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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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Highly Efficient Photocatalytic CO2 Methanation over Ru-Doped TiO2 with Tunable Oxygen Vacancies
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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
2026, 45(9): 100966
doi: 10.1016/j.cjsc.2026.100966
摘要:
We investigated Ni3FeN under high pressure through in situ synchrotron X-ray diffraction and resistance measurements. An irreversible structural phase transition from Pm-3m to Cmcm was observed at approximately 16.0 GPa. The transition is driven by the displacement of Fe along the b-axis and the pronounced tilting and distortion of NNi6 octahedra along the c-axis, which breaks the original cubic symmetry. This structural change leads to a significant softening of the mechanical properties, as evidenced by a more than 40% reduction in the bulk modulus (from 249.8(2) to 150.4(5) GPa) and an increase in average Ni–N bond length. Bond angle variance Bond angle variance and quadratic elongation are determined to validate distortions in NNi6 octahedron. Concurrently, analysis of the resistance-temperature (R-T) dependence reveals a crossover in scattering mechanisms, where the distorted octahedral network severely impedes electron conduction, resulting in an anomalous rise in resistance near the transition pressure, particularly at low temperatures. These findings extended the modification of structure and physical properties of Ni3FeN to high-pressure region, and laid foundation for future material design and applications in antiperovskites.
We investigated Ni3FeN under high pressure through in situ synchrotron X-ray diffraction and resistance measurements. An irreversible structural phase transition from Pm-3m to Cmcm was observed at approximately 16.0 GPa. The transition is driven by the displacement of Fe along the b-axis and the pronounced tilting and distortion of NNi6 octahedra along the c-axis, which breaks the original cubic symmetry. This structural change leads to a significant softening of the mechanical properties, as evidenced by a more than 40% reduction in the bulk modulus (from 249.8(2) to 150.4(5) GPa) and an increase in average Ni–N bond length. Bond angle variance Bond angle variance and quadratic elongation are determined to validate distortions in NNi6 octahedron. Concurrently, analysis of the resistance-temperature (R-T) dependence reveals a crossover in scattering mechanisms, where the distorted octahedral network severely impedes electron conduction, resulting in an anomalous rise in resistance near the transition pressure, particularly at low temperatures. These findings extended the modification of structure and physical properties of Ni3FeN to high-pressure region, and laid foundation for future material design and applications in antiperovskites.
2026, 45(9): 100967
doi: 10.1016/j.cjsc.2026.100967
摘要:
The electrochemical CO2 reduction reaction (CO2RR) offers a promising strategy to produce high-value-added C2+ products. Cu-based catalysts enable C-C coupling but suffer from low C2+ selectivity. Although electronic/structural engineering and cation effects have been widely studied, the role of anions in tuning interfacial water structure and CO2RR pathways remains insufficiently understood. Herein, a series of low-concentration anions were introduced into 1 M KOH to regulate the interfacial water environment over reconstructed CuO. By combining in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and electrochemical impedance spectroscopy, it is revealed that low-concentration anions in 1 M KOH increase the proportion of strong interfacial-water structure in the order of F- > Cl- > Br- > NO3-. Moreover, the moderate strong interfacial-water structure can accelerate *H transfer and promote *CO hydrogenation to *COH, thus favoring asymmetric C-C coupling to produce C2+ products. However, excessively stable interfacial water structure in F--containing electrolyte induces enhanced *H coverage and dominant H2 evolution. A volcano-type relationship is thus observed between C2+ selectivity and the proportion of strongly hydrogen-bonded water. This work emphasizes anion-mediated interfacial water regulation as an effective strategy to enhance C2+ selectivity for CO2RR.
The electrochemical CO2 reduction reaction (CO2RR) offers a promising strategy to produce high-value-added C2+ products. Cu-based catalysts enable C-C coupling but suffer from low C2+ selectivity. Although electronic/structural engineering and cation effects have been widely studied, the role of anions in tuning interfacial water structure and CO2RR pathways remains insufficiently understood. Herein, a series of low-concentration anions were introduced into 1 M KOH to regulate the interfacial water environment over reconstructed CuO. By combining in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and electrochemical impedance spectroscopy, it is revealed that low-concentration anions in 1 M KOH increase the proportion of strong interfacial-water structure in the order of F- > Cl- > Br- > NO3-. Moreover, the moderate strong interfacial-water structure can accelerate *H transfer and promote *CO hydrogenation to *COH, thus favoring asymmetric C-C coupling to produce C2+ products. However, excessively stable interfacial water structure in F--containing electrolyte induces enhanced *H coverage and dominant H2 evolution. A volcano-type relationship is thus observed between C2+ selectivity and the proportion of strongly hydrogen-bonded water. This work emphasizes anion-mediated interfacial water regulation as an effective strategy to enhance C2+ selectivity for CO2RR.
