 and a peak power density of 1.482 W cm-2 at 800 °C. Moreover, in CO2 electrolysis mode, it delivers an impressive current density of 2.30 A cm-2 at 1.8 V. These results establish nanofiber heterostructure films, enabled by current polarization assembly, as a powerful strategy to simultaneously enhance activity, durability, and mass transport, offering new opportunities for high-performance intermediate-temperature SOCs.
2026, 45(2): 100771
doi: 10.1016/j.cjsc.2025.100771
摘要:
Cobalt-based catalysts for peroxymonosulfate (PMS) activation are often hindered by metal leaching and structural instability, limiting their practical application. To address these challenges, we developed a novel Co9S8/Ni3S2 heterojunction catalyst via a hydrothermal method followed by thermal reduction, employing interface engineering to inhibit metal co leaching. The resulting Co9S8/Ni3S2/PMS system achieved complete tylosin degradation within 120 s. Notably, cobalt leaching was reduced by 4.5 times compared to pure Co9S8, demonstrating significantly enhanced catalyst stability. Furthermore, the system exhibited high efficiency in degrading a variety of antibiotics, good cyclic stability, and strong tolerance to diverse aqueous environments. The enhanced performance is attributed to the interface-engineered heterostructure, which not only improves the structural stability by suppresses metal cation leaching, but also facilitates enhanced PMS adsorption onto the catalyst surface. This improved PMS adsorption, particularly on cobalt active sites, results in substantial electron enrichment, thereby promoting efficient tylosin degradation. This work highlights the importance of interface engineering in designing advanced heterojunction catalysts for stable, and efficient antibiotic wastewater treatment.
Cobalt-based catalysts for peroxymonosulfate (PMS) activation are often hindered by metal leaching and structural instability, limiting their practical application. To address these challenges, we developed a novel Co9S8/Ni3S2 heterojunction catalyst via a hydrothermal method followed by thermal reduction, employing interface engineering to inhibit metal co leaching. The resulting Co9S8/Ni3S2/PMS system achieved complete tylosin degradation within 120 s. Notably, cobalt leaching was reduced by 4.5 times compared to pure Co9S8, demonstrating significantly enhanced catalyst stability. Furthermore, the system exhibited high efficiency in degrading a variety of antibiotics, good cyclic stability, and strong tolerance to diverse aqueous environments. The enhanced performance is attributed to the interface-engineered heterostructure, which not only improves the structural stability by suppresses metal cation leaching, but also facilitates enhanced PMS adsorption onto the catalyst surface. This improved PMS adsorption, particularly on cobalt active sites, results in substantial electron enrichment, thereby promoting efficient tylosin degradation. This work highlights the importance of interface engineering in designing advanced heterojunction catalysts for stable, and efficient antibiotic wastewater treatment.
2026, 45(2): 100772
doi: 10.1016/j.cjsc.2025.100772
摘要:
In the application of nonlinear optical components, ideal nonlinear optical media typically need to possess high nonlinear absorption coefficients and large modulation depths, among other characteristics. The extreme thinness of two-dimensional (2D) materials, typically at the atomic scale, offers significant advantages in miniaturized optoelectronic devices. However, this also reduces the effective light-matter interaction length, ultimately limiting the achievable interaction intensity. To enhance their nonlinear optical response and unlock their full potential in nanophotonics, current research primarily focuses on two directions: one is to develop novel 2D quantum-confined material systems with enhanced intrinsic nonlinear optical responses; the other is to design effective performance modulation strategies based on nonlinear optical theory to enable precise regulation of nonlinear optical properties. Here, recent progress in tailoring third-order nonlinear optical responses of 2D materials is systematically reviewed here. Various strategies for modulating and enhancing third-order nonlinear optical responses in 2D materials are comprehensively discussed, which can be systematically classified into intrinsic regulation and light-matter interaction modulation. Moreover, the remaining challenges in modulating third-order nonlinear optical responses of 2D materials and perspectives on future research directions are discussed.
In the application of nonlinear optical components, ideal nonlinear optical media typically need to possess high nonlinear absorption coefficients and large modulation depths, among other characteristics. The extreme thinness of two-dimensional (2D) materials, typically at the atomic scale, offers significant advantages in miniaturized optoelectronic devices. However, this also reduces the effective light-matter interaction length, ultimately limiting the achievable interaction intensity. To enhance their nonlinear optical response and unlock their full potential in nanophotonics, current research primarily focuses on two directions: one is to develop novel 2D quantum-confined material systems with enhanced intrinsic nonlinear optical responses; the other is to design effective performance modulation strategies based on nonlinear optical theory to enable precise regulation of nonlinear optical properties. Here, recent progress in tailoring third-order nonlinear optical responses of 2D materials is systematically reviewed here. Various strategies for modulating and enhancing third-order nonlinear optical responses in 2D materials are comprehensively discussed, which can be systematically classified into intrinsic regulation and light-matter interaction modulation. Moreover, the remaining challenges in modulating third-order nonlinear optical responses of 2D materials and perspectives on future research directions are discussed.
2026, 45(2): 100774
doi: 10.1016/j.cjsc.2025.100774
摘要:
Developing single-component all-inorganic perovskites with excitation-dependent multicolor emission remains a considerable challenge for next-generation anti-counterfeiting technologies. Herein, we report an excitation-dependent tunable photoluminescence (PL) switching behavior in all-inorganic CsCdCl3 perovskite, which arises from by its unique structural asymmetry featuring both isolated [CdCl6]4− octahedra (D3d symmetry) and face-sharing [Cd2Cl9]5− dimers (C3v symmetry). This dual-coordination environment facilitates the dual-band emissions at 500 nm and 590 nm, attributed to free exciton (FE) recombination in [CdCl6]4− octahedra and self-trapped exciton (STE) emission from [Cd2Cl9]5− dimers, respectively. The competitive excitation pathways between FE and STE enable the reversible color switching between green and orange emission via excitation-wavelength modulation. The excitation-wavelength sensitivity is governed by the emission intensity ratio, where 254 nm excitation favors the dimer-associated STE emission at 590 nm while 365 nm excitation selectively strengthens the octahedral FE emission at 500 nm. Density functional theory (DFT) calculations confirm the direct bandgap of CsCdCl3 (2.62 eV), and elucidate the electronic transition mechanism. The excitation-dependent color-switching capability of CsCdCl3 offers promising potential for advanced applications in anti-counterfeiting and information encryption technologies. This work establishes a paradigm for designing single-component emitters with excitation-controlled multicolor PL, thereby unlocking possibilities for developing high-security anti-counterfeiting technologies.
Developing single-component all-inorganic perovskites with excitation-dependent multicolor emission remains a considerable challenge for next-generation anti-counterfeiting technologies. Herein, we report an excitation-dependent tunable photoluminescence (PL) switching behavior in all-inorganic CsCdCl3 perovskite, which arises from by its unique structural asymmetry featuring both isolated [CdCl6]4− octahedra (D3d symmetry) and face-sharing [Cd2Cl9]5− dimers (C3v symmetry). This dual-coordination environment facilitates the dual-band emissions at 500 nm and 590 nm, attributed to free exciton (FE) recombination in [CdCl6]4− octahedra and self-trapped exciton (STE) emission from [Cd2Cl9]5− dimers, respectively. The competitive excitation pathways between FE and STE enable the reversible color switching between green and orange emission via excitation-wavelength modulation. The excitation-wavelength sensitivity is governed by the emission intensity ratio, where 254 nm excitation favors the dimer-associated STE emission at 590 nm while 365 nm excitation selectively strengthens the octahedral FE emission at 500 nm. Density functional theory (DFT) calculations confirm the direct bandgap of CsCdCl3 (2.62 eV), and elucidate the electronic transition mechanism. The excitation-dependent color-switching capability of CsCdCl3 offers promising potential for advanced applications in anti-counterfeiting and information encryption technologies. This work establishes a paradigm for designing single-component emitters with excitation-controlled multicolor PL, thereby unlocking possibilities for developing high-security anti-counterfeiting technologies.
2026, 45(2): 100788
doi: 10.1016/j.cjsc.2025.100788
摘要:
Four zinc borates, MNa9ZnB16O28(OH)4 (M = K, Rb, Cs; 1−3) and Na3ZnB5O10 (4) have been made under solvothermal conditions. Compounds 1−3 are isostructural and contain an unprecedented [B16O28(OH)4]12− cluster constructed from eight B3O3 rings sharing BO4 tetrahedra. The clusters further link with ZnO4 tetrahedra to form one-dimensional (1-D) chains, which further assemble into a 3-D supramolecular framework through hydrogen bonds. 4 was made by raising the reaction temperature of 1 and features a porous-layer structure composed of [B4O9]6−clusters, BO3 units and ZnO4 tetrahedra. All compounds exhibit short deep ultraviolet (DUV) cutoff edges below 190 nm. Notably, 1−3 crystallize in the acentric space group I−4 and display second harmonic generation (SHG) responses of approximately 1.26, 1.30 and 1.32 times that of KH2PO4 (KDP), respectively, highlighting their potential as DUV nonlinear optical materials.
Four zinc borates, MNa9ZnB16O28(OH)4 (M = K, Rb, Cs; 1−3) and Na3ZnB5O10 (4) have been made under solvothermal conditions. Compounds 1−3 are isostructural and contain an unprecedented [B16O28(OH)4]12− cluster constructed from eight B3O3 rings sharing BO4 tetrahedra. The clusters further link with ZnO4 tetrahedra to form one-dimensional (1-D) chains, which further assemble into a 3-D supramolecular framework through hydrogen bonds. 4 was made by raising the reaction temperature of 1 and features a porous-layer structure composed of [B4O9]6−clusters, BO3 units and ZnO4 tetrahedra. All compounds exhibit short deep ultraviolet (DUV) cutoff edges below 190 nm. Notably, 1−3 crystallize in the acentric space group I−4 and display second harmonic generation (SHG) responses of approximately 1.26, 1.30 and 1.32 times that of KH2PO4 (KDP), respectively, highlighting their potential as DUV nonlinear optical materials.
2026, 45(2): 100789
doi: 10.1016/j.cjsc.2025.100789
摘要:
Boron cage hybrid supramolecular metal-organic frameworks (BSFs) are a subclass of anion-pillared MOFs (APMOFs). This type of materials are formed through the self-assembly of borane cage anions, metal cations and organic ligands. They possess dense arrays of anionic binding sites within the one-dimensional pores, which can interact selectively with hydrocarbon molecules via B-H···H-C dihydrogen bonds. Therefore, the design of BSFs with appropriate pore properties holds significant potential for achieving highly efficient hydrocarbon separation. However, the current research on BSFs is still in its infancy when compared to other types of APMOFs. Due to the weak coordination ability of borane anions, the directional assembly of BSFs remains challenging. This review article targets to provide an overview of the development history of BSFs, and introduce in detail their design strategies and synthesis methods. In addition, this review will elaborate on the characteristics of BSFs and discuss their gas separation performance. Finally, the current challenges faced by BSFs are summarized, and reasonable suggestions for the future design, development, and industrial application of BSFs are put forward.
Boron cage hybrid supramolecular metal-organic frameworks (BSFs) are a subclass of anion-pillared MOFs (APMOFs). This type of materials are formed through the self-assembly of borane cage anions, metal cations and organic ligands. They possess dense arrays of anionic binding sites within the one-dimensional pores, which can interact selectively with hydrocarbon molecules via B-H···H-C dihydrogen bonds. Therefore, the design of BSFs with appropriate pore properties holds significant potential for achieving highly efficient hydrocarbon separation. However, the current research on BSFs is still in its infancy when compared to other types of APMOFs. Due to the weak coordination ability of borane anions, the directional assembly of BSFs remains challenging. This review article targets to provide an overview of the development history of BSFs, and introduce in detail their design strategies and synthesis methods. In addition, this review will elaborate on the characteristics of BSFs and discuss their gas separation performance. Finally, the current challenges faced by BSFs are summarized, and reasonable suggestions for the future design, development, and industrial application of BSFs are put forward.
2026, 45(2): 100790
doi: 10.1016/j.cjsc.2025.100790
摘要:
2026, 45(2): 100791
doi: 10.1016/j.cjsc.2025.100791
摘要:
Diatomic-site catalysts (DACs) have recently emerged as highly promising platforms for photocatalytic CO2 reduction, offering unique opportunities to control reaction thermodynamics and kinetics for selective C2+ product formation. By integrating two adjacent metal centers within well-defined architectures, DACs enable synergistic activation of CO2 and stabilization of key C–C coupling intermediates, surpassing the limitations of single-atom or bulk catalysts. This perspective highlights the recent advances in DAC synthesis strategies, characterization techniques, mechanistic insights into multi-carbon formation, and the fundamental reasons why DACs facilitate C–C bond formation with high selectivity. A critical discussion is presented on the mechanism of C2+ formation on these unique active sites. Furthermore, the role of defect engineering within the catalyst support or surrounding matrix in modulating the electronic structure and stability of DACs, is thoroughly examined. Finally, this perspective outlines future research directions to further unlock the full potential of DACs for efficient and selective photocatalytic CO2 reduction to C2+ products.
Diatomic-site catalysts (DACs) have recently emerged as highly promising platforms for photocatalytic CO2 reduction, offering unique opportunities to control reaction thermodynamics and kinetics for selective C2+ product formation. By integrating two adjacent metal centers within well-defined architectures, DACs enable synergistic activation of CO2 and stabilization of key C–C coupling intermediates, surpassing the limitations of single-atom or bulk catalysts. This perspective highlights the recent advances in DAC synthesis strategies, characterization techniques, mechanistic insights into multi-carbon formation, and the fundamental reasons why DACs facilitate C–C bond formation with high selectivity. A critical discussion is presented on the mechanism of C2+ formation on these unique active sites. Furthermore, the role of defect engineering within the catalyst support or surrounding matrix in modulating the electronic structure and stability of DACs, is thoroughly examined. Finally, this perspective outlines future research directions to further unlock the full potential of DACs for efficient and selective photocatalytic CO2 reduction to C2+ products.
2026, 45(2): 100793
doi: 10.1016/j.cjsc.2025.100793
摘要:
Crystalline porous organic frameworks (CPOFs), with their highly ordered pores and tunable organic structures, have shown immense promise as platforms for enzyme immobilization. However, research on enzyme@CPOF composites, particularly for biomedical applications, is still in its early stages and lacks comprehensive and systematic review. This article provides a thorough overview of recent advances in the rational design, synthesis, and application of enzyme@CPOF biocomposites. Emphasis is placed on immobilization strategies and the structure-performance relationships revealed through molecular-level investigations. Furthermore, we highlight emerging applications in biocatalysis and biomedical engineering, and discuss persistent challenges and future directions to advance CPOFs as versatile, high-performance substrates for enzyme immobilization.
Crystalline porous organic frameworks (CPOFs), with their highly ordered pores and tunable organic structures, have shown immense promise as platforms for enzyme immobilization. However, research on enzyme@CPOF composites, particularly for biomedical applications, is still in its early stages and lacks comprehensive and systematic review. This article provides a thorough overview of recent advances in the rational design, synthesis, and application of enzyme@CPOF biocomposites. Emphasis is placed on immobilization strategies and the structure-performance relationships revealed through molecular-level investigations. Furthermore, we highlight emerging applications in biocatalysis and biomedical engineering, and discuss persistent challenges and future directions to advance CPOFs as versatile, high-performance substrates for enzyme immobilization.
2026, 45(2): 100794
doi: 10.1016/j.cjsc.2025.100794
摘要:
2026, 45(2): 100795
doi: 10.1016/j.cjsc.2025.100795
摘要:
The advantages of transition metal compounds such as ultrahigh theoretical capacity and abundant active sites make them promising anode materials for high energy density lithium-ion batteries. Unfortunately, problems such as severe volume expansion and poor electrical conductivity seriously hinder their large-scale application. In general, reasonable optimization of composition and structure is an effective strategy for developing anode materials with excellent lithium storage properties. In this paper, ZnS/MnO composites were constructed by solvothermal sulfidation and calcination using Zn-Mn organic frameworks as self-sacrificing templates. From the perspective of material composition, both ZnS and MnO have excellent theoretical specific capacity, and the two-component metal center can provide more abundant active sites. From the perspective of structural optimization, the ZnS/MnO composites inherit the loose porous structure of the calcined metal-organic frameworks, which can not only effectively alleviate the volume expansion during the charge and discharge process, but can also help improve the conductivity of the composites and promote charge transport. Both experimental results and density functional theory calculations show that the two-component metal center of ZnS/MnO composites can improve the electronic conductivity and reduce the migration energy barrier, thus showing excellent cycle stability and remarkable rate performance. The study provides another idea for the development of high-performance anode materials for lithium-ion batteries.
The advantages of transition metal compounds such as ultrahigh theoretical capacity and abundant active sites make them promising anode materials for high energy density lithium-ion batteries. Unfortunately, problems such as severe volume expansion and poor electrical conductivity seriously hinder their large-scale application. In general, reasonable optimization of composition and structure is an effective strategy for developing anode materials with excellent lithium storage properties. In this paper, ZnS/MnO composites were constructed by solvothermal sulfidation and calcination using Zn-Mn organic frameworks as self-sacrificing templates. From the perspective of material composition, both ZnS and MnO have excellent theoretical specific capacity, and the two-component metal center can provide more abundant active sites. From the perspective of structural optimization, the ZnS/MnO composites inherit the loose porous structure of the calcined metal-organic frameworks, which can not only effectively alleviate the volume expansion during the charge and discharge process, but can also help improve the conductivity of the composites and promote charge transport. Both experimental results and density functional theory calculations show that the two-component metal center of ZnS/MnO composites can improve the electronic conductivity and reduce the migration energy barrier, thus showing excellent cycle stability and remarkable rate performance. The study provides another idea for the development of high-performance anode materials for lithium-ion batteries.
2026, 45(2): 100796
doi: 10.1016/j.cjsc.2025.100796
摘要:
Zinc-air batteries (ZABs) have emerged as promising candidates for next-generation energy storage systems due to their high energy density, safety, and environmental benignity. However, their efficiency is hindered by sluggish oxygen reduction reaction (ORR) kinetics. Constructing heterojunction with optimized interfacial electronic structure has emerged as a promising approach to enhance ORR activity. Herein, we report a Co–Mo2C heterojunction encapsulated within nitrogen-doped carbon (Co–Mo2C@NC) derived from a ZnCoMo-based metal–organic framework (ZnCoMo–HZIF). The intimate interface between Co and Mo2C enables the strong electronic coupling, which induces the interfacial charge redistribution and optimizes the d-band center of Co active sites. This electronic modulation significantly enhances the oxygen intermediate adsorption and lowers the energy barrier. As a result, Co–Mo2C@NC delivers outstanding ORR performance with a high half-wave potential (E1/2) of 0.85 V, a low Tafel slope of 94.7 mV dec-1, and a good long-term stability. Additionally, Co–Mo2C@NC as the air cathode in a zinc-air battery exhibits superior power performance and outstanding cycling stability.
Zinc-air batteries (ZABs) have emerged as promising candidates for next-generation energy storage systems due to their high energy density, safety, and environmental benignity. However, their efficiency is hindered by sluggish oxygen reduction reaction (ORR) kinetics. Constructing heterojunction with optimized interfacial electronic structure has emerged as a promising approach to enhance ORR activity. Herein, we report a Co–Mo2C heterojunction encapsulated within nitrogen-doped carbon (Co–Mo2C@NC) derived from a ZnCoMo-based metal–organic framework (ZnCoMo–HZIF). The intimate interface between Co and Mo2C enables the strong electronic coupling, which induces the interfacial charge redistribution and optimizes the d-band center of Co active sites. This electronic modulation significantly enhances the oxygen intermediate adsorption and lowers the energy barrier. As a result, Co–Mo2C@NC delivers outstanding ORR performance with a high half-wave potential (E1/2) of 0.85 V, a low Tafel slope of 94.7 mV dec-1, and a good long-term stability. Additionally, Co–Mo2C@NC as the air cathode in a zinc-air battery exhibits superior power performance and outstanding cycling stability.
2026, 45(2): 100797
doi: 10.1016/j.cjsc.2025.100797
摘要:
Surface-enhanced Raman scattering (SERS) spectroscopy based on transition metal oxide (TMO) substrates has emerged as a frontier research area, offering distinctive advantages in chemical stability, cost-effectiveness, and tunable optoelectronic properties compared to conventional noble metal substrates. This review systematically clarifies the dual enhancement mechanisms of TMO-based SERS including charge transfer (CT) resonance at the molecule-semiconductor interface and electromagnetic field amplification induced by localized surface plasmon resonance (LSPR); the two work synergistically to achieve signal amplification. In practical applications, TMO enable multi-scenario analysis via the controllable defect engineering-interfacial CT synergistic mechanism in SERS technology. These scenarios include ultrasensitive detection of biomarkers, dynamic tracking of cellular metabolism, real-time monitoring of environmental pollutants, and mechanistic analysis of catalytic reaction pathways. Nevertheless, critical challenges persist, particularly regarding quantitative reproducibility and long-term stability under operational conditions. This review focuses on discussing the SERS enhancement mechanisms of TMO, summarizing their diverse analytical applications across multiple fields, and briefly addressing existing limitations, aiming to provide insights for further advancement in TMO-based SERS research.
Surface-enhanced Raman scattering (SERS) spectroscopy based on transition metal oxide (TMO) substrates has emerged as a frontier research area, offering distinctive advantages in chemical stability, cost-effectiveness, and tunable optoelectronic properties compared to conventional noble metal substrates. This review systematically clarifies the dual enhancement mechanisms of TMO-based SERS including charge transfer (CT) resonance at the molecule-semiconductor interface and electromagnetic field amplification induced by localized surface plasmon resonance (LSPR); the two work synergistically to achieve signal amplification. In practical applications, TMO enable multi-scenario analysis via the controllable defect engineering-interfacial CT synergistic mechanism in SERS technology. These scenarios include ultrasensitive detection of biomarkers, dynamic tracking of cellular metabolism, real-time monitoring of environmental pollutants, and mechanistic analysis of catalytic reaction pathways. Nevertheless, critical challenges persist, particularly regarding quantitative reproducibility and long-term stability under operational conditions. This review focuses on discussing the SERS enhancement mechanisms of TMO, summarizing their diverse analytical applications across multiple fields, and briefly addressing existing limitations, aiming to provide insights for further advancement in TMO-based SERS research.
2026, 45(2): 100798
doi: 10.1016/j.cjsc.2025.100798
摘要:
The construction of heterojunctions at phase interfaces represents a crucial strategy for enhancing photocatalytic activity, but developing more cost-effective and higher-performance photocatalysts remains a challenge. Herein, we designed a S-scheme van der Waals heterojunctions (vdWHs) photocatalyst by in situ growth of Co9S8 on flower-like graphitic carbon nitride (FCN). The S-scheme heterojunction ensures efficient charge separation and significantly enhances redox capabilities, while the vdWHs specifically overcome the lattice mismatch limitation inherent in conventional S-scheme heterojunctions owing to its interfacial coupling. In situ XPS analysis was used to confirm the direction of interfacial charge transfer. Consequently, the photocatalyst achieved an optimal H2 evolution of 948.04 μmol h-1 g-1 without Pt cocatalysts. The tetracycline hydrochloride degradation reached 97.90% within 9 min through photocatalytic peroxymonosulfate activation that generated multiple reactive oxygen species. Liquid chromatography-mass spectrometry was employed to identify the possible reaction pathways and investigate the degradation products. This work advanced a rational design of S-scheme Co9S8/FCN vdWHs photocatalysts and offered promising solutions for both renewable energy production and wastewater remediation.
The construction of heterojunctions at phase interfaces represents a crucial strategy for enhancing photocatalytic activity, but developing more cost-effective and higher-performance photocatalysts remains a challenge. Herein, we designed a S-scheme van der Waals heterojunctions (vdWHs) photocatalyst by in situ growth of Co9S8 on flower-like graphitic carbon nitride (FCN). The S-scheme heterojunction ensures efficient charge separation and significantly enhances redox capabilities, while the vdWHs specifically overcome the lattice mismatch limitation inherent in conventional S-scheme heterojunctions owing to its interfacial coupling. In situ XPS analysis was used to confirm the direction of interfacial charge transfer. Consequently, the photocatalyst achieved an optimal H2 evolution of 948.04 μmol h-1 g-1 without Pt cocatalysts. The tetracycline hydrochloride degradation reached 97.90% within 9 min through photocatalytic peroxymonosulfate activation that generated multiple reactive oxygen species. Liquid chromatography-mass spectrometry was employed to identify the possible reaction pathways and investigate the degradation products. This work advanced a rational design of S-scheme Co9S8/FCN vdWHs photocatalysts and offered promising solutions for both renewable energy production and wastewater remediation.
2026, 45(2): 100799
doi: 10.1016/j.cjsc.2025.100799
摘要:
2026, 45(2): 100801
doi: 10.1016/j.cjsc.2025.100801
摘要:
The control of magnetic state is crucial for spintronic applications but remains a significant challenge. Traditionally, controlling magnetic state relies on physical approaches, such as applying external magnetic fields or utilizing spin-orbit coupling. In our previous work, we proposed a novel chemical approach to manipulate the magnetic state of a system through lactim-lactam tautomerization. Here, by first principles calculations, we extend the type of tautomerization to intramolecular hydrogen migration, and reveal that hydrogen migration can modulate magnetic coupling and lead to distinct magnetic configurations in two-dimensional (2D) metal-organic frameworks (MOFs) composed of diradical porphyrinoid and Fe. The migration of hydrogen atoms within porphyrinoid results in four isometric MOFs with notable changes in spin density distribution on organic linkers, which subsequently alters the magnetic coupling between the metal node and organic linkers, leading to ferromagnetic-ferrimagnetic transition in the framework. The magnetic coupling strength also changes significantly, with the Curie temperature enhanced from 5.2 K to 100.1 K. Furthermore, accompanying with the magnetic transition, the MOFs experience an electronic transition from normal half semiconductors (with band gaps of 0.11 and 0.03 eV), where the valence band (VB) and conduction band (CB) share the same spin channel, to bipolar magnetic semiconductors (with band gaps of 0.06 and 0.13 eV), where the VB and CB become fully spin-polarized in opposite directions.
The control of magnetic state is crucial for spintronic applications but remains a significant challenge. Traditionally, controlling magnetic state relies on physical approaches, such as applying external magnetic fields or utilizing spin-orbit coupling. In our previous work, we proposed a novel chemical approach to manipulate the magnetic state of a system through lactim-lactam tautomerization. Here, by first principles calculations, we extend the type of tautomerization to intramolecular hydrogen migration, and reveal that hydrogen migration can modulate magnetic coupling and lead to distinct magnetic configurations in two-dimensional (2D) metal-organic frameworks (MOFs) composed of diradical porphyrinoid and Fe. The migration of hydrogen atoms within porphyrinoid results in four isometric MOFs with notable changes in spin density distribution on organic linkers, which subsequently alters the magnetic coupling between the metal node and organic linkers, leading to ferromagnetic-ferrimagnetic transition in the framework. The magnetic coupling strength also changes significantly, with the Curie temperature enhanced from 5.2 K to 100.1 K. Furthermore, accompanying with the magnetic transition, the MOFs experience an electronic transition from normal half semiconductors (with band gaps of 0.11 and 0.03 eV), where the valence band (VB) and conduction band (CB) share the same spin channel, to bipolar magnetic semiconductors (with band gaps of 0.06 and 0.13 eV), where the VB and CB become fully spin-polarized in opposite directions.
