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Chinese Journal of Structural Chemistry
Chinese Journal of Structural Chemistry
主管 : 中国科学院
刊期 : 月刊主编 : 洪茂椿
语种 : 英文主办 : 中国科学院福建物质结构研究所、中国化学会
ISSN : 0254-5861 CN : 35-1112/TQ展开 >The Chinese Journal of Structural Chemistry, founded in 1982 by Prof. Jiaxi Lu, is an international peer-reviewed journal published in English. It publishes original research works about the structure and property of matter, including but not limited to coordination chemistry, organometallic chemistry, catalysis, energy, nanomaterial, theory/computation, structural characterization, pharmacy and life science. Published monthly by Fujian Institute of Research on the Structure of Matter, CAS, in the form of Articles, Communications, Reviews, Perspectives, and News & Views. - 影响因子: 10.3
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Recent Advances of Cu-Based Materials for Electrochemical Nitrate Reduction to Ammonia
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Transition Metal Boride-Based Materials for Electrocatalytic Water Splitting
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Uncovering the Mechanism for Urea Electrochemical Synthesis by Coupling N2 and CO2 on Mo2C-MXene
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Methods to Make Conductive Covalent Organic Frameworks for Electrocatalytic Applications
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2025, 44(12): 100718
doi: 10.1016/j.cjsc.2025.100718
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2025, 44(12): 100720
doi: 10.1016/j.cjsc.2025.100720
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2025, 44(12): 100721
doi: 10.1016/j.cjsc.2025.100721
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2025, 44(12): 100722
doi: 10.1016/j.cjsc.2025.100722
摘要:
A novel double-stranded trinuclear bis(tridipyrrin) zinc(II) complex, constructed from a linear π-conjugated tridipyrrin ligand, was synthesized and characterized. The complex featuring six directly linked dipyrrin units exhibits a stable double-helical structure with two non-superimposable P and M enantiomers, as confirmed by X-ray crystallography. Chirality was further demonstrated through HPLC separation and mirror-image circular dichroism (CD) spectra. The complex shows strong near-infrared (NIR) absorption and excellent solubility in various solvents, attributed to its sterically hindered structure. Spectroscopic, electrochemical, and theoretical studies revealed its unique electronic properties and redox behavior. This work advances the design of chiral NIR-active metallo-supramolecular systems and highlights potential applications in chiroptical materials.
A novel double-stranded trinuclear bis(tridipyrrin) zinc(II) complex, constructed from a linear π-conjugated tridipyrrin ligand, was synthesized and characterized. The complex featuring six directly linked dipyrrin units exhibits a stable double-helical structure with two non-superimposable P and M enantiomers, as confirmed by X-ray crystallography. Chirality was further demonstrated through HPLC separation and mirror-image circular dichroism (CD) spectra. The complex shows strong near-infrared (NIR) absorption and excellent solubility in various solvents, attributed to its sterically hindered structure. Spectroscopic, electrochemical, and theoretical studies revealed its unique electronic properties and redox behavior. This work advances the design of chiral NIR-active metallo-supramolecular systems and highlights potential applications in chiroptical materials.
2025, 44(12): 100729
doi: 10.1016/j.cjsc.2025.100729
摘要:
The quantitative detection of biological metabolites is a crucial route for early diagnosis of human diseases. Exhaled ammonia (NH3), originating from abnormal metabolism, is normally recognized as the biomarker for liver and kidney lesions. Therefore, developing highly sensitive fluorescent sensing materials is expected to replace the traditional clinical blood tests and facilitate painless diagnosis and telemedicine for patients. However, the weak interaction for ammonia and the small color switching range of fluorescence sensors become the most pressing problem at present. Herein, a porphyrin-based hydrogen-bonded organic framework (HOF-6) with abundant supermolecule interactions in the confined pore space is developed for highly sensitive ammonia detection. The strong interactions between ammonia and the framework greatly promote the electron rearrangement and enhance the intensity of fluorescence, enabling HOF-6 to successfully achieve trace amounts of ammonia sensing with the limit detection of 0.2 ppm. With the ultrahigh selectivity for ammonia, HOF-6 can accurately determine the amount of ammonia in breath of patients, and the test results are highly consistent with blood ammonia levels. The tailor-made multiple interactions in the confined pore space provide an effective approach for highly sensitive ammonia detection, as well as brings good news to liver and kidney patients for non-invasive diagnosis and real-time health monitoring.
The quantitative detection of biological metabolites is a crucial route for early diagnosis of human diseases. Exhaled ammonia (NH3), originating from abnormal metabolism, is normally recognized as the biomarker for liver and kidney lesions. Therefore, developing highly sensitive fluorescent sensing materials is expected to replace the traditional clinical blood tests and facilitate painless diagnosis and telemedicine for patients. However, the weak interaction for ammonia and the small color switching range of fluorescence sensors become the most pressing problem at present. Herein, a porphyrin-based hydrogen-bonded organic framework (HOF-6) with abundant supermolecule interactions in the confined pore space is developed for highly sensitive ammonia detection. The strong interactions between ammonia and the framework greatly promote the electron rearrangement and enhance the intensity of fluorescence, enabling HOF-6 to successfully achieve trace amounts of ammonia sensing with the limit detection of 0.2 ppm. With the ultrahigh selectivity for ammonia, HOF-6 can accurately determine the amount of ammonia in breath of patients, and the test results are highly consistent with blood ammonia levels. The tailor-made multiple interactions in the confined pore space provide an effective approach for highly sensitive ammonia detection, as well as brings good news to liver and kidney patients for non-invasive diagnosis and real-time health monitoring.
2025, 44(12): 100734
doi: 10.1016/j.cjsc.2025.100734
摘要:
Stimuli-responsive luminescent switching materials with multifunctional properties are highly essential for advanced photonic applications, yet achieving such capabilities in halide perovskites continues to pose a significant challenge. In this work, we explore a new water-stimuli-responsive zero-dimensional (0D) Sb-based halide of [PhPz]2SbCl7·2H2O (PhPz = phenylpiperazine), which consists of isolated [SbCl6]3− octahedra in [PhPz]2+ cationic matrix with guest H2O molecules. Under UV excitation, [PhPz]2SbCl7·2H2O emits intense broadband red light with maximum emission at 645 nm, and combined optical characterization and theoretical calculations confirm that this luminescence originates from self-trapped excitons (STEs). Interestingly, the free water molecules can reversibly leave and entry the crystal lattice during heating-cooling cycles accompanied by the formation of dehydrated phase, which displays strong yellow emission with maximum peak at 580 nm. Therefore, reversible luminescent switching between red and yellow emission is achieved through controllable removal and adsorption process of guest H2O. By virtue of this reversible thermochromic switching, this halide can be used to detect the trace amount of water in various organic solvents and humidity of moist air. In addition, such switchable dual emission further realizes application in anti-counterfeiting and information encryption-decryption. This work deepens the understanding of structure-property relationships and expands the application range of 0D metal halides.