2026, 45(9): 100968
doi: 10.1016/j.cjsc.2026.100968
摘要:
The demonstration of this superlattice architecture provides a compelling new strategy for the design of advanced photocatalytic materials. Rather than relying on local atomic coordination tuning, this approach utilizes precise epitaxial strain to generate macroscopic electrostatic fields, thereby governing internal charge dynamics. This methodology provides a generalizable strategy: exploiting the QCSE can be extended to other polar material systems—such as transition metal dichalcogenides or polar perovskites—to promote long-lived excitons for various energy conversion applications. Moving forward, addressing the gradual degradation over extended operational periods (e.g., >500 hours) will be crucial for practical applications. Specifically, the chemical leaching of transition metal co-catalysts in harsh saline environments, as observed in the seawater tests, can lead to a continuous loss of active surface redox sites and a subsequent decline in overall catalytic efficiency. To mitigate this issue and enhance long-term durability, future research could focus on employing conformal protective layers, such as those deposited via atomic layer deposition (ALD), or engineering stronger metal-support interactions to anchor the co-catalyst clusters more firmly to the nitride nanowire surfaces. As research increasingly focuses on improving the long-term stability of active sites in such demanding environments, the structural principles demonstrated in this excitonic architecture offer a robust foundation for developing scalable and practically viable artificial photosynthesis systems.
The demonstration of this superlattice architecture provides a compelling new strategy for the design of advanced photocatalytic materials. Rather than relying on local atomic coordination tuning, this approach utilizes precise epitaxial strain to generate macroscopic electrostatic fields, thereby governing internal charge dynamics. This methodology provides a generalizable strategy: exploiting the QCSE can be extended to other polar material systems—such as transition metal dichalcogenides or polar perovskites—to promote long-lived excitons for various energy conversion applications. Moving forward, addressing the gradual degradation over extended operational periods (e.g., >500 hours) will be crucial for practical applications. Specifically, the chemical leaching of transition metal co-catalysts in harsh saline environments, as observed in the seawater tests, can lead to a continuous loss of active surface redox sites and a subsequent decline in overall catalytic efficiency. To mitigate this issue and enhance long-term durability, future research could focus on employing conformal protective layers, such as those deposited via atomic layer deposition (ALD), or engineering stronger metal-support interactions to anchor the co-catalyst clusters more firmly to the nitride nanowire surfaces. As research increasingly focuses on improving the long-term stability of active sites in such demanding environments, the structural principles demonstrated in this excitonic architecture offer a robust foundation for developing scalable and practically viable artificial photosynthesis systems.
2026, 45(9): 100969
doi: 10.1016/j.cjsc.2026.100969
摘要:
Photocatalytic conversion of CO2 into chemical fuels represents a promising route toward achieving carbon neutrality. However, its practical large-scale deployment is severely hampered, primarily due to high charge-transfer resistance and sluggish kinetics. Herein, a high-crystalline g-C3N4/BiOIO3 (CCN/BIO) S-scheme is constructed through a one-step KI molten salt method, which offers a greener and simpler alternative to conventional systems while enhancing the crystallinity of CCN and enabling the in-situ deposition of BIO. Benefiting from the high lattice matching between the two components, robust N-O-Bi interfacial chemical bonds are formed, serving as efficient channels for charge migration. As a result, the optimized CCN/BIO composite exhibits a markedly enhanced activity of photocatalytic reduction of CO2, with the total yield of CO and CH4 reaching 4.9 and 3.2 times those of pristine BIO and CCN, respectively. Combined density functional theory (DFT) calculations, in-situ irradiated X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) analyses systematically verify the S-scheme charge transfer pathway, which is synergistically driven by the internal electric field and interfacial chemical bonds. This work provides new insights into the rational design of visible-light-responsive S-scheme heterojunction photocatalysts.
Photocatalytic conversion of CO2 into chemical fuels represents a promising route toward achieving carbon neutrality. However, its practical large-scale deployment is severely hampered, primarily due to high charge-transfer resistance and sluggish kinetics. Herein, a high-crystalline g-C3N4/BiOIO3 (CCN/BIO) S-scheme is constructed through a one-step KI molten salt method, which offers a greener and simpler alternative to conventional systems while enhancing the crystallinity of CCN and enabling the in-situ deposition of BIO. Benefiting from the high lattice matching between the two components, robust N-O-Bi interfacial chemical bonds are formed, serving as efficient channels for charge migration. As a result, the optimized CCN/BIO composite exhibits a markedly enhanced activity of photocatalytic reduction of CO2, with the total yield of CO and CH4 reaching 4.9 and 3.2 times those of pristine BIO and CCN, respectively. Combined density functional theory (DFT) calculations, in-situ irradiated X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) analyses systematically verify the S-scheme charge transfer pathway, which is synergistically driven by the internal electric field and interfacial chemical bonds. This work provides new insights into the rational design of visible-light-responsive S-scheme heterojunction photocatalysts.
2026, 45(9): 100970
doi: 10.1016/j.cjsc.2026.100970
摘要:
Birefringent crystals are critical for advanced photonic technologies, yet achieving substantial optical anisotropy through rational structural design remains a challenge. Herein, we propose a multiscale structural engineering strategy that couples anisotropic functional building units (FBUs) with cation-sulfur mediated dimensional modulation to enhance optical anisotropy. Three new birefringent crystals, K4(2-ABS)4·H2O (I), Rb4(2-ABS)4·H2O (II), and Cs(2-ABS) (III) were identified by mediating the spatial matching between distinct cations and sulfurs to trigger structural evolution. Notably, the structural evolution from a quasi-2D layered arrangement (I and II) to a quasi-1D chain (III) leads to a significant enhancement in birefringence from 0.167 and 0.155 to 0.344 at 532 nm, nearly two orders of magnitude larger than that of K2SO4 and exceeding widely used commercial birefringent crystals. Structural analysis and first-principles calculations reveal a distinct dimensional transition from quasi-2D frameworks (I and II) to a quasi-1D structure (III), where dimensional reduction synergistically cooperates with the intrinsic polarizability anisotropy of [2-ABS]- to markedly enhance birefringence. This work demonstrates the effectiveness and general applicability of multiscale structural modulation as a design principle for birefringent crystal architectures.
Birefringent crystals are critical for advanced photonic technologies, yet achieving substantial optical anisotropy through rational structural design remains a challenge. Herein, we propose a multiscale structural engineering strategy that couples anisotropic functional building units (FBUs) with cation-sulfur mediated dimensional modulation to enhance optical anisotropy. Three new birefringent crystals, K4(2-ABS)4·H2O (I), Rb4(2-ABS)4·H2O (II), and Cs(2-ABS) (III) were identified by mediating the spatial matching between distinct cations and sulfurs to trigger structural evolution. Notably, the structural evolution from a quasi-2D layered arrangement (I and II) to a quasi-1D chain (III) leads to a significant enhancement in birefringence from 0.167 and 0.155 to 0.344 at 532 nm, nearly two orders of magnitude larger than that of K2SO4 and exceeding widely used commercial birefringent crystals. Structural analysis and first-principles calculations reveal a distinct dimensional transition from quasi-2D frameworks (I and II) to a quasi-1D structure (III), where dimensional reduction synergistically cooperates with the intrinsic polarizability anisotropy of [2-ABS]- to markedly enhance birefringence. This work demonstrates the effectiveness and general applicability of multiscale structural modulation as a design principle for birefringent crystal architectures.
2026, 45(9): 100971
doi: 10.1016/j.cjsc.2026.100971
摘要:
Photocatalytic technology, which enables the direct conversion of solar energy into chemical energy, presents a compelling and sustainable approach to mitigating the pressing issues of the global energy crisis and environmental degradation. S-Scheme heterojunctions have garnered significant attention in photocatalysis due to their exceptional charge separation efficiency and enhanced redox properties. Bismuth-based semiconductors, characterized by their unique layered structures, tunable electronic band configurations, and responsiveness to visible light, offer substantial advantages in the fabrication of S-Scheme heterojunctions. This review systematically summarizes recent advances in Bi-based S-Scheme heterojunctions for photocatalytic applications, focusing on the improvement of charge separation and utilization efficiency. We first elucidate the fundamental charge transfer mechanism of S-Scheme heterojunctions, followed by a comprehensive overview of construction methods including in situ hydrothermal/solvothermal synthesis, electrospinning, calcination, and electrostatically driven assembly. Advanced characterization techniques such as Kelvin Probe Force Microscopy (KPFM), in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS), and femtosecond transient absorption spectroscopy (fs-TAS) for verifying the S-Scheme charge transfer mechanism are discussed in detail. Various modulation strategies to improve photocatalytic performance are thoroughly examined, including electronic structure regulation (element doping and defect engineering), interface structure regulation (electron bridges and crystal facet engineering), and morphology/dimension engineering to optimize the surface reaction. Moreover, the applications of Bi-based S-Scheme heterojunctions in photocatalytic water splitting for hydrogen production, CO2 reduction, pollutant degradation and H2O2 generation are comprehensively summarized. Finally, the current challenges and future perspectives for the development of high-performance Bi-based S-Scheme heterojunction photocatalysts are presented. This review aims to provide profound theoretical insights and strategic frameworks for the rational design of high-efficiency Bi-based S-Scheme photocatalysts.
Photocatalytic technology, which enables the direct conversion of solar energy into chemical energy, presents a compelling and sustainable approach to mitigating the pressing issues of the global energy crisis and environmental degradation. S-Scheme heterojunctions have garnered significant attention in photocatalysis due to their exceptional charge separation efficiency and enhanced redox properties. Bismuth-based semiconductors, characterized by their unique layered structures, tunable electronic band configurations, and responsiveness to visible light, offer substantial advantages in the fabrication of S-Scheme heterojunctions. This review systematically summarizes recent advances in Bi-based S-Scheme heterojunctions for photocatalytic applications, focusing on the improvement of charge separation and utilization efficiency. We first elucidate the fundamental charge transfer mechanism of S-Scheme heterojunctions, followed by a comprehensive overview of construction methods including in situ hydrothermal/solvothermal synthesis, electrospinning, calcination, and electrostatically driven assembly. Advanced characterization techniques such as Kelvin Probe Force Microscopy (KPFM), in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS), and femtosecond transient absorption spectroscopy (fs-TAS) for verifying the S-Scheme charge transfer mechanism are discussed in detail. Various modulation strategies to improve photocatalytic performance are thoroughly examined, including electronic structure regulation (element doping and defect engineering), interface structure regulation (electron bridges and crystal facet engineering), and morphology/dimension engineering to optimize the surface reaction. Moreover, the applications of Bi-based S-Scheme heterojunctions in photocatalytic water splitting for hydrogen production, CO2 reduction, pollutant degradation and H2O2 generation are comprehensively summarized. Finally, the current challenges and future perspectives for the development of high-performance Bi-based S-Scheme heterojunction photocatalysts are presented. This review aims to provide profound theoretical insights and strategic frameworks for the rational design of high-efficiency Bi-based S-Scheme photocatalysts.
2026, 45(9): 100972
doi: 10.1016/j.cjsc.2026.100972
摘要:
Metal–ligand coordination complexes serve as versatile platforms for the targeted detection of metal ions. However, the relationship between molecular structure, binding interactions, and sensing performance remains dispersed across different sensing systems. This review provides a structure–function perspective on metal–ligand coordination sensors, highlighting how ligand architecture, donor atom types, coordination geometry, and secondary supramolecular interactions collectively influence metal-ion recognition and signal transduction. Particular attention is given to the interaction between primary coordination bonds and auxiliary forces such as hydrogen bonding, π–π stacking, and electrostatic interactions, which together govern binding affinity, selectivity, and sensing behavior. The review discusses key sensing architectures—including preorganized ligands, multidentate chelating probes, supramolecular cages, coordination polymers, and metal–organic frameworks—and demonstrates how structural design principles yield distinct optical and electrochemical responses, such as photoinduced electron transfer, chelation-enhanced fluorescence, and charge-transfer modulation. By connecting molecular design with sensing mechanisms and analytical results, this review establishes a unified framework for understanding metal–ligand coordination-based sensing systems. Finally, emerging strategies to enhance selectivity, stability, and suitability for real-world applications are discussed, offering guidance for designing the next generation of metal-ion sensors for environmental monitoring, biological analysis, and industrial use.
Metal–ligand coordination complexes serve as versatile platforms for the targeted detection of metal ions. However, the relationship between molecular structure, binding interactions, and sensing performance remains dispersed across different sensing systems. This review provides a structure–function perspective on metal–ligand coordination sensors, highlighting how ligand architecture, donor atom types, coordination geometry, and secondary supramolecular interactions collectively influence metal-ion recognition and signal transduction. Particular attention is given to the interaction between primary coordination bonds and auxiliary forces such as hydrogen bonding, π–π stacking, and electrostatic interactions, which together govern binding affinity, selectivity, and sensing behavior. The review discusses key sensing architectures—including preorganized ligands, multidentate chelating probes, supramolecular cages, coordination polymers, and metal–organic frameworks—and demonstrates how structural design principles yield distinct optical and electrochemical responses, such as photoinduced electron transfer, chelation-enhanced fluorescence, and charge-transfer modulation. By connecting molecular design with sensing mechanisms and analytical results, this review establishes a unified framework for understanding metal–ligand coordination-based sensing systems. Finally, emerging strategies to enhance selectivity, stability, and suitability for real-world applications are discussed, offering guidance for designing the next generation of metal-ion sensors for environmental monitoring, biological analysis, and industrial use.
2026, 45(9): 100973
doi: 10.1016/j.cjsc.2026.100973
摘要:
Photocatalytic overall seawater splitting represents a sustainable route to hydrogen production but is fundamentally limited by chloride-induced catalyst corrosion and competing chlorine evolution reactions. Polymeric photocatalysts are attractive for this process; however, intrinsic chlorine tolerance remains elusive. Here we report that poly (triazine imide) single crystals with exposed {1010} facets enable efficient and stable photocatalytic overall seawater splitting. A surface-bound Cl- layer forms an electrostatic shield that suppresses chloride corrosion, while preferential Na+ adsorption generates a strong interfacial electric field that enhances charge separation and extends carrier lifetimes. Consequently, continuous H₂ and O₂ evolution with a stoichiometric 2:1 ratio and without detectable chlorine by-products is achieved under irradiation in natural seawater. These results reveal an ion–framework cooperative mechanism and establish a feasible design principle for chlorine-tolerant polymeric photocatalysts.
Photocatalytic overall seawater splitting represents a sustainable route to hydrogen production but is fundamentally limited by chloride-induced catalyst corrosion and competing chlorine evolution reactions. Polymeric photocatalysts are attractive for this process; however, intrinsic chlorine tolerance remains elusive. Here we report that poly (triazine imide) single crystals with exposed {1010} facets enable efficient and stable photocatalytic overall seawater splitting. A surface-bound Cl- layer forms an electrostatic shield that suppresses chloride corrosion, while preferential Na+ adsorption generates a strong interfacial electric field that enhances charge separation and extends carrier lifetimes. Consequently, continuous H₂ and O₂ evolution with a stoichiometric 2:1 ratio and without detectable chlorine by-products is achieved under irradiation in natural seawater. These results reveal an ion–framework cooperative mechanism and establish a feasible design principle for chlorine-tolerant polymeric photocatalysts.
2026, 45(9): 100974
doi: 10.1016/j.cjsc.2026.100974
摘要:
In summary, this study reports a novel single-site cooperativity mechanism that enables high-capacity CO capture, representing a paradigm shift by moving beyond conventional dependence on long-range structural phase transitions. Unlike traditional cooperative systems, which incur substantial energy penalties during regeneration, this localized strategy achieves positive cooperativity through tandem spin transition and reversible migratory insertion at isolated Co(II)-methyl sites. This approach effectively resolves the long-standing trade-off between selectivity and regeneration energy. Effective implementation of this strategy requires integrating spin-active sites within a porous framework. However, several practical challenges remain to be addressed before practical application. For instance, the reactive cobalt-methyl bonds exhibit high sensitivity to atmospheric oxygen and moisture, and the approach also demands precise metal-ligand pairing. Despite these limitations, the mechanism of single-site cooperativity holds promise for extension to the capture or activation of other π-acidic gases, such as NO or SO2, through deliberate engineering of the coordination environment.
In summary, this study reports a novel single-site cooperativity mechanism that enables high-capacity CO capture, representing a paradigm shift by moving beyond conventional dependence on long-range structural phase transitions. Unlike traditional cooperative systems, which incur substantial energy penalties during regeneration, this localized strategy achieves positive cooperativity through tandem spin transition and reversible migratory insertion at isolated Co(II)-methyl sites. This approach effectively resolves the long-standing trade-off between selectivity and regeneration energy. Effective implementation of this strategy requires integrating spin-active sites within a porous framework. However, several practical challenges remain to be addressed before practical application. For instance, the reactive cobalt-methyl bonds exhibit high sensitivity to atmospheric oxygen and moisture, and the approach also demands precise metal-ligand pairing. Despite these limitations, the mechanism of single-site cooperativity holds promise for extension to the capture or activation of other π-acidic gases, such as NO or SO2, through deliberate engineering of the coordination environment.
2026, 45(9): 100975
doi: 10.1016/j.cjsc.2026.100975
摘要:
In summary, this work establishes a new paradigm for the precision engineering of 2D mesoporous materials. The interface-confined anisotropic assembly strategy not only overcomes long-standing challenges in structural control but also provides a versatile platform for designing advanced functional materials. By decoupling and independently tuning critical structural parameters, this approach opens new avenues for optimizing performance in a wide range of applications, from catalysis and energy storage to smart diagnostics and next-generation therapeutic platforms.
In summary, this work establishes a new paradigm for the precision engineering of 2D mesoporous materials. The interface-confined anisotropic assembly strategy not only overcomes long-standing challenges in structural control but also provides a versatile platform for designing advanced functional materials. By decoupling and independently tuning critical structural parameters, this approach opens new avenues for optimizing performance in a wide range of applications, from catalysis and energy storage to smart diagnostics and next-generation therapeutic platforms.
2026, 45(9): 100976
doi: 10.1016/j.cjsc.2026.100976
摘要:
Fluorescence lifetime (FL)-based thermometry has been widely applied in diverse technological fields owing to its self-referencing capability, high sensitivity, and reliability. However, conventional FL thermometers generally rely on thermally activated nonradiative relaxation processes, limiting their use for cryogenic sensing below liquid nitrogen temperature (77 K). Herein, we report a new FL thermometric method based on Te4+-doped 0D Cs2ScCl5·H2O crystals, which operates independently of nonradiative relaxation and enables accurate and reliable cryogenic temperature detection down to liquid helium temperature (4 K), achieving a maximum relative sensitivity of 8.5% K–1 at 10 K. Specifically, we demonstrate that the photoluminescence (PL) in Cs2ScCl5·H2O: Te4+ originates from the 3P0,1 → 1S0 transitions of isolated Te4+ centers. This is evidenced by the strong temperature dependence of the dual-band emissions at low temperatures (induced by a dynamic Jahn-Teller effect) and the PL lifetime dictated by the interplay between spin-forbidden and spin−orbital allowed transitions. These findings not only provide fundamental insights into the excited-state dynamics of Te4+ in metal halides, but also establish a general approach for ultralow-temperature FL sensing utilizing main-group s-electron ions.
Fluorescence lifetime (FL)-based thermometry has been widely applied in diverse technological fields owing to its self-referencing capability, high sensitivity, and reliability. However, conventional FL thermometers generally rely on thermally activated nonradiative relaxation processes, limiting their use for cryogenic sensing below liquid nitrogen temperature (77 K). Herein, we report a new FL thermometric method based on Te4+-doped 0D Cs2ScCl5·H2O crystals, which operates independently of nonradiative relaxation and enables accurate and reliable cryogenic temperature detection down to liquid helium temperature (4 K), achieving a maximum relative sensitivity of 8.5% K–1 at 10 K. Specifically, we demonstrate that the photoluminescence (PL) in Cs2ScCl5·H2O: Te4+ originates from the 3P0,1 → 1S0 transitions of isolated Te4+ centers. This is evidenced by the strong temperature dependence of the dual-band emissions at low temperatures (induced by a dynamic Jahn-Teller effect) and the PL lifetime dictated by the interplay between spin-forbidden and spin−orbital allowed transitions. These findings not only provide fundamental insights into the excited-state dynamics of Te4+ in metal halides, but also establish a general approach for ultralow-temperature FL sensing utilizing main-group s-electron ions.
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:
