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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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1
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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3
Uncovering the Mechanism for Urea Electrochemical Synthesis by Coupling N2 and CO2 on Mo2C-MXene
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Highly Efficient Photocatalytic CO2 Methanation over Ru-Doped TiO2 with Tunable Oxygen Vacancies
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Methods to Make Conductive Covalent Organic Frameworks for Electrocatalytic Applications
2026, 45(5): 100863
doi: 10.1016/j.cjsc.2025.100863
摘要:
Self-powered X-ray detectors that combine high sensitivity with low detection limits have emerged as a critical focus in radiation detection research. This work pioneers the application of lead magnesium niobate-lead titanate (PMN-PT) single crystal, renowned for its piezoelectric properties, as a material in self-powered X-ray detectors. Due to its super internal electrostatic field, the PMN-PT single crystal self-powered detector exhibits a sensitivity of 346 μC Gyair-1 cm-2 and a detection limit of 0.43 nGyair s-1 under 40 keV X-rays, which is 17 times and 0.008% as those of the commercial α-Se detector, respectively. Notably, the detector maintains a high sensitivity of 157 μC Gyair-1 cm-2 even under hard 120 keV, surpassing the performance of most reported perovskite self-powered detectors. Furthermore, the detector exhibits a significantly reduced baseline drift (∼1.0 pA) and excellent operational stability in self-powered mode. This study conclusively demonstrates that polar piezoelectric crystals, which incorporate heavy metal elements, are highly promising candidates for developing high-performance self-powered X-ray detectors.
Self-powered X-ray detectors that combine high sensitivity with low detection limits have emerged as a critical focus in radiation detection research. This work pioneers the application of lead magnesium niobate-lead titanate (PMN-PT) single crystal, renowned for its piezoelectric properties, as a material in self-powered X-ray detectors. Due to its super internal electrostatic field, the PMN-PT single crystal self-powered detector exhibits a sensitivity of 346 μC Gyair-1 cm-2 and a detection limit of 0.43 nGyair s-1 under 40 keV X-rays, which is 17 times and 0.008% as those of the commercial α-Se detector, respectively. Notably, the detector maintains a high sensitivity of 157 μC Gyair-1 cm-2 even under hard 120 keV, surpassing the performance of most reported perovskite self-powered detectors. Furthermore, the detector exhibits a significantly reduced baseline drift (∼1.0 pA) and excellent operational stability in self-powered mode. This study conclusively demonstrates that polar piezoelectric crystals, which incorporate heavy metal elements, are highly promising candidates for developing high-performance self-powered X-ray detectors.
2026, 45(5): 100864
doi: 10.1016/j.cjsc.2026.100864
摘要:
Antimony selenide (Sb2Se3) has emerged as a promising absorbing material in photocathode for photoelectrochemical (PEC) hydrogen evolution, exhibiting a development trajectory that outpaces many traditional semiconductors. Despite growing research interest, few reviews have provided a comprehensive roadmap for this class of photocathodes. In this review, starting from the scope and fundamentals of PEC systems, we will introduce how the quasi-one-dimensional (1D) crystal structure of Sb2Se3 enables anisotropic carrier transport, benign grain boundaries, and intrinsic stability. Advances in both vacuum and solution-based deposition techniques have yielded high-quality and scalable thin films, while recent progress in crystal orientation control, interface engineering, and co-catalyst integration has markedly improved efficiency. In parallel, the application of protection layers and bubble management strategies has extended operational stability. Beyond hydrogen evolution, Sb2Se3 has also shown potential for alternative solar-driven reactions. Nevertheless, challenges such as defect-induced recombination, interfacial mismatches, and long-term durability remain critical bottlenecks. Future progress will rely on integrated efforts in interface engineering, defect and crystal quality control, advanced protection and bubble management strategies, and the development of earth-abundant co-catalysts for alternative reactions, thereby linking fundamental material optimization with practical device deployment in solar-to-fuel technologies.
Antimony selenide (Sb2Se3) has emerged as a promising absorbing material in photocathode for photoelectrochemical (PEC) hydrogen evolution, exhibiting a development trajectory that outpaces many traditional semiconductors. Despite growing research interest, few reviews have provided a comprehensive roadmap for this class of photocathodes. In this review, starting from the scope and fundamentals of PEC systems, we will introduce how the quasi-one-dimensional (1D) crystal structure of Sb2Se3 enables anisotropic carrier transport, benign grain boundaries, and intrinsic stability. Advances in both vacuum and solution-based deposition techniques have yielded high-quality and scalable thin films, while recent progress in crystal orientation control, interface engineering, and co-catalyst integration has markedly improved efficiency. In parallel, the application of protection layers and bubble management strategies has extended operational stability. Beyond hydrogen evolution, Sb2Se3 has also shown potential for alternative solar-driven reactions. Nevertheless, challenges such as defect-induced recombination, interfacial mismatches, and long-term durability remain critical bottlenecks. Future progress will rely on integrated efforts in interface engineering, defect and crystal quality control, advanced protection and bubble management strategies, and the development of earth-abundant co-catalysts for alternative reactions, thereby linking fundamental material optimization with practical device deployment in solar-to-fuel technologies.
2026, 45(5): 100865
doi: 10.1016/j.cjsc.2026.100865
摘要:
Nickel-cobalt (NiCo) alloys with bimetallic electronic modulation are considered promising candidates for urea electrolysis. However, their highly occupied d-band states limit the adsorption of reaction intermediates, resulting in insufficient activity toward urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). Herein, a phosphorus-doped amorphous NiCo alloy is synthesized, in which P incorporation modulates the electronic structure and upshifts the d-band center of NiCo alloy, thus optimizing the adsorption of OH− and urea molecules. The sample with optimal P content exhibits low potentials for UOR (E10/1000 = 1.28/1.65 VRHE) and HER (E−10/−1000 = −67/−206 mVRHE). Furthermore, it achieves an industrial-level current density of 500 mA cm−2 at a cell voltage of 1.72 V in the membrane electrode assembly, while maintaining stable activity for 150 h. Therefore, this work provides a new strategy to optimize reactant adsorption and ultimately enhance the electrocatalytic activity by modulating the d-band center.
Nickel-cobalt (NiCo) alloys with bimetallic electronic modulation are considered promising candidates for urea electrolysis. However, their highly occupied d-band states limit the adsorption of reaction intermediates, resulting in insufficient activity toward urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). Herein, a phosphorus-doped amorphous NiCo alloy is synthesized, in which P incorporation modulates the electronic structure and upshifts the d-band center of NiCo alloy, thus optimizing the adsorption of OH− and urea molecules. The sample with optimal P content exhibits low potentials for UOR (E10/1000 = 1.28/1.65 VRHE) and HER (E−10/−1000 = −67/−206 mVRHE). Furthermore, it achieves an industrial-level current density of 500 mA cm−2 at a cell voltage of 1.72 V in the membrane electrode assembly, while maintaining stable activity for 150 h. Therefore, this work provides a new strategy to optimize reactant adsorption and ultimately enhance the electrocatalytic activity by modulating the d-band center.
Photosynthesis of CH4 and H2O2 from CO2 and H2O over Pd/SnNb2O6 via strong metal-support interaction
2026, 45(5): 100866
doi: 10.1016/j.cjsc.2026.100866
摘要:
The construction of bifunctional photocatalysts that integrate oxidative and reductive sites for concurrent CO2-to-CH4 and H2O-to-H2O2 conversion under visible light remains a formidable challenge. Herein, a facile photo-deposition route was designed to support Pd nanoparticles (4.5 nm) onto SnNb2O6 nanosheets (3.5 nm) for constructing a photocatalyst (Pd-PNS). Under visible-light irradiation (λ ≥ 400 nm) and without any sacrificial agent, the optimized Pd-PNS catalyst achieves CH4 and H2O2 evolution rates of 24.3 and 79.2 μmol g-1 h-1, respectively (1:4 stoichiometry), with an apparent quantum efficiency (CH4) of 0.40 % at 420 nm, outperforming most reported systems operated under equivalent conditions. The results of characterizations reveal the formation of a strong metal-support interaction (SMSI) and a Schottky junction between Pd and SnNb2O6. SMSI causes the loss of lattice oxygens, thus generating Nb4+ and O vacancies. The Schottky junction induces the migration of photogenerated electrons to Pd NPs, while holes are trapped at lattice oxygen sites (around Nb4+), thereby improving charge transfer and separation. CO2 is reduced to CH4 on Pd NPs, while H2O is oxidized to H2O2 on Nb4+ sites, validating a true dual-site photocatalytic cycle (CO2 + 6 H2O → CH4 + 4H2O2). This work offers a valuable strategy for sacrificial-free co-production of solar fuel and green oxidant by photoinducing SMSI in a photocatalyst.
The construction of bifunctional photocatalysts that integrate oxidative and reductive sites for concurrent CO2-to-CH4 and H2O-to-H2O2 conversion under visible light remains a formidable challenge. Herein, a facile photo-deposition route was designed to support Pd nanoparticles (4.5 nm) onto SnNb2O6 nanosheets (3.5 nm) for constructing a photocatalyst (Pd-PNS). Under visible-light irradiation (λ ≥ 400 nm) and without any sacrificial agent, the optimized Pd-PNS catalyst achieves CH4 and H2O2 evolution rates of 24.3 and 79.2 μmol g-1 h-1, respectively (1:4 stoichiometry), with an apparent quantum efficiency (CH4) of 0.40 % at 420 nm, outperforming most reported systems operated under equivalent conditions. The results of characterizations reveal the formation of a strong metal-support interaction (SMSI) and a Schottky junction between Pd and SnNb2O6. SMSI causes the loss of lattice oxygens, thus generating Nb4+ and O vacancies. The Schottky junction induces the migration of photogenerated electrons to Pd NPs, while holes are trapped at lattice oxygen sites (around Nb4+), thereby improving charge transfer and separation. CO2 is reduced to CH4 on Pd NPs, while H2O is oxidized to H2O2 on Nb4+ sites, validating a true dual-site photocatalytic cycle (CO2 + 6 H2O → CH4 + 4H2O2). This work offers a valuable strategy for sacrificial-free co-production of solar fuel and green oxidant by photoinducing SMSI in a photocatalyst.
2026, 45(5): 100867
doi: 10.1016/j.cjsc.2026.100867
摘要:
As food safety concerns grow, controlling organophosphorus pesticide residues and food spoilage substances has become a priority. Effectively degrading contaminants like dichlorvos (DDVP) on chili peppers and histamine (HA) in sardines is crucial for food safety. This study explores the rapid degradation and mechanism of DDVP on chili pepper surfaces and HA in sardines using S-scheme Al6Si2O13/g-C3N4 (ASO/CN) nanocomposites. Rapid detection methods analyzed standard solutions of DDVP and HA. The synthesized ASO/CN nanocomposites showed excellent photocatalytic activity, reducing DDVP from 100% to 17.7% in 100 min, outperforming individual ASO and CN. The catalyst maintained high degradation efficiency over five cycles (500 min). The ASO/CN nanocomposites also degraded HA in sardines, lowering it from 100% to 9.2% in 70 min, with stable performance over five cycles (350 min). Characterization techniques, including in situ X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscopy (KPFM), femtosecond transient absorption spectroscopy (fs-TAS), and differential charge density calculations, confirmed an S-scheme photocatalytic mechanism that enhanced radical formation. Based on these findings, practical tests under natural conditions were conducted. The catalyst reduced DDVP on chili peppers from 100% to 39.2% over seven days, outperforming the control (100% to 78%). In sardines, HA in the ASO/CN-treated group increased from 25.1% to 71.6% over five days, while the untreated group increased from 25% to 90.5%. These results offer a new approach for organophosphorus pesticide degradation and meat preservation.
As food safety concerns grow, controlling organophosphorus pesticide residues and food spoilage substances has become a priority. Effectively degrading contaminants like dichlorvos (DDVP) on chili peppers and histamine (HA) in sardines is crucial for food safety. This study explores the rapid degradation and mechanism of DDVP on chili pepper surfaces and HA in sardines using S-scheme Al6Si2O13/g-C3N4 (ASO/CN) nanocomposites. Rapid detection methods analyzed standard solutions of DDVP and HA. The synthesized ASO/CN nanocomposites showed excellent photocatalytic activity, reducing DDVP from 100% to 17.7% in 100 min, outperforming individual ASO and CN. The catalyst maintained high degradation efficiency over five cycles (500 min). The ASO/CN nanocomposites also degraded HA in sardines, lowering it from 100% to 9.2% in 70 min, with stable performance over five cycles (350 min). Characterization techniques, including in situ X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscopy (KPFM), femtosecond transient absorption spectroscopy (fs-TAS), and differential charge density calculations, confirmed an S-scheme photocatalytic mechanism that enhanced radical formation. Based on these findings, practical tests under natural conditions were conducted. The catalyst reduced DDVP on chili peppers from 100% to 39.2% over seven days, outperforming the control (100% to 78%). In sardines, HA in the ASO/CN-treated group increased from 25.1% to 71.6% over five days, while the untreated group increased from 25% to 90.5%. These results offer a new approach for organophosphorus pesticide degradation and meat preservation.
2026, 45(5): 100868
doi: 10.1016/j.cjsc.2026.100868
摘要:
Mn-activated phosphors have attracted great attention, but the inevitable self-reduction of Mn4+ to Mn2+ and precise regulation of Mn4+/Mn2+ content remain serious challenges. Herein, through solid-state reaction in air, we demonstrate that the degree of self-reduction and valence of Mn can be accurately manipulated in normal spinel ZnGa2O4 (ZGO) by incorporation of Li+ and F-, achieving color-tunable photoluminescence (PL) as desired, from blue self-luminescence to red/green emission of Mn4+/Mn2+. Both theoretical (i.e., density functional theory, bond energy theory) and experimental (i.e., dynamic/static spectroscopy) analyses indicate that Li+ occupying the tetrahedral Zn2+ site can push Mn4+ into the octahedral Ga3+ site and restrain self-reduction of Mn4+ owing to localized charge accumulation around Li+ that depletes excess electrons. Furthermore, F− substitution can repair intrinsic oxygen vacancies, further suppressing self-reduction and detrimental electron-capturing effects. Meanwhile, Li+/F− incorporation can distort ZGO and break the forbidden transition of Mn4+, leading to broadened PL and enhanced efficiency. The long-persistent PL (LPL) of ZGO: Mn/Li/F with wide shallow/deep traps is also explored in depth. Finally, the Li/F-dependent tunable PL and LPL of ZGO: Mn/Li/F show great potential for applications in ratiometric optical thermometers, plant lighting, white LEDs, and dynamic anticounterfeiting.
Mn-activated phosphors have attracted great attention, but the inevitable self-reduction of Mn4+ to Mn2+ and precise regulation of Mn4+/Mn2+ content remain serious challenges. Herein, through solid-state reaction in air, we demonstrate that the degree of self-reduction and valence of Mn can be accurately manipulated in normal spinel ZnGa2O4 (ZGO) by incorporation of Li+ and F-, achieving color-tunable photoluminescence (PL) as desired, from blue self-luminescence to red/green emission of Mn4+/Mn2+. Both theoretical (i.e., density functional theory, bond energy theory) and experimental (i.e., dynamic/static spectroscopy) analyses indicate that Li+ occupying the tetrahedral Zn2+ site can push Mn4+ into the octahedral Ga3+ site and restrain self-reduction of Mn4+ owing to localized charge accumulation around Li+ that depletes excess electrons. Furthermore, F− substitution can repair intrinsic oxygen vacancies, further suppressing self-reduction and detrimental electron-capturing effects. Meanwhile, Li+/F− incorporation can distort ZGO and break the forbidden transition of Mn4+, leading to broadened PL and enhanced efficiency. The long-persistent PL (LPL) of ZGO: Mn/Li/F with wide shallow/deep traps is also explored in depth. Finally, the Li/F-dependent tunable PL and LPL of ZGO: Mn/Li/F show great potential for applications in ratiometric optical thermometers, plant lighting, white LEDs, and dynamic anticounterfeiting.
2026, 45(5): 100869
doi: 10.1016/j.cjsc.2026.100869
摘要:
Photocatalytic synthesis of hydrogen peroxide (H2O2) from water and oxygen is a promising yet challenging green route, primarily limited by severe charge recombination and the inefficient activation of inert O2 molecules. To address these dual bottlenecks, this work constructs an organic/inorganic step-scheme (S-scheme) heterojunction by intimately coupling C3N4 with Bi2O3. This unique architecture, as deciphered by in-situ XPS and femtosecond transient absorption spectroscopy, drives efficient S-scheme charge transfer. This process not only achieves spatial separation of powerful photogenerated carriers but also retains their high redox potential. Crucially, density functional theory calculations reveal that the interfacial electronic coupling induces a significant electron redistribution, which dramatically enhances the adsorption and activation of O2 molecules—a finding corroborated by oxygen temperature-programmed desorption. Consequently, the optimized C3N4/Bi2O3 photocatalyst delivers a remarkably high H2O2 production rate of 4.03 g-1 h-1 under simulated sunlight. The in-situ generated H2O2 further translates into superior disinfection efficacy, achieving 99.9% inactivation of E. coli within 60 min. This work elucidates the charge dynamics at organic/inorganic S-scheme interfaces and showcases a viable pathway for designing efficient photocatalysts for coupled solar fuel production and environmental applications.
Photocatalytic synthesis of hydrogen peroxide (H2O2) from water and oxygen is a promising yet challenging green route, primarily limited by severe charge recombination and the inefficient activation of inert O2 molecules. To address these dual bottlenecks, this work constructs an organic/inorganic step-scheme (S-scheme) heterojunction by intimately coupling C3N4 with Bi2O3. This unique architecture, as deciphered by in-situ XPS and femtosecond transient absorption spectroscopy, drives efficient S-scheme charge transfer. This process not only achieves spatial separation of powerful photogenerated carriers but also retains their high redox potential. Crucially, density functional theory calculations reveal that the interfacial electronic coupling induces a significant electron redistribution, which dramatically enhances the adsorption and activation of O2 molecules—a finding corroborated by oxygen temperature-programmed desorption. Consequently, the optimized C3N4/Bi2O3 photocatalyst delivers a remarkably high H2O2 production rate of 4.03 g-1 h-1 under simulated sunlight. The in-situ generated H2O2 further translates into superior disinfection efficacy, achieving 99.9% inactivation of E. coli within 60 min. This work elucidates the charge dynamics at organic/inorganic S-scheme interfaces and showcases a viable pathway for designing efficient photocatalysts for coupled solar fuel production and environmental applications.
2026, 45(5): 100870
doi: 10.1016/j.cjsc.2026.100870
摘要:
Efficient spatial separation and orderly migration of charge carriers, as well as robust kinetics at catalytic sites, constitute the fundamental and core issues in enhancing the conversion of solar energy into hydrogen from water splitting. Herein, surface localization polarization engineering has been confirmed to be effective to accelerate the oriented charge migration dynamics behaviour and collaboratively activate redox crystal facets on the constructed Co3O4/In2S3 S-scheme heterojunction. Theoretical calculations and ultrafast atomic-scale spatiotemporal analysis demonstrate that, Co3O4/In2S3 heterojunction endows the surface localized field pointing from the hexagonal In2S3{102} to cubic Co3O4{111} with an increased field strength on the basis of Co3O4 from 0.27 μV to 2.19 μV and lifetime from 260.99 ns to 975.18 ns for charge carrier transfer to the surface of the redox crystal facets. Polarization-state charge uneven distribution reduces and enhances the binding energy of components on active crystal facets thus with correspondingly increasing and decreasing onsite electron density for promoting chemical adsorption of *H and *OH, respectively. Solar to H2 of 1.32% at AM 1.5G is achieved along with high photocatalytic stability. Surface polarization engineering plays a pivotal role in our study, enabling substantial tuning of charge transfer behavior and crystal facet surface activation within S-scheme heterojunctions for the improved photocatalytic H2 generation.
Efficient spatial separation and orderly migration of charge carriers, as well as robust kinetics at catalytic sites, constitute the fundamental and core issues in enhancing the conversion of solar energy into hydrogen from water splitting. Herein, surface localization polarization engineering has been confirmed to be effective to accelerate the oriented charge migration dynamics behaviour and collaboratively activate redox crystal facets on the constructed Co3O4/In2S3 S-scheme heterojunction. Theoretical calculations and ultrafast atomic-scale spatiotemporal analysis demonstrate that, Co3O4/In2S3 heterojunction endows the surface localized field pointing from the hexagonal In2S3{102} to cubic Co3O4{111} with an increased field strength on the basis of Co3O4 from 0.27 μV to 2.19 μV and lifetime from 260.99 ns to 975.18 ns for charge carrier transfer to the surface of the redox crystal facets. Polarization-state charge uneven distribution reduces and enhances the binding energy of components on active crystal facets thus with correspondingly increasing and decreasing onsite electron density for promoting chemical adsorption of *H and *OH, respectively. Solar to H2 of 1.32% at AM 1.5G is achieved along with high photocatalytic stability. Surface polarization engineering plays a pivotal role in our study, enabling substantial tuning of charge transfer behavior and crystal facet surface activation within S-scheme heterojunctions for the improved photocatalytic H2 generation.
2026, 45(5): 100884
doi: 10.1016/j.cjsc.2026.100884
摘要:
Hydrogenolytic debenzylation is a crucial step to restore the activity of the protected functional groups for targeted compounds while avoiding the formation of by-products. However, conventional methods suffer from low catalytic efficiency due to slow mass transport and/or severe leaching or agglomeration of active species. It highlighted the urgent need to develop catalysts that enable the coexistence of high mass transport and abundant active sites. In this work, as a proof of concept, a series of bimetallic PdM catalysts (M=Fe, Ni, Cu) anchored on hierarchically ordered porous skeletons were developed to enable the fast hydrogenolytic debenzylation of tetraacetyldibenzylhexaazaisowurtzitane (TADBIW) into tetraacetylhexaazaisowurtzitane (TAIW). We demonstrate that a hierarchically ordered macroporous N-doped carbon (DOM-NC) scaffold can simultaneously guarantee rapid diffusion of the bulky substrate (TADBIW) and stabilize electron-rich Pd(0) species when a trace amount of Ni is co-introduced. The resulting PdNi/DOM-NC catalyst delivers 97.3 % yield of TAIW within 2.5 h at an ultra-low Pd loading (Pd: TADBIW = 2.5 wt ‰) and retains >95 % activity after four cycles without detectable Pd loss. Structural and theoretical analyses reveal that (i) the 3DOM architecture shortens diffusion lengths, (ii) adjacent Ni atoms transfer electron density to Pd, increasing the surface Pd(0) fraction, and (iii) the Ni–Pd synergy lowers the H2 dissociation barrier and accelerates the rate-determining second debenzylation step. This study provides new insights into the rational design of highly efficient noble-metal-based heterogeneous catalysts and offers guidance for developing catalysts for other macromolecular hydrogenolysis reactions.
Hydrogenolytic debenzylation is a crucial step to restore the activity of the protected functional groups for targeted compounds while avoiding the formation of by-products. However, conventional methods suffer from low catalytic efficiency due to slow mass transport and/or severe leaching or agglomeration of active species. It highlighted the urgent need to develop catalysts that enable the coexistence of high mass transport and abundant active sites. In this work, as a proof of concept, a series of bimetallic PdM catalysts (M=Fe, Ni, Cu) anchored on hierarchically ordered porous skeletons were developed to enable the fast hydrogenolytic debenzylation of tetraacetyldibenzylhexaazaisowurtzitane (TADBIW) into tetraacetylhexaazaisowurtzitane (TAIW). We demonstrate that a hierarchically ordered macroporous N-doped carbon (DOM-NC) scaffold can simultaneously guarantee rapid diffusion of the bulky substrate (TADBIW) and stabilize electron-rich Pd(0) species when a trace amount of Ni is co-introduced. The resulting PdNi/DOM-NC catalyst delivers 97.3 % yield of TAIW within 2.5 h at an ultra-low Pd loading (Pd: TADBIW = 2.5 wt ‰) and retains >95 % activity after four cycles without detectable Pd loss. Structural and theoretical analyses reveal that (i) the 3DOM architecture shortens diffusion lengths, (ii) adjacent Ni atoms transfer electron density to Pd, increasing the surface Pd(0) fraction, and (iii) the Ni–Pd synergy lowers the H2 dissociation barrier and accelerates the rate-determining second debenzylation step. This study provides new insights into the rational design of highly efficient noble-metal-based heterogeneous catalysts and offers guidance for developing catalysts for other macromolecular hydrogenolysis reactions.
2026, 45(5): 100885
doi: 10.1016/j.cjsc.2026.100885
摘要:
2026, 45(5): 100886
doi: 10.1016/j.cjsc.2026.100886
摘要:
The incorporation of a third component to ternary organic solar cells (T-OSCs) is an effective strategy for enhancing the power conversion efficiency (PCE). While the fluorination extent of acceptor molecules is critical for modulating energy levels, molecular packing, and blend compatibility, systematic studies on the fluorination pattern remain scarce. In this work, we synthesized three novel fluorinated acceptors (o-2F, p-2F, and t-4F) with varied fluorine substitution patterns on the central benzene core via an atom-economical direct C–H arylation route. The influence of the fluorine substitution motif on molecular conformation, aggregation behavior, and device performance was systematically investigated. Theoretical calculations revealed that increased fluorination significantly enhances molecular planarity. Device performance tests demonstrated that the ortho-difluorinated acceptor o-2F promotes favorable nanoscale phase separation and facilitates efficient charge transport. Consequently, the PM6:Y6:o-2F-based TOSCs achieved a notable improvement in PCE from 16.16% to 17.41% compared to the PM6:Y6 binary counterpart, accompanied by concurrent enhancements in open-circuit voltage (from 0.83 V to 0.85 V), short-circuit current (from 26.45 to 27.19 mA cm-2), and fill factor (from 73.56% to 75.33%). In contrast, the excessively fluorinated t-4F led to overly enhanced crystallinity, resulting in limited morphological optimization and marginal PCE improvement. This study underscores the importance of balancing molecular planarity and aggregation through rational fluorination design, providing valuable guidance for developing high-performance acceptor materials for T-OSCs.
The incorporation of a third component to ternary organic solar cells (T-OSCs) is an effective strategy for enhancing the power conversion efficiency (PCE). While the fluorination extent of acceptor molecules is critical for modulating energy levels, molecular packing, and blend compatibility, systematic studies on the fluorination pattern remain scarce. In this work, we synthesized three novel fluorinated acceptors (o-2F, p-2F, and t-4F) with varied fluorine substitution patterns on the central benzene core via an atom-economical direct C–H arylation route. The influence of the fluorine substitution motif on molecular conformation, aggregation behavior, and device performance was systematically investigated. Theoretical calculations revealed that increased fluorination significantly enhances molecular planarity. Device performance tests demonstrated that the ortho-difluorinated acceptor o-2F promotes favorable nanoscale phase separation and facilitates efficient charge transport. Consequently, the PM6:Y6:o-2F-based TOSCs achieved a notable improvement in PCE from 16.16% to 17.41% compared to the PM6:Y6 binary counterpart, accompanied by concurrent enhancements in open-circuit voltage (from 0.83 V to 0.85 V), short-circuit current (from 26.45 to 27.19 mA cm-2), and fill factor (from 73.56% to 75.33%). In contrast, the excessively fluorinated t-4F led to overly enhanced crystallinity, resulting in limited morphological optimization and marginal PCE improvement. This study underscores the importance of balancing molecular planarity and aggregation through rational fluorination design, providing valuable guidance for developing high-performance acceptor materials for T-OSCs.
2026, 45(5): 100888
doi: 10.1016/j.cjsc.2026.100888
摘要:
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.