Stimuli-responsive luminescent switching materials with multifunctional properties are highly essential for advanced photonic applications, yet achieving such capabilities in halide perovskites continues to pose a significant challenge. In this work, we explore a new water-stimuli-responsive zero-dimensional (0D) Sb-based halide of [PhPz]2SbCl7·2H2O (PhPz = phenylpiperazine), which consists of isolated [SbCl6]3− octahedra in [PhPz]2+ cationic matrix with guest H2O molecules. Under UV excitation, [PhPz]2SbCl7·2H2O emits intense broadband red light with maximum emission at 645 nm, and combined optical characterization and theoretical calculations confirm that this luminescence originates from self-trapped excitons (STEs). Interestingly, the free water molecules can reversibly leave and entry the crystal lattice during heating-cooling cycles accompanied by the formation of dehydrated phase, which displays strong yellow emission with maximum peak at 580 nm. Therefore, reversible luminescent switching between red and yellow emission is achieved through controllable removal and adsorption process of guest H2O. By virtue of this reversible thermochromic switching, this halide can be used to detect the trace amount of water in various organic solvents and humidity of moist air. In addition, such switchable dual emission further realizes application in anti-counterfeiting and information encryption-decryption. This work deepens the understanding of structure-property relationships and expands the application range of 0D metal halides.
2025, 44(12): 100744
doi: 10.1016/j.cjsc.2025.100744
摘要:
Separation of ternary C4 olefins (n-butene, iso-butene and 1,3-butadiene) is very challenging but crucial in the petrol-chemical industry due to their similar molecular sizes and properties. Herein, to optimize the separation efficiency for separation of C4 olefins, a new Hofmann-type MOF, [Ni(piz)Ni(CN)4] (piz = piperazine)—isostructural to the typical one [Ni(pyz)Ni(CN)4] (pyz = pyrazine), has been synthesized by a facile method from aqueous solution. The pore size reduction of [Ni(piz)Ni(CN)4] (3.62 Å, in contrast to 3.85 Å in [Ni(pyz)Ni(CN)4]) results in negligible iso-butene (i-C4H8) uptake (from 2.92 to 0.04 mmol g−1) whereas retaining significant uptake for 1,3-butadiene (1,3-C4H6, 1.96 mmol g−1) and n-butene (n-C4H8, 1.47 mmol g−1), showing much higher uptake ratios of 1,3-C4H6/i-C4H8 (47) and n-C4H8/i-C4H8 (35) that outperform most of the benchmark porous materials for separating C4 olefins. Breakthrough experiments demonstrate successful separation of high-purity (99.9999%) i-C4H8 and 1,3-C4H6 from equimolar 1,3-C4H6/i-C4H8, n-C4H8/i-C4H8 and 1,3-C4H6/n-C4H8/i-C4H8 mixtures.
Separation of ternary C4 olefins (n-butene, iso-butene and 1,3-butadiene) is very challenging but crucial in the petrol-chemical industry due to their similar molecular sizes and properties. Herein, to optimize the separation efficiency for separation of C4 olefins, a new Hofmann-type MOF, [Ni(piz)Ni(CN)4] (piz = piperazine)—isostructural to the typical one [Ni(pyz)Ni(CN)4] (pyz = pyrazine), has been synthesized by a facile method from aqueous solution. The pore size reduction of [Ni(piz)Ni(CN)4] (3.62 Å, in contrast to 3.85 Å in [Ni(pyz)Ni(CN)4]) results in negligible iso-butene (i-C4H8) uptake (from 2.92 to 0.04 mmol g−1) whereas retaining significant uptake for 1,3-butadiene (1,3-C4H6, 1.96 mmol g−1) and n-butene (n-C4H8, 1.47 mmol g−1), showing much higher uptake ratios of 1,3-C4H6/i-C4H8 (47) and n-C4H8/i-C4H8 (35) that outperform most of the benchmark porous materials for separating C4 olefins. Breakthrough experiments demonstrate successful separation of high-purity (99.9999%) i-C4H8 and 1,3-C4H6 from equimolar 1,3-C4H6/i-C4H8, n-C4H8/i-C4H8 and 1,3-C4H6/n-C4H8/i-C4H8 mixtures.
High-entropy PdPtRhFeCuMo metallene nanoribbons for electro-reforming PET plastic into glycolic acid
2025, 44(12): 100745
doi: 10.1016/j.cjsc.2025.100745
摘要:
The electrochemical upgrading of polyethylene terephthalate (PET) plastics represents a highly promising strategy for achieving high-value utilization of waste resources, and its efficiency is highly related to identify active electrocatalysts for PET-derived ethylene glycol oxidation reaction (EGOR). In this work, atomically thin high-entropy PdPtRhFeCuMo metallene nanoribbons (PdPtRhFeCuMo HMRs) have been synthesized and served as high-performance catalysts for electro-reforming PET plastic, which possess a high current density of 180 mA cm−2 at a low potential of 0.9 V for EGOR, with excellent Faraday efficiency (FE) of 96.81% for highly efficient and selective conversion of EG into high-value-added glycolic acid (GA). Experimental and theoretical results reveal that the multi-metallic synergistic effect of PdPtRhFeCuMo HMRs effectively modulates adsorption behavior of intermediates and reduce the EGOR energy barrier, thus promoting the selective EG-to-GA conversion. This study proposes the reasonable design of high-entropy metallene nanoribbons for the electrochemical upgrading of PET plastics to high-value C2 products.
The electrochemical upgrading of polyethylene terephthalate (PET) plastics represents a highly promising strategy for achieving high-value utilization of waste resources, and its efficiency is highly related to identify active electrocatalysts for PET-derived ethylene glycol oxidation reaction (EGOR). In this work, atomically thin high-entropy PdPtRhFeCuMo metallene nanoribbons (PdPtRhFeCuMo HMRs) have been synthesized and served as high-performance catalysts for electro-reforming PET plastic, which possess a high current density of 180 mA cm−2 at a low potential of 0.9 V for EGOR, with excellent Faraday efficiency (FE) of 96.81% for highly efficient and selective conversion of EG into high-value-added glycolic acid (GA). Experimental and theoretical results reveal that the multi-metallic synergistic effect of PdPtRhFeCuMo HMRs effectively modulates adsorption behavior of intermediates and reduce the EGOR energy barrier, thus promoting the selective EG-to-GA conversion. This study proposes the reasonable design of high-entropy metallene nanoribbons for the electrochemical upgrading of PET plastics to high-value C2 products.
2025, 44(12): 100747
doi: 10.1016/j.cjsc.2025.100747
摘要:
The development of robust, cost-effective and high-performance electrocatalysts is essential for industrial-scale green hydrogen production under high-current operating conditions (> 500 mA/cm2) to ensure both high output and economic efficiency. Herein, a binder-free bimetallic vanadium-nickel-boride-phosphide (VNiBP) spherical electrocatalyst (SE) is synthesized via a simple hydrothermal method, followed by post-annealing. The VNiBP catalyst exhibits low overpotentials of 91 mV for the hydrogen evolution reaction (HER) and 270 mV for the oxygen evolution reaction (OER) at 100 mA/cm2 in 1 M KOH with stable operation over 150 h, surpassing most of the state-of-the-art electrocatalysts. The bifunctional VNiBP (–, +) exhibits a low turnover voltage of 1.57 V at 100 mA/cm2 and outperforms the Pt/C||RuO2 benchmark system up to 2000 mA/cm2 high-current density. The Pt/C||VNiBP hybrid configuration shows a low 2-E cell voltage of 2.55 V at 2000 mA/cm2 under industrially relevant conditions (6 M KOH, 60 °C). Notably, the VNiBP demonstrates exceptional long-term stability, maintaining continuous operation for over 6 days in both 1 M and 6 M KOH at 1000 mA/cm2. The outstanding overall water splitting (OWS) performance can be attributed to the synergistic combination of rapid intermediate formation, optimized adsorption/desorption kinetics, high electrochemical surface area and low charge transfer resistance offered by favorable composition and spherical morphology.
The development of robust, cost-effective and high-performance electrocatalysts is essential for industrial-scale green hydrogen production under high-current operating conditions (> 500 mA/cm2) to ensure both high output and economic efficiency. Herein, a binder-free bimetallic vanadium-nickel-boride-phosphide (VNiBP) spherical electrocatalyst (SE) is synthesized via a simple hydrothermal method, followed by post-annealing. The VNiBP catalyst exhibits low overpotentials of 91 mV for the hydrogen evolution reaction (HER) and 270 mV for the oxygen evolution reaction (OER) at 100 mA/cm2 in 1 M KOH with stable operation over 150 h, surpassing most of the state-of-the-art electrocatalysts. The bifunctional VNiBP (–, +) exhibits a low turnover voltage of 1.57 V at 100 mA/cm2 and outperforms the Pt/C||RuO2 benchmark system up to 2000 mA/cm2 high-current density. The Pt/C||VNiBP hybrid configuration shows a low 2-E cell voltage of 2.55 V at 2000 mA/cm2 under industrially relevant conditions (6 M KOH, 60 °C). Notably, the VNiBP demonstrates exceptional long-term stability, maintaining continuous operation for over 6 days in both 1 M and 6 M KOH at 1000 mA/cm2. The outstanding overall water splitting (OWS) performance can be attributed to the synergistic combination of rapid intermediate formation, optimized adsorption/desorption kinetics, high electrochemical surface area and low charge transfer resistance offered by favorable composition and spherical morphology.
2025, 44(12): 100749
doi: 10.1016/j.cjsc.2025.100749
摘要:
Metal-organic frameworks (MOFs) hold great promise for wound healing applications due to their high surface area, tunable pore structures, and tailored functionalities. However, a significant challenge lies in transforming pristine MOFs powders into ultrathin and flexible dressings that are compatible with soft biological systems. The current limitations of MOFs in practical usability and versatility hinder their integration into advanced wound dressings. Herein, we integrate MOF (ZIF-8) with an ultrathin cellulose membrane to form MOF-based matrix membranes (MMMs) that exhibit high transparency, exceptional mechanical stability, and satisfactory antimicrobial functionality for effective bacterial wound healing. The resulting MMMs can be fabricated into multifunctional dressings of various shapes and sizes, optimized for tissue applications, while maintaining excellent water-vapor permeability and patient compliance. Both in vitro and in vivo experiments demonstrated that the MMMs exhibit outstanding biocompatibility, antibacterial activity, and antioxidant properties, significantly accelerating the healing of bacterial-infected wounds. This work presents a transformative approach to wound care, establishing a foundation for next-generation dressings that combine the multifunctionality of MOFs with the mechanical and biological compatibility required for clinical applications.
Metal-organic frameworks (MOFs) hold great promise for wound healing applications due to their high surface area, tunable pore structures, and tailored functionalities. However, a significant challenge lies in transforming pristine MOFs powders into ultrathin and flexible dressings that are compatible with soft biological systems. The current limitations of MOFs in practical usability and versatility hinder their integration into advanced wound dressings. Herein, we integrate MOF (ZIF-8) with an ultrathin cellulose membrane to form MOF-based matrix membranes (MMMs) that exhibit high transparency, exceptional mechanical stability, and satisfactory antimicrobial functionality for effective bacterial wound healing. The resulting MMMs can be fabricated into multifunctional dressings of various shapes and sizes, optimized for tissue applications, while maintaining excellent water-vapor permeability and patient compliance. Both in vitro and in vivo experiments demonstrated that the MMMs exhibit outstanding biocompatibility, antibacterial activity, and antioxidant properties, significantly accelerating the healing of bacterial-infected wounds. This work presents a transformative approach to wound care, establishing a foundation for next-generation dressings that combine the multifunctionality of MOFs with the mechanical and biological compatibility required for clinical applications.
2025, 44(12): 100751
doi: 10.1016/j.cjsc.2025.100751
摘要:
Since their discovery by Hugo Schiff in 1864, Schiff bases and their metal complexes have gained recognition for their catalytic and biological properties. These compounds exhibit diverse functionalities, serving as catalysts in synthetic processes and displaying notable biological activities such as antifungal, antibacterial, anti-malarial, and antiviral effects. In various applications, Schiff bases serve as versatile tools, particularly in sensing applications. Through coordination with various metal ions, they form stable complexes. They are utilized as fluorescent turn-on/turn-off sensors for detecting a wide range of analytes. The coordination ability makes them valuable as chemosensor for detecting environmentally and biologically important analytes. This review provides a thorough overview of Schiff base chemosensors designed for the detection of environmental and biological significance including metal cations, anions, and neutral analytes. It is structured into four focused sections. The first section addresses the use of Schiff base chemosensor for the selective detection of various metal cations, including Ca2+, Al3+, Cr3+, Mn2+, Fe3+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, and Pb2+; The second section examines the application of fluorescent Schiff base sensors in detecting diverse anions such as F−, CN−, I−, and HSO4−; The third section investigates the use of Schiff base fluorescent probes for accurate pH detection and determination; and the fourth section explores the utilization of Schiff base sensors for detecting environmentally and biologically important neutral analytes, including insecticides, pesticides, and others. Additionally, the Schiff base chemosensors for metal cations and anions section are concluded with a table, summarizing the reviewed fluorescent Schiff base sensors for enhanced clarity.
Since their discovery by Hugo Schiff in 1864, Schiff bases and their metal complexes have gained recognition for their catalytic and biological properties. These compounds exhibit diverse functionalities, serving as catalysts in synthetic processes and displaying notable biological activities such as antifungal, antibacterial, anti-malarial, and antiviral effects. In various applications, Schiff bases serve as versatile tools, particularly in sensing applications. Through coordination with various metal ions, they form stable complexes. They are utilized as fluorescent turn-on/turn-off sensors for detecting a wide range of analytes. The coordination ability makes them valuable as chemosensor for detecting environmentally and biologically important analytes. This review provides a thorough overview of Schiff base chemosensors designed for the detection of environmental and biological significance including metal cations, anions, and neutral analytes. It is structured into four focused sections. The first section addresses the use of Schiff base chemosensor for the selective detection of various metal cations, including Ca2+, Al3+, Cr3+, Mn2+, Fe3+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, and Pb2+; The second section examines the application of fluorescent Schiff base sensors in detecting diverse anions such as F−, CN−, I−, and HSO4−; The third section investigates the use of Schiff base fluorescent probes for accurate pH detection and determination; and the fourth section explores the utilization of Schiff base sensors for detecting environmentally and biologically important neutral analytes, including insecticides, pesticides, and others. Additionally, the Schiff base chemosensors for metal cations and anions section are concluded with a table, summarizing the reviewed fluorescent Schiff base sensors for enhanced clarity.
2025, 44(12): 100752
doi: 10.1016/j.cjsc.2025.100752
摘要:
Plastics, renowned for their flexibility, stability, and cost-effectiveness, have become indispensable materials in modern life. However, their extensive use has led to a global environmental and health crisis. Especially, plastic products infiltrate agroecosystems through atmospheric deposition, irrigation water, soil contamination, and the degradation of plastic mulch films, posing significant risks to vegetable quality and safety. Traditional disposal methods, such as incineration and landfilling, are energy-intensive and ecologically harmful, necessitating the development and application of innovative technologies for plastic removal. This paper reviews representative advanced (micro)plastic removal technologies, with a particular focus on frameworks-containing photocatalysis as a promising green method for processing (micro)plastics. First, we analyze and compare traditional, then discuss emerging removal technologies. Next, we elaborate on the principles of photocatalytic degradation of plastic products, discuss key influencing factors, and classify various photocatalysts. Additionally, we highlight the limitations of conventional photocatalysts, such as TiO2 and ZnO, and emphasize the advantages of framework materials (e.g., MOFs, COFs, ZIFs) in photocatalytic degradation, including their structural tunability and development potential. Finally, based on the current progress and applications of framework photocatalysts, we identify existing limitations and propose future research directions. This review provides a theoretical foundation and innovative technological insights to address the global challenge of plastic pollution.
Plastics, renowned for their flexibility, stability, and cost-effectiveness, have become indispensable materials in modern life. However, their extensive use has led to a global environmental and health crisis. Especially, plastic products infiltrate agroecosystems through atmospheric deposition, irrigation water, soil contamination, and the degradation of plastic mulch films, posing significant risks to vegetable quality and safety. Traditional disposal methods, such as incineration and landfilling, are energy-intensive and ecologically harmful, necessitating the development and application of innovative technologies for plastic removal. This paper reviews representative advanced (micro)plastic removal technologies, with a particular focus on frameworks-containing photocatalysis as a promising green method for processing (micro)plastics. First, we analyze and compare traditional, then discuss emerging removal technologies. Next, we elaborate on the principles of photocatalytic degradation of plastic products, discuss key influencing factors, and classify various photocatalysts. Additionally, we highlight the limitations of conventional photocatalysts, such as TiO2 and ZnO, and emphasize the advantages of framework materials (e.g., MOFs, COFs, ZIFs) in photocatalytic degradation, including their structural tunability and development potential. Finally, based on the current progress and applications of framework photocatalysts, we identify existing limitations and propose future research directions. This review provides a theoretical foundation and innovative technological insights to address the global challenge of plastic pollution.
2025, 44(12): 100753
doi: 10.1016/j.cjsc.2025.100753
摘要:
Photochromic materials attract significant attention for their applications in anticounterfeiting devices, optical switches and molecular sensors. However, the influence of solvent molecules, particularly coordinated solvents, on electron transfer (ET) photochromic systems remains poorly understood. In this study, we synthesized a series of isostructural metal-organic complexes (MOCs), [Mn(ADC)(L)]n (ADC = 9,10-anthracenedicarboxylic acid, L = DMF for 1, DMA for 2, MEA for 3, and DMSO for 4) to investigate the solvent-chromic behavior. All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature. It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate. Among the compounds studied, compound 1 exhibits the fastest response, while compound 3 shows the slowest. This variation in rate correlates with differences in the optimal ET path length within their structures. Specifically, solvent molecules regulate the C–H···π interaction distance through their steric hindrance and electronic properties. Shorter C–H···π paths facilitate more efficient ET upon photoexcitation, thus leading to faster photochromic response rates. Furthermore, illumination actuates magnetic couplings between photogenerated radicals and Mn2+ centers, resulting in a significant increase in room-temperature magnetization, demonstrating a photomagnetic response. This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior, providing new insights for designing advanced photoactive materials.
Photochromic materials attract significant attention for their applications in anticounterfeiting devices, optical switches and molecular sensors. However, the influence of solvent molecules, particularly coordinated solvents, on electron transfer (ET) photochromic systems remains poorly understood. In this study, we synthesized a series of isostructural metal-organic complexes (MOCs), [Mn(ADC)(L)]n (ADC = 9,10-anthracenedicarboxylic acid, L = DMF for 1, DMA for 2, MEA for 3, and DMSO for 4) to investigate the solvent-chromic behavior. All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature. It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate. Among the compounds studied, compound 1 exhibits the fastest response, while compound 3 shows the slowest. This variation in rate correlates with differences in the optimal ET path length within their structures. Specifically, solvent molecules regulate the C–H···π interaction distance through their steric hindrance and electronic properties. Shorter C–H···π paths facilitate more efficient ET upon photoexcitation, thus leading to faster photochromic response rates. Furthermore, illumination actuates magnetic couplings between photogenerated radicals and Mn2+ centers, resulting in a significant increase in room-temperature magnetization, demonstrating a photomagnetic response. This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior, providing new insights for designing advanced photoactive materials.
2025, 44(12): 100756
doi: 10.1016/j.cjsc.2025.100756
摘要:
Perylene diimide (PDI) derivatives have emerged as a class of important organic fluorescent materials owing to their high extinction coefficient, excellent thermal and photostability, and versatile structural tunability. However, due to its intrinsic rigid planar structure, π-π stacking is easy to occur, resulting in aggregation-caused quenching (ACQ). In recent years, extensive efforts have been devoted to overcome this challenge and enhance the fluorescence performance of PDIs. This review systematically summarizes representative strategies from three major perspectives: (i) Rational molecular design, including the introduction of bulky aromatic substituents, dendritic or polyhedral oligomeric silsesquioxane (POSS) units to provide steric hindrance, as well as the activation of aggregation-induced emission (AIE); (ii) Polymer-based regulation strategies, including physical blending with polymer hosts and covalent integration into polymer backbones, which provide spatial isolation and structural robustness; and (iii) Supramolecular assembly, where host-guest inclusion and self-assembly pathways precisely tune intermolecular packing and excitonic coupling. These strategies have enabled significant improvements in fluorescence quantum yield (FLQY) across solution, aggregate, and solid states. Furthermore, highly emissive perylene diimide (PDI) derivatives have demonstrated broad applicability in biomedicine, sensing and anti-counterfeiting, and optoelectronic devices such as organic light-emitting diodes (OLEDs). This review highlights the fundamental design principles, performance optimization strategies, and emerging application frontiers of PDI-based luminescent materials, providing guidance for their further development toward multifunctional and sustainable optoelectronic technologies.
Perylene diimide (PDI) derivatives have emerged as a class of important organic fluorescent materials owing to their high extinction coefficient, excellent thermal and photostability, and versatile structural tunability. However, due to its intrinsic rigid planar structure, π-π stacking is easy to occur, resulting in aggregation-caused quenching (ACQ). In recent years, extensive efforts have been devoted to overcome this challenge and enhance the fluorescence performance of PDIs. This review systematically summarizes representative strategies from three major perspectives: (i) Rational molecular design, including the introduction of bulky aromatic substituents, dendritic or polyhedral oligomeric silsesquioxane (POSS) units to provide steric hindrance, as well as the activation of aggregation-induced emission (AIE); (ii) Polymer-based regulation strategies, including physical blending with polymer hosts and covalent integration into polymer backbones, which provide spatial isolation and structural robustness; and (iii) Supramolecular assembly, where host-guest inclusion and self-assembly pathways precisely tune intermolecular packing and excitonic coupling. These strategies have enabled significant improvements in fluorescence quantum yield (FLQY) across solution, aggregate, and solid states. Furthermore, highly emissive perylene diimide (PDI) derivatives have demonstrated broad applicability in biomedicine, sensing and anti-counterfeiting, and optoelectronic devices such as organic light-emitting diodes (OLEDs). This review highlights the fundamental design principles, performance optimization strategies, and emerging application frontiers of PDI-based luminescent materials, providing guidance for their further development toward multifunctional and sustainable optoelectronic technologies.
2025, 44(12): 100757
doi: 10.1016/j.cjsc.2025.100757
摘要:
Diamond-like AgGaS2 (DL AGS), as the typical infrared nonlinear optical (IR NLO) material, has suffered from its intrinsic drawbacks like narrow band gap (Eg) and low laser-induced damage threshold (LIDT). In this work, by first introducing [NaS8] polyhedral unit into the A2IQVI-Ag2QVI-C2IIIQ3VI system, a new Ag-based sulfide NaAg3Ga8S14 with diamond-like framework (DLF) has been successfully synthesized via a high-temperature solid-state method in experiment. The compound shows a wide Eg (∼3.0 eV), high LIDT (3.0 × AGS) and moderate phase-matching NLO response (∼0.7 × AGS), effectively balancing the Eg (≥ 3.0 eV) and NLO response (≥ 0.5 × AGS), demonstrating its promise for IR NLO applications. Theoretical calculations elucidate the orbital hybridization between Na 3s, Ag 4d5s and S 3p enhances Eg, and the aligned NLO-active units ([AgS4] and [GaS4]) induce moderate NLO response in the compound. These findings not only expand the chemical and structural diversities of Ag-based chalcogenides, but also provide effective strategies for designing DLF functional materials derived from diamond-like structures.
Diamond-like AgGaS2 (DL AGS), as the typical infrared nonlinear optical (IR NLO) material, has suffered from its intrinsic drawbacks like narrow band gap (Eg) and low laser-induced damage threshold (LIDT). In this work, by first introducing [NaS8] polyhedral unit into the A2IQVI-Ag2QVI-C2IIIQ3VI system, a new Ag-based sulfide NaAg3Ga8S14 with diamond-like framework (DLF) has been successfully synthesized via a high-temperature solid-state method in experiment. The compound shows a wide Eg (∼3.0 eV), high LIDT (3.0 × AGS) and moderate phase-matching NLO response (∼0.7 × AGS), effectively balancing the Eg (≥ 3.0 eV) and NLO response (≥ 0.5 × AGS), demonstrating its promise for IR NLO applications. Theoretical calculations elucidate the orbital hybridization between Na 3s, Ag 4d5s and S 3p enhances Eg, and the aligned NLO-active units ([AgS4] and [GaS4]) induce moderate NLO response in the compound. These findings not only expand the chemical and structural diversities of Ag-based chalcogenides, but also provide effective strategies for designing DLF functional materials derived from diamond-like structures.
2025, 44(12): 100758
doi: 10.1016/j.cjsc.2025.100758
摘要:
Metal-supported solid oxide fuel cells (MS-SOFCs) have recently gained significant attention as an advanced SOFC technology, owing to their excellent mechanical robustness, ease of handling, and high manufacturability. The use of metal substrates enables improved durability under thermal and redox cycling, and allows for thinner electrolyte layers, contributing to enhanced performance. However, their fabrication typically requires high-temperature sintering to ensure adequate material properties and adhesion, as most SOFC components are ceramic. These high-temperature processes can lead to undesirable effects, including metal support oxidation, chemical side reactions, and accelerated particle growth, which degrade cell performance. This study introduces an ultra-fast sintering approach for MS-SOFC fabrication by directly integrating stainless-steel metal supports with nickel-yttria-stabilized zirconia (Ni-YSZ) composite anode active layers. The application of flash light sintering—an innovative ultra-fast technique—effectively suppressed Ni catalyst particle growth, expanding the electrochemical reaction area while minimizing material diffusion between the metal support and anode layer. As a result, the fabricated cells achieved a stable open-circuit voltage (OCV) exceeding 1 V at 650 °C and a peak power density of 412 mW/cm2, representing an approximately 426.3% performance improvement over conventionally sintered cells. This research presents a transformative strategy for SOFC manufacturing, addressing the challenges of conventional long-duration heat treatments and demonstrating significant potential for advancing energy conversion technologies.
Metal-supported solid oxide fuel cells (MS-SOFCs) have recently gained significant attention as an advanced SOFC technology, owing to their excellent mechanical robustness, ease of handling, and high manufacturability. The use of metal substrates enables improved durability under thermal and redox cycling, and allows for thinner electrolyte layers, contributing to enhanced performance. However, their fabrication typically requires high-temperature sintering to ensure adequate material properties and adhesion, as most SOFC components are ceramic. These high-temperature processes can lead to undesirable effects, including metal support oxidation, chemical side reactions, and accelerated particle growth, which degrade cell performance. This study introduces an ultra-fast sintering approach for MS-SOFC fabrication by directly integrating stainless-steel metal supports with nickel-yttria-stabilized zirconia (Ni-YSZ) composite anode active layers. The application of flash light sintering—an innovative ultra-fast technique—effectively suppressed Ni catalyst particle growth, expanding the electrochemical reaction area while minimizing material diffusion between the metal support and anode layer. As a result, the fabricated cells achieved a stable open-circuit voltage (OCV) exceeding 1 V at 650 °C and a peak power density of 412 mW/cm2, representing an approximately 426.3% performance improvement over conventionally sintered cells. This research presents a transformative strategy for SOFC manufacturing, addressing the challenges of conventional long-duration heat treatments and demonstrating significant potential for advancing energy conversion technologies.
2025, 44(12): 100759
doi: 10.1016/j.cjsc.2025.100759
摘要:
Chiral metal-organic clusters (MOCs) integrating lanthanide ions (Ln3+) and organic luminophores present a promising platform for modulating circularly polarized luminescence (CPL). However, achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge. Herein, two enantiomeric pairs of heterometallic Eu-Sn oxo clusters, designated as Sn2EuL2-R/S and Sn2EuL4-R/S, were strategically synthesized using axially chiral binaphthol-phosphonate ligands. These hybrid clusters exhibit dual emission, characterized by a broad ligand-derived fluorescence band superimposed with sharp, characteristic Eu3+ f-f transitions, which enables excitation-dependent luminescence color tuning. Their emission profiles and quantum yields were found to be exquisitely adjusted by the distinct coordination environments of Sn4+ centers. Notably, Sn2EuL2-R/S demonstrates CPL activity in both the near-UV (|glum| = 1.7 × 10-3) and visible (|glum| = 3.1 × 10-2) regions. This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.
Chiral metal-organic clusters (MOCs) integrating lanthanide ions (Ln3+) and organic luminophores present a promising platform for modulating circularly polarized luminescence (CPL). However, achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge. Herein, two enantiomeric pairs of heterometallic Eu-Sn oxo clusters, designated as Sn2EuL2-R/S and Sn2EuL4-R/S, were strategically synthesized using axially chiral binaphthol-phosphonate ligands. These hybrid clusters exhibit dual emission, characterized by a broad ligand-derived fluorescence band superimposed with sharp, characteristic Eu3+ f-f transitions, which enables excitation-dependent luminescence color tuning. Their emission profiles and quantum yields were found to be exquisitely adjusted by the distinct coordination environments of Sn4+ centers. Notably, Sn2EuL2-R/S demonstrates CPL activity in both the near-UV (|glum| = 1.7 × 10-3) and visible (|glum| = 3.1 × 10-2) regions. This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.
2025, 44(8): 100625
doi: 10.1016/j.cjsc.2025.100625
摘要:
Metal-organic frameworks (MOFs) with new topologies and enhanced properties can be obtained by connecting metal-organic layers (MOLs) using multifunctional linkers. However, new topologies constructed by this method using linear-shaped ligands have not yet been explored. Herein, we present the design of NUT-123 by incorporating a near-linear perylene diimide (PDI) derivate, PDI–CH3–COOH, into the preselected zirconium-based MOLs. 3D electron diffraction confirms the successful construction of a novel topology in NUT-123. Furthermore, the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI–CH3–COOH. NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility, achieving 100% conversion of various organic sulfides. Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer. This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.
Metal-organic frameworks (MOFs) with new topologies and enhanced properties can be obtained by connecting metal-organic layers (MOLs) using multifunctional linkers. However, new topologies constructed by this method using linear-shaped ligands have not yet been explored. Herein, we present the design of NUT-123 by incorporating a near-linear perylene diimide (PDI) derivate, PDI–CH3–COOH, into the preselected zirconium-based MOLs. 3D electron diffraction confirms the successful construction of a novel topology in NUT-123. Furthermore, the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI–CH3–COOH. NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility, achieving 100% conversion of various organic sulfides. Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer. This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.
2025, 44(8): 100626
doi: 10.1016/j.cjsc.2025.100626
摘要:
Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes. The method of metal coordination has emerged as a robust methodology for chirality induction in many systems. In this work, we engineered two rigid and flexible chiral organic ligands (L1 and L2) by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties. They demonstrate versatile coordination capabilities toward both 3d- and 4f-block metals, enabling modulation of luminescent characteristics with blue, green and red emissions. Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L1/L2 with Zn2+, Eu3+, and Tb3+. The coordination processes effectively rigidify molecular conformations, leading to an enhanced CPL performance. Particularly, the Tb-L2 complex displays superior lanthanide-centered emission with a fluorescence quantum yield of ∼55% and an emission dissymmetry factor glum = 5.5 × 10−3. By engineering the substitution on pillar[5]arene scaffolds, we have established a metal-coordination platform with CPL characteristics, which paves the way in the design of new metal-based luminescent materials.
Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes. The method of metal coordination has emerged as a robust methodology for chirality induction in many systems. In this work, we engineered two rigid and flexible chiral organic ligands (L1 and L2) by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties. They demonstrate versatile coordination capabilities toward both 3d- and 4f-block metals, enabling modulation of luminescent characteristics with blue, green and red emissions. Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L1/L2 with Zn2+, Eu3+, and Tb3+. The coordination processes effectively rigidify molecular conformations, leading to an enhanced CPL performance. Particularly, the Tb-L2 complex displays superior lanthanide-centered emission with a fluorescence quantum yield of ∼55% and an emission dissymmetry factor glum = 5.5 × 10−3. By engineering the substitution on pillar[5]arene scaffolds, we have established a metal-coordination platform with CPL characteristics, which paves the way in the design of new metal-based luminescent materials.
2025, 44(8): 100627
doi: 10.1016/j.cjsc.2025.100627
摘要:
Ethylene glycol oxidation reaction (EGOR) is important to address the environmental issues caused by the increased production of polyethylene terephthalate (PET). Metal organic frameworks (MOFs) with superior stability, high specific surface area and excellent catalytic performance can convert PET into valuable products through EGOR and hydrogen evolution reaction (HER). Herein, a microbial template strategy was adopted to prepare carbon sphere-supported orthogonal nanosheet bimetallic MOF catalysts. The prepared catalyst needs only 1.42 V, 307 mV, and 1.83 V at a current density of 100 mA cm−2 for EGOR, HER, and EGOR//HER, respectively. More importantly, it can stably perform for at least 160 h at a current density of 500 mA cm−2. The high specific surface area of bimetallic MOF and the synergistic effect of yeast carbon shell increase the contact area between the intrinsic active sites and ∗OH and EG, thus improving the EGOR and HER catalytic activity and stability. This work provides a novel strategy to construct bimetallic orthogonal electrocatalysts with efficient HER//EGOR performance, which is of great significance for achieving sustainable energy conversion and environmental purification.
Ethylene glycol oxidation reaction (EGOR) is important to address the environmental issues caused by the increased production of polyethylene terephthalate (PET). Metal organic frameworks (MOFs) with superior stability, high specific surface area and excellent catalytic performance can convert PET into valuable products through EGOR and hydrogen evolution reaction (HER). Herein, a microbial template strategy was adopted to prepare carbon sphere-supported orthogonal nanosheet bimetallic MOF catalysts. The prepared catalyst needs only 1.42 V, 307 mV, and 1.83 V at a current density of 100 mA cm−2 for EGOR, HER, and EGOR//HER, respectively. More importantly, it can stably perform for at least 160 h at a current density of 500 mA cm−2. The high specific surface area of bimetallic MOF and the synergistic effect of yeast carbon shell increase the contact area between the intrinsic active sites and ∗OH and EG, thus improving the EGOR and HER catalytic activity and stability. This work provides a novel strategy to construct bimetallic orthogonal electrocatalysts with efficient HER//EGOR performance, which is of great significance for achieving sustainable energy conversion and environmental purification.
2025, 44(8): 100628
doi: 10.1016/j.cjsc.2025.100628
摘要:
Wearable sensors represent a promising technology to monitor human health and movement, however, it is pivotal and challenging to tailor-make highly conductive hydrogels to achieve high sensitivity and environmental weatherability for application at extreme temperature conditions. Herein, the dual-conductive hydrogels consisting of ion-conductive deep eutectic solvents (DES) and electron-conductive MXene within polymer matrix have been presented. The increment of ion and electron migration path could generate substantial resistance variation and thus improves the sensitivity of hydrogels under small strain and large strain, resembling those in low and high frequency sound discrimination of auditory transduction. Additionally, the hydrogen bonding interactions among water molecules, DES and MXene as well as polymers endow the hydrogels with superior anti-freezing and water-retaining performance. The resultant hydrogel sensor achieves ultra-fast strain response time of 0.01 s and high sensitivity over 1.0 in wide strain ranges from 1% to 150%. High sensitivity, anti-freezing and water-retaining performance enable the hydrogels to monitor strain at extreme temperature conditions from −20 to 60 °C and could detect human motion in real time. This work provides a rational approach to the construction of high-sensitivity and environmental weatherable hydrogels based on the dual-conductive fillers for the development of advanced wearable sensors.
Wearable sensors represent a promising technology to monitor human health and movement, however, it is pivotal and challenging to tailor-make highly conductive hydrogels to achieve high sensitivity and environmental weatherability for application at extreme temperature conditions. Herein, the dual-conductive hydrogels consisting of ion-conductive deep eutectic solvents (DES) and electron-conductive MXene within polymer matrix have been presented. The increment of ion and electron migration path could generate substantial resistance variation and thus improves the sensitivity of hydrogels under small strain and large strain, resembling those in low and high frequency sound discrimination of auditory transduction. Additionally, the hydrogen bonding interactions among water molecules, DES and MXene as well as polymers endow the hydrogels with superior anti-freezing and water-retaining performance. The resultant hydrogel sensor achieves ultra-fast strain response time of 0.01 s and high sensitivity over 1.0 in wide strain ranges from 1% to 150%. High sensitivity, anti-freezing and water-retaining performance enable the hydrogels to monitor strain at extreme temperature conditions from −20 to 60 °C and could detect human motion in real time. This work provides a rational approach to the construction of high-sensitivity and environmental weatherable hydrogels based on the dual-conductive fillers for the development of advanced wearable sensors.
2025, 44(8): 100629
doi: 10.1016/j.cjsc.2025.100629
摘要:
UiO-66-H MOFs can effectively catalyze the direct selective oxidation of methane (DSOM) to high value-added oxygenates under mild conditions. However, UiO-66-NH2 with benzene-1,4-dicarboxylate (NH2-BDC) ligand modifying the Zr-oxo nodes exhibits relatively inferior catalytic performance for DSOM. Here, a combination of density functional theory (DFT) calculations and experiments was employed to explore the underlying reasons for the limited catalytic activity of UiO-66-NH2. The results indicate that the methane hydroxylation performance of UiO-66-NH2 is almost unaffected by the increase of •OH concentration. This is attributed to the formation of substantial non-covalent hydrogen bonds between the oxygen atoms of oxygenic species on the Zr-oxo nodes and the hydrogen atoms of –NH2 groups, which diminishes the spin density distribution on the active sites of (•OH)m/UiO-66-NH2, leading to minimal change of the adsorption energy of CH4. Additionally, the calculated adsorption energies (Eads) of CH4 exhibit a linear relationship with the catalytic activity of UiO-66-NH2 for DSOM reaction.
UiO-66-H MOFs can effectively catalyze the direct selective oxidation of methane (DSOM) to high value-added oxygenates under mild conditions. However, UiO-66-NH2 with benzene-1,4-dicarboxylate (NH2-BDC) ligand modifying the Zr-oxo nodes exhibits relatively inferior catalytic performance for DSOM. Here, a combination of density functional theory (DFT) calculations and experiments was employed to explore the underlying reasons for the limited catalytic activity of UiO-66-NH2. The results indicate that the methane hydroxylation performance of UiO-66-NH2 is almost unaffected by the increase of •OH concentration. This is attributed to the formation of substantial non-covalent hydrogen bonds between the oxygen atoms of oxygenic species on the Zr-oxo nodes and the hydrogen atoms of –NH2 groups, which diminishes the spin density distribution on the active sites of (•OH)m/UiO-66-NH2, leading to minimal change of the adsorption energy of CH4. Additionally, the calculated adsorption energies (Eads) of CH4 exhibit a linear relationship with the catalytic activity of UiO-66-NH2 for DSOM reaction.
2025, 44(8): 100630
doi: 10.1016/j.cjsc.2025.100630
摘要:
Solar-driven photocatalytic overall water splitting (POWS) has emerged as a sustainable pathway for hydrogen production, yet faces intrinsic challenges in developing robust catalysts that balance efficiency, stability, and cost-effectiveness. Polymeric carbon nitride (PCN) represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability. Nevertheless, limited by rapid charge recombination and insufficient oxidative capability, little success has been achieved on pristine PCN photocatalyst in POWS. In this context, recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance. Based on the fundamental principles of photocatalysis, this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems. With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems, modification strategies including crystallinity engineering, supramolecular precursor design, cocatalyst modulation, and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years. Future perspectives for PCN-based photocatalysts are proposed, aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
Solar-driven photocatalytic overall water splitting (POWS) has emerged as a sustainable pathway for hydrogen production, yet faces intrinsic challenges in developing robust catalysts that balance efficiency, stability, and cost-effectiveness. Polymeric carbon nitride (PCN) represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability. Nevertheless, limited by rapid charge recombination and insufficient oxidative capability, little success has been achieved on pristine PCN photocatalyst in POWS. In this context, recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance. Based on the fundamental principles of photocatalysis, this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems. With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems, modification strategies including crystallinity engineering, supramolecular precursor design, cocatalyst modulation, and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years. Future perspectives for PCN-based photocatalysts are proposed, aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
2025, 44(8): 100631
doi: 10.1016/j.cjsc.2025.100631
摘要:
Transition metal oxides (TMOs) have received extensive attention for their unique physical and chemical properties. It is worth noting that Fe-based materials stand out because of their rich natural resources, low toxicity, low price and other advantages, but at the same time confront with critical challenges such as capacity attenuation and volume expansion. Here, a universal synthesis method of MO/MFe2O4 (M = Ni, Cu, Zn) nanomaterials derived from Prussian blue analogues (PBAs) is proposed based on the self-sacrificing template strategy of metal-organic frameworks (MOFs). The calcined products retain the porous structure and small particle size of PBAs, which shorten the ion transport path, provide abundant electroactive sites and void space, effectively alleviate the effect of volume expansion, and improve the reaction kinetics. These MO/MFe2O4 anode materials exhibit excellent cyclic reversibility and stability during repeated charge/discharge process, among which, NiO/NiFe2O4 shows the best electrochemical performance, retaining a superior specific capacity of 1301.7 mAh g−1 following 230 cycles at 0.1 A g−1. In addition, the lithium adsorption capacity of the materials was further explored through the calculation of density functional theory (DFT). The research perspectives and strategies reported in this paper have strong universality and offer innovative insights for the synthesis of alternative advanced materials.
Transition metal oxides (TMOs) have received extensive attention for their unique physical and chemical properties. It is worth noting that Fe-based materials stand out because of their rich natural resources, low toxicity, low price and other advantages, but at the same time confront with critical challenges such as capacity attenuation and volume expansion. Here, a universal synthesis method of MO/MFe2O4 (M = Ni, Cu, Zn) nanomaterials derived from Prussian blue analogues (PBAs) is proposed based on the self-sacrificing template strategy of metal-organic frameworks (MOFs). The calcined products retain the porous structure and small particle size of PBAs, which shorten the ion transport path, provide abundant electroactive sites and void space, effectively alleviate the effect of volume expansion, and improve the reaction kinetics. These MO/MFe2O4 anode materials exhibit excellent cyclic reversibility and stability during repeated charge/discharge process, among which, NiO/NiFe2O4 shows the best electrochemical performance, retaining a superior specific capacity of 1301.7 mAh g−1 following 230 cycles at 0.1 A g−1. In addition, the lithium adsorption capacity of the materials was further explored through the calculation of density functional theory (DFT). The research perspectives and strategies reported in this paper have strong universality and offer innovative insights for the synthesis of alternative advanced materials.
2025, 44(8): 100632
doi: 10.1016/j.cjsc.2025.100632
摘要:
Dry reforming of methane (DRM) has gained significant attention as a promising route to convert two major greenhouse gases (CO2 and CH4) to syngas. The development of efficient catalysts is critical for the engineering applications. In this study, the CexZr1–xO2/ZSM-5 composites with different oxygen vacancy concentrations were synthesized by tuning the Ce/Zr ratio, followed by the deposition of metal Ni to island-like CexZr1–xO2 on ZSM-5, forming a variety of Ni-CexZr1–xO2/ZSM-5 catalysts, which were applied for the DRM reaction under 750 °C. Combined with various characterizations, it was found that the oxygen vacancy concentration illustrated the volcanic tendency with the decreased Ce/Zr ratio, and the interaction between metal Ni and CexZr1–xO2 exhibited a positive relationship with oxygen vacancy concentration. The enhanced between Ni and CexZr1–xO2 interaction could improve the strength and amount of Ni–O–M (M = Ce/Zr) species, making the d-band centers of catalysts closer to the Fermi energy level, which was beneficial to the CH4 and CO2 activation, along with the improved capacity to resist sintering and coking. Especially, the C1Z3 (Ni–Ce0.25Zr0.75O2/ZSM-5) catalyst with the Ce/Zr ratio of 1/3 demonstrated the optimal catalytic performance with 91.9% CH4 and 93.8% CO2 conversions within 50 h, accompanied by the best structural and catalytic stability after 100 h. In-situ DRIFTS was employed to study the reaction path and mechanism, discovering that significant amounts of strengthened Ni–O–M species were conducive to activating adsorbed CH4 and CO2, and desorbing the linear CO species.
Dry reforming of methane (DRM) has gained significant attention as a promising route to convert two major greenhouse gases (CO2 and CH4) to syngas. The development of efficient catalysts is critical for the engineering applications. In this study, the CexZr1–xO2/ZSM-5 composites with different oxygen vacancy concentrations were synthesized by tuning the Ce/Zr ratio, followed by the deposition of metal Ni to island-like CexZr1–xO2 on ZSM-5, forming a variety of Ni-CexZr1–xO2/ZSM-5 catalysts, which were applied for the DRM reaction under 750 °C. Combined with various characterizations, it was found that the oxygen vacancy concentration illustrated the volcanic tendency with the decreased Ce/Zr ratio, and the interaction between metal Ni and CexZr1–xO2 exhibited a positive relationship with oxygen vacancy concentration. The enhanced between Ni and CexZr1–xO2 interaction could improve the strength and amount of Ni–O–M (M = Ce/Zr) species, making the d-band centers of catalysts closer to the Fermi energy level, which was beneficial to the CH4 and CO2 activation, along with the improved capacity to resist sintering and coking. Especially, the C1Z3 (Ni–Ce0.25Zr0.75O2/ZSM-5) catalyst with the Ce/Zr ratio of 1/3 demonstrated the optimal catalytic performance with 91.9% CH4 and 93.8% CO2 conversions within 50 h, accompanied by the best structural and catalytic stability after 100 h. In-situ DRIFTS was employed to study the reaction path and mechanism, discovering that significant amounts of strengthened Ni–O–M species were conducive to activating adsorbed CH4 and CO2, and desorbing the linear CO species.
2025, 44(8): 100633
doi: 10.1016/j.cjsc.2025.100633
摘要:
Plasmon-induced hot electron can transfer from noble metal to its cohesive semiconductor in their heterostructure to initiate the photocatalytic reaction upon resonance excitation. However, the co-excitation of semiconductor in the heterostructure would also lead to the inversus transfer of photo-electron from semiconductor to noble metal, which inevitably limits the use of active electrons. After co-excitation of both localized surface plasmon resonance (LSPR) of noble metal and interband transition of semiconductor, the interfacial electron transfer process strongly depends on the energy band configuration of their heterostructure. When the Au content in the AuAg alloy nanoparticles (NPs) changes from 0 to 100 at.%, the interfacial energy band configuration at AuAg NPs/TiO2 NPs in the electrospun nanofibers (NFs) shifts from Ohmic to Schottky contacts. Further investigation finds that the optimal Schottky barrier configuration in Au0.25Ag0.75/TiO2 NFs can not only boost the plasmon-induced hot electron transfer from Au0.25Ag0.75 to TiO2 NPs, but also suppresses the backflow of photo-electrons from TiO2 to Au0.25Ag0.75 NPs in NFs. Thus, upon UV-visible light irradiation, the CO2 photo-reduction activity of Au0.25Ag0.75/TiO2 NFs is ∼3 and ∼2 times higher than that of either Ag/TiO2 or Au/TiO2 NFs.
Plasmon-induced hot electron can transfer from noble metal to its cohesive semiconductor in their heterostructure to initiate the photocatalytic reaction upon resonance excitation. However, the co-excitation of semiconductor in the heterostructure would also lead to the inversus transfer of photo-electron from semiconductor to noble metal, which inevitably limits the use of active electrons. After co-excitation of both localized surface plasmon resonance (LSPR) of noble metal and interband transition of semiconductor, the interfacial electron transfer process strongly depends on the energy band configuration of their heterostructure. When the Au content in the AuAg alloy nanoparticles (NPs) changes from 0 to 100 at.%, the interfacial energy band configuration at AuAg NPs/TiO2 NPs in the electrospun nanofibers (NFs) shifts from Ohmic to Schottky contacts. Further investigation finds that the optimal Schottky barrier configuration in Au0.25Ag0.75/TiO2 NFs can not only boost the plasmon-induced hot electron transfer from Au0.25Ag0.75 to TiO2 NPs, but also suppresses the backflow of photo-electrons from TiO2 to Au0.25Ag0.75 NPs in NFs. Thus, upon UV-visible light irradiation, the CO2 photo-reduction activity of Au0.25Ag0.75/TiO2 NFs is ∼3 and ∼2 times higher than that of either Ag/TiO2 or Au/TiO2 NFs.
2025, 44(8): 100648
doi: 10.1016/j.cjsc.2025.100648
摘要:
2025, 44(8): 100649
doi: 10.1016/j.cjsc.2025.100649
摘要:
The reduction of N2 to NH3 is an important reaction for the industrial production of ammonia gas. Here, we theoretically studied the thermal synthesis of ammonia catalyzed by Ru1@Mo2COx single-atom catalyst, where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx. The results show that Ru1@Mo2COx exhibits excellent stability. Moreover, Ru1@Mo2COx can effectively adsorb and activate N2, owing to up to −0.87 |e| charge transfer from Ru1@Mo2COx to N2. The optimal pathway of N2-to-NH3 conversion is association pathway I, of which the rate-determining step is *NH2→*NH3 with of barrier energy of 1.26 eV. Especially, the Mo2COx center functions as an electron reservoir, donating electrons to the NxHy species, while the Ru single atom serves as a charge transfer pathway, thereby enhancing the reaction activity. This finding provides a theoretical foundation for the rational design of MXene-based single-atom catalysts for thermal catalytic NH3 synthesis.
The reduction of N2 to NH3 is an important reaction for the industrial production of ammonia gas. Here, we theoretically studied the thermal synthesis of ammonia catalyzed by Ru1@Mo2COx single-atom catalyst, where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx. The results show that Ru1@Mo2COx exhibits excellent stability. Moreover, Ru1@Mo2COx can effectively adsorb and activate N2, owing to up to −0.87 |e| charge transfer from Ru1@Mo2COx to N2. The optimal pathway of N2-to-NH3 conversion is association pathway I, of which the rate-determining step is *NH2→*NH3 with of barrier energy of 1.26 eV. Especially, the Mo2COx center functions as an electron reservoir, donating electrons to the NxHy species, while the Ru single atom serves as a charge transfer pathway, thereby enhancing the reaction activity. This finding provides a theoretical foundation for the rational design of MXene-based single-atom catalysts for thermal catalytic NH3 synthesis.
2025, 44(8): 100650
doi: 10.1016/j.cjsc.2025.100650
摘要:
