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无机化学学报
Chinese Journal of Inorganic Chemistry
主管 : 中国科学技术协会
刊期 : 月刊主编 : 游效曾
语种 : 中文主办 : 中国化学会
ISSN : 1001-4861 CN : 32-1185/O6展开 >《无机化学学报》由中国化学会主办，是展示我国无机化学研究成果的学术性期刊，月刊。1985年由化学前辈戴安邦院士（发起）创刊，现任主编游效曾院士。编辑部设在南京大学化学化工学院化学楼。报道我国无机化学领域的基础研究和应用基础研究的创新成果，内容涉及固体无机化学、配位化学、无机材料化学、生物无机化学、有机金属化学、理论无机化学、超分子化学和应用无机化学、催化等，着重报道新的和已知化合物的合成、热力学、动力学性质、谱学、结构和成键等。设有综述、研究快报及论文等栏目。
本刊所刊论文均为美国《科学引文索引》（SCI）网络版、美国《化学文摘》(CA)、《中国学术期刊文摘》（中、英文版）、《中国科技论文与引文数据库（CSTPCD）》、《中国科学引文数据库》、《中文科技期刊数据库》、《中国期刊全文数据库》、《中国核心期刊（遴选）数据库》、中国台湾华艺《中文电子期刊服务》等国内外多种著名检索刊物和文献数据库摘引和收录。
《无机化学学报》2011年每期200页，定价28.00元、全年定价336.00元。本刊由各地邮局征订，邮发代号28-133。也可直接向编辑部订阅。
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2026, 42(9): 1793-1806
doi: 10.11862/CJIC.20260035
摘要:
水系多价金属离子电池是基于水系电解液，通过多价金属离子在电极材料中嵌入/脱出工作的新型储能设备。该类电池兼具高安全性、高离子电导率和高理论容量等显著优势，近年来受到广泛关注。然而，多价金属离子具有较高的电荷密度，导致其在水系电解液中具有较高的去溶剂化能垒，而且其在正极材料中的固相扩散又面临动力学扩散障碍，这严重限制了其电化学性能与进一步发展。针对上述面临的关键挑战，开发具有快速离子传输通道的正极材料至关重要。在众多候选材料中，普鲁士蓝类似物(PBAs)由于具有开放的三维框架结构、可调的氧化还原活性中心及易于规模化制备等特点，被广泛应用于水系多价金属离子电池正极。然而，PBAs在实际应用中仍面临导电性不佳和结构稳定性不足等挑战。针对这些问题，当前研究主要通过构筑多金属活性位点、与高导电材料复合等手段，优化PBAs的电荷传输动力学与结构稳定性。本文系统综述了PBA基复合材料的合理设计策略及其在水系多价金属离子电池正极中的应用，为高性能储能设备的开发提供具有参考价值的研究思路。
水系多价金属离子电池是基于水系电解液，通过多价金属离子在电极材料中嵌入/脱出工作的新型储能设备。该类电池兼具高安全性、高离子电导率和高理论容量等显著优势，近年来受到广泛关注。然而，多价金属离子具有较高的电荷密度，导致其在水系电解液中具有较高的去溶剂化能垒，而且其在正极材料中的固相扩散又面临动力学扩散障碍，这严重限制了其电化学性能与进一步发展。针对上述面临的关键挑战，开发具有快速离子传输通道的正极材料至关重要。在众多候选材料中，普鲁士蓝类似物(PBAs)由于具有开放的三维框架结构、可调的氧化还原活性中心及易于规模化制备等特点，被广泛应用于水系多价金属离子电池正极。然而，PBAs在实际应用中仍面临导电性不佳和结构稳定性不足等挑战。针对这些问题，当前研究主要通过构筑多金属活性位点、与高导电材料复合等手段，优化PBAs的电荷传输动力学与结构稳定性。本文系统综述了PBA基复合材料的合理设计策略及其在水系多价金属离子电池正极中的应用，为高性能储能设备的开发提供具有参考价值的研究思路。
2026, 42(9): 1845-1870
doi: 10.11862/CJIC.20260059
摘要:
水电解制氢是实现大规模绿色氢能的关键技术，其能量转换效率受限于阳极析氧反应(oxygen evolution reaction，OER)缓慢的动力学过程，同时催化剂在苛刻工况下的稳定性亦面临挑战。传统实验“试错法”在广阔的化学空间中探索高性能阳极材料难度巨大。近年来，结合基于密度泛函理论(density functional theory，DFT)的高通量计算(high-throughput computing，HTC)与机器学习(machine learning，ML)技术，利用理论模拟与数据挖掘驱动新材料的发现，为高性能OER催化剂的研发提供了创新解决方案。本文综述了该研究范式在OER催化剂设计中的进展：首先概述了OER的反应机制、计算框架及高通量计算工作流程，并介绍了涵盖多模态数据集构建、物理特征工程与先进算法架构的ML工作流；其次，重点探讨了3类典型材料体系的探索成果，包括贵金属(Ir/Ru基)氧化物、廉价金属氧化物/氢氧化物(如层状水滑石、钙钛矿等)以及高熵合金及其衍生的氧化物；最后，总结了当前领域在数据标准化、模型泛化能力及真实工况模拟等方面的挑战，展望了生成式人工智能(AI-generated content，AIGC)与无人实验室在未来全流程自动化材料研发中的前景。
水电解制氢是实现大规模绿色氢能的关键技术，其能量转换效率受限于阳极析氧反应(oxygen evolution reaction，OER)缓慢的动力学过程，同时催化剂在苛刻工况下的稳定性亦面临挑战。传统实验“试错法”在广阔的化学空间中探索高性能阳极材料难度巨大。近年来，结合基于密度泛函理论(density functional theory，DFT)的高通量计算(high-throughput computing，HTC)与机器学习(machine learning，ML)技术，利用理论模拟与数据挖掘驱动新材料的发现，为高性能OER催化剂的研发提供了创新解决方案。本文综述了该研究范式在OER催化剂设计中的进展：首先概述了OER的反应机制、计算框架及高通量计算工作流程，并介绍了涵盖多模态数据集构建、物理特征工程与先进算法架构的ML工作流；其次，重点探讨了3类典型材料体系的探索成果，包括贵金属(Ir/Ru基)氧化物、廉价金属氧化物/氢氧化物(如层状水滑石、钙钛矿等)以及高熵合金及其衍生的氧化物；最后，总结了当前领域在数据标准化、模型泛化能力及真实工况模拟等方面的挑战，展望了生成式人工智能(AI-generated content，AIGC)与无人实验室在未来全流程自动化材料研发中的前景。
2026, 42(9): 1871-1892
doi: 10.11862/CJIC.20260168
摘要:
金属有机框架(MOFs)具有高比表面积、可调的活性位点及结构多样性等独特优势，使其在电催化尿素氧化反应(UOR)中展现出巨大的应用潜力。本文从电催化剂设计策略、合成方法、性能评价方法及反应机制类型4个方面出发，系统综述MOF基电催化剂在UOR中的研究进展，以揭示MOF基催化剂结构与UOR性能之间的内在构效关系，总结当前研究面临的关键挑战，并为高效MOF基UOR电催化剂的精准设计与开发提供参考。
金属有机框架(MOFs)具有高比表面积、可调的活性位点及结构多样性等独特优势，使其在电催化尿素氧化反应(UOR)中展现出巨大的应用潜力。本文从电催化剂设计策略、合成方法、性能评价方法及反应机制类型4个方面出发，系统综述MOF基电催化剂在UOR中的研究进展，以揭示MOF基催化剂结构与UOR性能之间的内在构效关系，总结当前研究面临的关键挑战，并为高效MOF基UOR电催化剂的精准设计与开发提供参考。
2026, 42(9): 1893-1909
doi: 10.11862/CJIC.20260144
摘要:
电催化二氧化碳还原反应(eCO2RR)为实现碳资源循环利用与碳中和目标提供了重要途径。金属有机框架材料(MOFs)凭借结构可设计性强、孔道可调及活性位点高度分散等优势，在eCO2RR领域展现出良好的应用前景，但其在反应过程中的结构重构与真实活性物种的识别方面仍面临挑战。本文系统综述了原位傅里叶红外光谱、原位拉曼光谱、原位紫外可见吸收光谱、原位X射线吸收光谱、原位X射线衍射、原位差分电化学质谱及循环伏安法等原位表征技术在MOFs基催化剂的eCO2RR研究中的进展，重点阐述了各类技术在中间体识别、金属价态演变、配位环境变化、结构重构行为及产物生成路径解析等各方面中的作用与优势。与已有综述侧重表征技术自身介绍不同，本文以MOFs动态重构与真实活性位点溯源为主线，系统梳理了多尺度原位表征如何揭示MOFs本征结构的重构与催化性能之间的关系。此外，本文还展望了多技术联用、时空分辨率提升以及原位数据与理论计算/机器学习深度融合等未来发展方向。通过整合上述原位表征信息，为深入认识真实活性位点、阐明反应机理以及设计高效MOFs基电催化体系提供参考。
电催化二氧化碳还原反应(eCO2RR)为实现碳资源循环利用与碳中和目标提供了重要途径。金属有机框架材料(MOFs)凭借结构可设计性强、孔道可调及活性位点高度分散等优势，在eCO2RR领域展现出良好的应用前景，但其在反应过程中的结构重构与真实活性物种的识别方面仍面临挑战。本文系统综述了原位傅里叶红外光谱、原位拉曼光谱、原位紫外可见吸收光谱、原位X射线吸收光谱、原位X射线衍射、原位差分电化学质谱及循环伏安法等原位表征技术在MOFs基催化剂的eCO2RR研究中的进展，重点阐述了各类技术在中间体识别、金属价态演变、配位环境变化、结构重构行为及产物生成路径解析等各方面中的作用与优势。与已有综述侧重表征技术自身介绍不同，本文以MOFs动态重构与真实活性位点溯源为主线，系统梳理了多尺度原位表征如何揭示MOFs本征结构的重构与催化性能之间的关系。此外，本文还展望了多技术联用、时空分辨率提升以及原位数据与理论计算/机器学习深度融合等未来发展方向。通过整合上述原位表征信息，为深入认识真实活性位点、阐明反应机理以及设计高效MOFs基电催化体系提供参考。
2026, 42(9): 1910-1932
doi: 10.11862/CJIC.20260188
摘要:
锂硫电池因超高的理论能量密度(2 600 Wh·kg-1)和环境友好性，被认为是下一代能量存储系统的有力候选者。然而，多硫化锂(LiPS)的穿梭效应、锂枝晶的生长以及硫正极的体积膨胀等问题的存在，严重限制了锂硫电池的商业化进程。金属有机框架(MOF)衍生材料因具有高比表面积、丰富的活性位点及优异的结构稳定性，可高效阻止LiPS穿梭，加快氧化还原动力学进程，是锂硫电池隔膜理想的改性材料，具有独特优势。本文主要介绍了MOF衍生材料在锂硫电池隔膜中的应用，以所得金属基材料的种类(如金属纳米颗粒、氧化物、硫化物与其他金属化合物等)为依据，首先阐述了常见MOF衍生材料的合成策略，然后深入分析了其在隔膜中的作用机制及效果，最后展望了其在锂硫电池隔膜中应用的发展方向，旨在为未来的研究提供理论依据。
锂硫电池因超高的理论能量密度(2 600 Wh·kg-1)和环境友好性，被认为是下一代能量存储系统的有力候选者。然而，多硫化锂(LiPS)的穿梭效应、锂枝晶的生长以及硫正极的体积膨胀等问题的存在，严重限制了锂硫电池的商业化进程。金属有机框架(MOF)衍生材料因具有高比表面积、丰富的活性位点及优异的结构稳定性，可高效阻止LiPS穿梭，加快氧化还原动力学进程，是锂硫电池隔膜理想的改性材料，具有独特优势。本文主要介绍了MOF衍生材料在锂硫电池隔膜中的应用，以所得金属基材料的种类(如金属纳米颗粒、氧化物、硫化物与其他金属化合物等)为依据，首先阐述了常见MOF衍生材料的合成策略，然后深入分析了其在隔膜中的作用机制及效果，最后展望了其在锂硫电池隔膜中应用的发展方向，旨在为未来的研究提供理论依据。
2026, 42(9): 1807-1815
doi: 10.11862/CJIC.20250363
摘要:
The development of efficient catalysts for water oxidation is pivotal for advancing sustainable energy technologies, such as overall water splitting and carbon dioxide reduction. While molecular catalysts offer precise tunability at the atomic level, their practical application is hindered by instability and poor recyclability. Recent advances in metal covalent organic frameworks (MCOFs) have bridged homogeneous molecular catalysts and robust heterogeneous materials, offering a promising platform for durable water oxidation. This review highlights recent progress in the development of MCOF-based water oxidation catalysts, with a focus on design strategies, structure-activity relationships, and mechanistic insights.
The development of efficient catalysts for water oxidation is pivotal for advancing sustainable energy technologies, such as overall water splitting and carbon dioxide reduction. While molecular catalysts offer precise tunability at the atomic level, their practical application is hindered by instability and poor recyclability. Recent advances in metal covalent organic frameworks (MCOFs) have bridged homogeneous molecular catalysts and robust heterogeneous materials, offering a promising platform for durable water oxidation. This review highlights recent progress in the development of MCOF-based water oxidation catalysts, with a focus on design strategies, structure-activity relationships, and mechanistic insights.
2026, 42(9): 1816-1844
doi: 10.11862/CJIC.20250383
摘要:
In the context of the global energy transition, lithium-ion batteries have emerged as the predominant energy storage technology. However, their fast-charging capabilities continue to be limited by challenges such as lithium dendrite formation, electrode volume expansion, and interfacial instability. Metal-organic frameworks (MOFs) offer promising opportunities to improve battery performance owing to their high specific surface area, tunable pore architectures, and abundant redox-active sites. Their ordered porous structure not only promotes efficient ion transport and electrolyte penetration but also enables the incorporation of numerous active sites through precise structural design. This review systematically outlines recent progress in the use of MOFs and their derivatives for fast-charging lithium-ion batteries, with a focus on their applications in electrode materials and critical battery components, as well as the associated enhancement mechanisms. It aims to provide guidance for the design and development of high-performance MOF-based materials for fast-charging batteries.
In the context of the global energy transition, lithium-ion batteries have emerged as the predominant energy storage technology. However, their fast-charging capabilities continue to be limited by challenges such as lithium dendrite formation, electrode volume expansion, and interfacial instability. Metal-organic frameworks (MOFs) offer promising opportunities to improve battery performance owing to their high specific surface area, tunable pore architectures, and abundant redox-active sites. Their ordered porous structure not only promotes efficient ion transport and electrolyte penetration but also enables the incorporation of numerous active sites through precise structural design. This review systematically outlines recent progress in the use of MOFs and their derivatives for fast-charging lithium-ion batteries, with a focus on their applications in electrode materials and critical battery components, as well as the associated enhancement mechanisms. It aims to provide guidance for the design and development of high-performance MOF-based materials for fast-charging batteries.
2026, 42(9): 1933-1944
doi: 10.11862/CJIC.20250373
摘要:
Developing high-performance electrocatalysts for the alkaline hydrogen oxidation reaction (HOR) is essential for advancing alkaline hydrogen fuel cells. Here, we report the synthesis of ruthenium (Ru) catalysts with tuned crystallinity and oxidation degree. By combining template-assisted synthesis with controlled thermal treatment, amorphous, partially crystalline, highly crystalline, and partially oxidized Ru products were successfully obtained. Catalysts with moderate crystallinity and partial oxidation exhibit enhanced catalytic activity toward the alkaline hydrogen oxidation reaction. The optimized Ru-RuO2 catalyst achieved a mass activity of 81.66 mA·mgRu-1, which was 2.27 times that of commercial Pt/C under identical conditions. The improved activity is attributed to the synergistic effect of moderate crystallinity and partial oxidation, which favors a favorable Tafel-Volmer reaction pathway.
Developing high-performance electrocatalysts for the alkaline hydrogen oxidation reaction (HOR) is essential for advancing alkaline hydrogen fuel cells. Here, we report the synthesis of ruthenium (Ru) catalysts with tuned crystallinity and oxidation degree. By combining template-assisted synthesis with controlled thermal treatment, amorphous, partially crystalline, highly crystalline, and partially oxidized Ru products were successfully obtained. Catalysts with moderate crystallinity and partial oxidation exhibit enhanced catalytic activity toward the alkaline hydrogen oxidation reaction. The optimized Ru-RuO2 catalyst achieved a mass activity of 81.66 mA·mgRu-1, which was 2.27 times that of commercial Pt/C under identical conditions. The improved activity is attributed to the synergistic effect of moderate crystallinity and partial oxidation, which favors a favorable Tafel-Volmer reaction pathway.
2026, 42(9): 1945-1958
doi: 10.11862/CJIC.20260147
摘要:
To overcome the non-radiative energy dissipation that weakens the intrinsic emission of metal-organic frameworks (MOFs), a fluorophore functionalization strategy was applied to restrict intramolecular ligand motion and to enhance the photoluminescence. Two analogous frameworks were synthesized and systematically compared: {[Cd(4bpyttz)(CDA)]·2DMF}n (MOF 1), constructed from a ligand with a rigidly fused thiazolo[5,4-d]thiazole (TTZ) core, and [Cd(4bbpy)(CDA)]n (MOF 2), which incorporates a freely rotatable phenyl core (4bpyttz=2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, 4bbpy=1,4-bis(pyridin-4-yl)benzene, H2CDA=4,4′-carbonyldibenzoic acid). Photophysical and density functional theory (DFT) studies reveal that the TTZ core localizes both the HOMO and LUMO on itself, thereby deactivating the ligand-to-ligand charge transfer (LLCT) pathway present in MOF 1. This core rigidification enforces ordered π…π stacking and suppresses non-radiative decay, leading to dramatically enhanced solid-state photoluminescence. Consequently, MOF 1 functions as a highly selective turn-off fluorescent sensor for nitrofuran antibiotics in aqueous media, achieving limits of detection of 1.59 μmol·L-1 for nitrofurazone (NZF) and 2.77 μmol·L-1 for nitrofurantoin (NFT). Mechanistic studies show that this rapid quenching is primarily governed by the inner filter effect (IFE) coupled with photoinduced electron transfer (PET).
To overcome the non-radiative energy dissipation that weakens the intrinsic emission of metal-organic frameworks (MOFs), a fluorophore functionalization strategy was applied to restrict intramolecular ligand motion and to enhance the photoluminescence. Two analogous frameworks were synthesized and systematically compared: {[Cd(4bpyttz)(CDA)]·2DMF}n (MOF 1), constructed from a ligand with a rigidly fused thiazolo[5,4-d]thiazole (TTZ) core, and [Cd(4bbpy)(CDA)]n (MOF 2), which incorporates a freely rotatable phenyl core (4bpyttz=2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, 4bbpy=1,4-bis(pyridin-4-yl)benzene, H2CDA=4,4′-carbonyldibenzoic acid). Photophysical and density functional theory (DFT) studies reveal that the TTZ core localizes both the HOMO and LUMO on itself, thereby deactivating the ligand-to-ligand charge transfer (LLCT) pathway present in MOF 1. This core rigidification enforces ordered π…π stacking and suppresses non-radiative decay, leading to dramatically enhanced solid-state photoluminescence. Consequently, MOF 1 functions as a highly selective turn-off fluorescent sensor for nitrofuran antibiotics in aqueous media, achieving limits of detection of 1.59 μmol·L-1 for nitrofurazone (NZF) and 2.77 μmol·L-1 for nitrofurantoin (NFT). Mechanistic studies show that this rapid quenching is primarily governed by the inner filter effect (IFE) coupled with photoinduced electron transfer (PET).
2026, 42(9): 1959-1973
doi: 10.11862/CJIC.20260015
摘要:
We developed a facile in situ partial oxidation strategy to construct a MoS2-MoO3 heterojunction, which was employed as a modified layer on a commercial polypropylene (PP) separator. The constructed heterojunction catalyst promotes the complete reduction of lithium polysulfides (LiPSs) via tandem catalysis, facilitating both liquid-liquid and liquid-solid conversion processes. The modified LSBs exhibited a high reversible capacity of 402.9 mAh·g-1 after 1 000 cycles at 1C, with an ultralow capacity decay rate of only 0.05% per cycle.
We developed a facile in situ partial oxidation strategy to construct a MoS2-MoO3 heterojunction, which was employed as a modified layer on a commercial polypropylene (PP) separator. The constructed heterojunction catalyst promotes the complete reduction of lithium polysulfides (LiPSs) via tandem catalysis, facilitating both liquid-liquid and liquid-solid conversion processes. The modified LSBs exhibited a high reversible capacity of 402.9 mAh·g-1 after 1 000 cycles at 1C, with an ultralow capacity decay rate of only 0.05% per cycle.
2026, 42(9): 1974-1983
doi: 10.11862/CJIC.20260154
摘要:
以咪唑基功能化的H3ITTA为有机桥联配体，分别与2类3连接钒氧簇[V6ⅣO6(OCH3)9(SO4)(CO2)3]2-({V6S})和[V6ⅣO6(OCH3)9(PyPO3)(CO2)3]2-({V6P})进行定向组装，成功构筑了2例功能化钒多酸-有机多面体(VMOPs)：具有本征笼腔结构的(TMA)8{[V6O6(OCH3)9(SO4)]4(ITTA)4}·17CH3OH·20DMF (TMA-VMOT-S-1)，以及笼腔内修饰吡啶-4-基膦酸(PyPO3H2)活性位点的(TMA)8{[V6O6(OCH3)9(PyPO3)]4 (ITTA)4}·26CH3OH·8DMF (TMA-VMOT-P-1)，其中H3ITTA=4，4′，4″-(1H-咪唑-2，4，5-三基)三苯甲酸，TMA+=(CH3)4N+。采用单晶X射线衍射、粉末X射线衍射、红外光谱及热重分析等手段对2例化合物进行了系统的理化性质表征。结构分析表明，腔内功能基团的引入使TMA-VMOT-P-1的笼状结构发生轻微扩张，同时其有效空腔体积有所缩减。碘吸附实验表明，TMA-VMOT-S-1与TMA-VMOT-P-1表现出相近的吸附容量与吸附动力学速率。
以咪唑基功能化的H3ITTA为有机桥联配体，分别与2类3连接钒氧簇[V6ⅣO6(OCH3)9(SO4)(CO2)3]2-({V6S})和[V6ⅣO6(OCH3)9(PyPO3)(CO2)3]2-({V6P})进行定向组装，成功构筑了2例功能化钒多酸-有机多面体(VMOPs)：具有本征笼腔结构的(TMA)8{[V6O6(OCH3)9(SO4)]4(ITTA)4}·17CH3OH·20DMF (TMA-VMOT-S-1)，以及笼腔内修饰吡啶-4-基膦酸(PyPO3H2)活性位点的(TMA)8{[V6O6(OCH3)9(PyPO3)]4 (ITTA)4}·26CH3OH·8DMF (TMA-VMOT-P-1)，其中H3ITTA=4，4′，4″-(1H-咪唑-2，4，5-三基)三苯甲酸，TMA+=(CH3)4N+。采用单晶X射线衍射、粉末X射线衍射、红外光谱及热重分析等手段对2例化合物进行了系统的理化性质表征。结构分析表明，腔内功能基团的引入使TMA-VMOT-P-1的笼状结构发生轻微扩张，同时其有效空腔体积有所缩减。碘吸附实验表明，TMA-VMOT-S-1与TMA-VMOT-P-1表现出相近的吸附容量与吸附动力学速率。
2026, 42(9): 1984-1996
doi: 10.11862/CJIC.20250372
摘要:
通过一步水热反应法，制备了高熵多元金属硫化物(NiCoSnZnFeSx)与还原氧化石墨烯(rGO)的复合材料(NiCoSnZnFeSx-rGO)，并对其微观结构和形貌、电化学储锂性能进行了研究。结果表明，NiCoSnZnFeSx纳米粒子显示了杂化纳米晶的微观结构，并较好地分散在rGO的表面。与单金属硫化物与rGO的复合材料(SnS2-rGO、CoS2-rGO和NiS2-rGO)相比，NiCoSnZnFeSx-rGO显示了显著增强的电化学储锂性能，其初始可逆比容量为1 230 mAh·g-1，在2.0 A·g-1电流密度下的可逆比容量为869 mAh·g-1，而且充放电循环900次后，在1.0 A·g-1依然保持996 mAh·g-1的可逆比容量，显示了较好的倍率性能和稳定的长循环性能。NiCoSnZnFeSx-rGO优异的电化学储锂性能主要是源于其组成元素的多样性和不同金属硫化物的协同作用，从而显著增强了储锂转化反应的可逆性和循环稳定性。
通过一步水热反应法，制备了高熵多元金属硫化物(NiCoSnZnFeSx)与还原氧化石墨烯(rGO)的复合材料(NiCoSnZnFeSx-rGO)，并对其微观结构和形貌、电化学储锂性能进行了研究。结果表明，NiCoSnZnFeSx纳米粒子显示了杂化纳米晶的微观结构，并较好地分散在rGO的表面。与单金属硫化物与rGO的复合材料(SnS2-rGO、CoS2-rGO和NiS2-rGO)相比，NiCoSnZnFeSx-rGO显示了显著增强的电化学储锂性能，其初始可逆比容量为1 230 mAh·g-1，在2.0 A·g-1电流密度下的可逆比容量为869 mAh·g-1，而且充放电循环900次后，在1.0 A·g-1依然保持996 mAh·g-1的可逆比容量，显示了较好的倍率性能和稳定的长循环性能。NiCoSnZnFeSx-rGO优异的电化学储锂性能主要是源于其组成元素的多样性和不同金属硫化物的协同作用，从而显著增强了储锂转化反应的可逆性和循环稳定性。
2026, 42(9): 1997-2007
doi: 10.11862/CJIC.20260109
摘要:
通过在Cu2O催化剂表面修饰一系列具有明确结构的三嗪基共价有机框架，系统探究了多孔材料的孔道微环境对CO2传质行为的影响。实验结果表明，在系列复合材料中，一种兼具高疏水性与大孔径特征、负载Cu2O的氟掺杂亚胺共价三嗪框架(Cu2O/F-Imine-CTF-2.5%)表现出最优性能，其最大乙烯法拉第效率(FEmax)对应的电流密度可达800 mA·cm-2，是纯Cu2O的2倍，乙烯的分电流密度显著提升。研究结果表明，在水系电解液环境下，多孔材料传质的强化不仅依赖于其对CO2的吸附亲和力，更取决于其疏水性对水分子的排斥能力以及孔道尺寸对扩散阻力的降低。
通过在Cu2O催化剂表面修饰一系列具有明确结构的三嗪基共价有机框架，系统探究了多孔材料的孔道微环境对CO2传质行为的影响。实验结果表明，在系列复合材料中，一种兼具高疏水性与大孔径特征、负载Cu2O的氟掺杂亚胺共价三嗪框架(Cu2O/F-Imine-CTF-2.5%)表现出最优性能，其最大乙烯法拉第效率(FEmax)对应的电流密度可达800 mA·cm-2，是纯Cu2O的2倍，乙烯的分电流密度显著提升。研究结果表明，在水系电解液环境下，多孔材料传质的强化不仅依赖于其对CO2的吸附亲和力，更取决于其疏水性对水分子的排斥能力以及孔道尺寸对扩散阻力的降低。
2026, 42(9): 2008-2020
doi: 10.11862/CJIC.20260050
摘要:
采用固相合成法对SrTiO3进行B掺杂得到B-SrTiO3，而后负载Rh、Cr、Co助催化剂(RCC)得到B-SrTiO3-RCC光催化剂。所制备的催化剂在375 nm波长照射下实现了水的全分解，表观量子效率(AQE)达到82.06%，产氢速率达到4.92 mmol·g-1·h-1，且在约600 h长时间循环测试中表现出优异的稳定性。B掺杂填补了部分Ti3+缺陷，诱导产生了更多的表面羟基，促进了光生载流子的有效分离和转移，进而有效提高了SrTiO3的全分解水产氢活性。
采用固相合成法对SrTiO3进行B掺杂得到B-SrTiO3，而后负载Rh、Cr、Co助催化剂(RCC)得到B-SrTiO3-RCC光催化剂。所制备的催化剂在375 nm波长照射下实现了水的全分解，表观量子效率(AQE)达到82.06%，产氢速率达到4.92 mmol·g-1·h-1，且在约600 h长时间循环测试中表现出优异的稳定性。B掺杂填补了部分Ti3+缺陷，诱导产生了更多的表面羟基，促进了光生载流子的有效分离和转移，进而有效提高了SrTiO3的全分解水产氢活性。
2026, 42(9): 2021-2032
doi: 10.11862/CJIC.20260080
摘要:
通过植酸中磷酸基团与Fe3+的强配位策略，成功构建了具有稳定Fe—P结构的FeP和Fe2P活性物种。所合成的N掺杂多孔碳(NC)负载FeP和Fe2P催化剂(FeP/Fe2P-NC)保持了NC的载体形貌。X射线光电子能谱(XPS)分析表明，P原子通过电子调控作用优化了Fe位点的电子结构，显著提升了其电催化性能。在0.1 mol·L-1 KOH电解液中，该催化剂表现出优异的氧还原反应活性(半波电位E1/2=0.861 V)，显著优于商业Pt/C催化剂，并具有出色的稳定性、甲醇耐受性和电化学活性表面积。此外，其析氧反应(OER)过电势和电荷转移电阻均低于对比样品。应用于锌-空气电池时，催化剂展现出优异的开路电压、峰值功率密度和高比容量，且在长时间循环测试中保持稳定的充放电性能。
通过植酸中磷酸基团与Fe3+的强配位策略，成功构建了具有稳定Fe—P结构的FeP和Fe2P活性物种。所合成的N掺杂多孔碳(NC)负载FeP和Fe2P催化剂(FeP/Fe2P-NC)保持了NC的载体形貌。X射线光电子能谱(XPS)分析表明，P原子通过电子调控作用优化了Fe位点的电子结构，显著提升了其电催化性能。在0.1 mol·L-1 KOH电解液中，该催化剂表现出优异的氧还原反应活性(半波电位E1/2=0.861 V)，显著优于商业Pt/C催化剂，并具有出色的稳定性、甲醇耐受性和电化学活性表面积。此外，其析氧反应(OER)过电势和电荷转移电阻均低于对比样品。应用于锌-空气电池时，催化剂展现出优异的开路电压、峰值功率密度和高比容量，且在长时间循环测试中保持稳定的充放电性能。
2026, 42(9): 2033-2040
doi: 10.11862/CJIC.20260111
摘要:
采用水热法在碳布(CC)上制备了Mo掺杂MnO2正极材料(Mo-MnO2@CC)，通过X射线衍射、X射线光电子能谱等表征方法证实了Mo掺杂有效增大了MnO2的晶格间距，为Zn2+的嵌入/脱出提供了传输通道，并引入了更多的活性位点，显著提升了材料的电化学性能。以Mo-MnO2@CC为正极材料组装成的纽扣电池，在0.1 A·g-1的电流密度下，初始放电容量能够达到517.7 mAh·g-1，并且在1 A·g-1的电流密度下经过3 000次循环后，Mo-MnO2@CC的容量保持率仍为77.9%，这证明Mo掺杂可以提高电极的比容量和循环稳定性。
采用水热法在碳布(CC)上制备了Mo掺杂MnO2正极材料(Mo-MnO2@CC)，通过X射线衍射、X射线光电子能谱等表征方法证实了Mo掺杂有效增大了MnO2的晶格间距，为Zn2+的嵌入/脱出提供了传输通道，并引入了更多的活性位点，显著提升了材料的电化学性能。以Mo-MnO2@CC为正极材料组装成的纽扣电池，在0.1 A·g-1的电流密度下，初始放电容量能够达到517.7 mAh·g-1，并且在1 A·g-1的电流密度下经过3 000次循环后，Mo-MnO2@CC的容量保持率仍为77.9%，这证明Mo掺杂可以提高电极的比容量和循环稳定性。
2026, 42(9): 2041-2050
doi: 10.11862/CJIC.20260153
摘要:
为提升镍锌电池的能量密度与循环稳定性，通过水热法成功制备出Y3+掺杂的Ni(OH)2(Ni1-xYx(OH)2，x=0.01、0.03、0.05、0.07、0.10、0.15、0.20)。X射线衍射(XRD)结果表明，随着Y3+掺杂量的增加，Ni1-xYx(OH)2晶相结构从β相逐步转变为α-β中间相(Ni0.93Y0.07(OH)2)，最终转变为α相(Ni0.80Y0.20(OH)2)；扫描电镜(SEM)和透射电镜(TEM)结果显示，随着掺杂量的变化，产物形貌从纳米粒子、片状结构过渡到粒子团聚体；能量色散X射线谱(EDS)与X射线光电子能谱(XPS)分析证实Y3+成功掺杂进入Ni(OH)2晶格并保持稳定的+3价。循环伏安法(CV)、电化学阻抗谱(EIS)及循环寿命测试表明，当Y3+掺杂量(物质的量分数)为7%时，Ni0.93Y0.07(OH)2的电化学性能最优。将α-β中间相的Ni0.93Y0.07(OH)2作为正极与锌片负极组装成镍锌软包电池，结果显示，1 600次循环后，电池能量密度仍保持为182.03 Wh·kg-1，库仑效率维持在94%以上，优于未掺杂Ni(OH)2(β-Ni(OH)2)电极组装的电池。
为提升镍锌电池的能量密度与循环稳定性，通过水热法成功制备出Y3+掺杂的Ni(OH)2(Ni1-xYx(OH)2，x=0.01、0.03、0.05、0.07、0.10、0.15、0.20)。X射线衍射(XRD)结果表明，随着Y3+掺杂量的增加，Ni1-xYx(OH)2晶相结构从β相逐步转变为α-β中间相(Ni0.93Y0.07(OH)2)，最终转变为α相(Ni0.80Y0.20(OH)2)；扫描电镜(SEM)和透射电镜(TEM)结果显示，随着掺杂量的变化，产物形貌从纳米粒子、片状结构过渡到粒子团聚体；能量色散X射线谱(EDS)与X射线光电子能谱(XPS)分析证实Y3+成功掺杂进入Ni(OH)2晶格并保持稳定的+3价。循环伏安法(CV)、电化学阻抗谱(EIS)及循环寿命测试表明，当Y3+掺杂量(物质的量分数)为7%时，Ni0.93Y0.07(OH)2的电化学性能最优。将α-β中间相的Ni0.93Y0.07(OH)2作为正极与锌片负极组装成镍锌软包电池，结果显示，1 600次循环后，电池能量密度仍保持为182.03 Wh·kg-1，库仑效率维持在94%以上，优于未掺杂Ni(OH)2(β-Ni(OH)2)电极组装的电池。
2026, 42(5): 897-905
doi: 10.11862/CJIC.20250358
摘要:
合成了3种含吡啶基水杨醛席夫碱过渡金属配合物[Co(L)2]Cl (1)、[Ni(L)2(CH3OH)2] (2)和[Cu(L)2] (3)(HL=4-(二乙氨基)水杨醛缩2-(2-吡啶基)乙胺席夫碱)，利用红外光谱、元素分析和单晶X射线衍射等测试手段对配合物1~3进行了结构表征。采用MTT法对该系列配合物进行了体外抗肿瘤活性实验，结果表明：配体HL和配合物1对人卵巢癌细胞A2780、人非小细胞肺癌细胞A549和人三阴乳腺癌细胞MDA-MB-231的抗肿瘤活性都优于顺铂，其中，配合物1对人三阴乳腺癌细胞MDA-MB-231的抑制作用最强，其半数抑制浓度(IC50)为(7.8±0.3) μmol·L-1；细胞刮板实验表明随着配合物1浓度的增加，其对人三阴乳腺癌细胞MDA-MB-231的杀伤作用增强，其杀伤作用呈剂量依赖性。此外，还研究了配体HL和配合物1~3对金黄色葡萄球菌、大肠杆菌以及白色念珠菌的抑菌活性，结果表明：HL及其配合物1和3对金黄色葡萄球菌和白色念珠菌都有较好的抑菌活性，其中，配合物1对金黄色葡萄球菌抑菌效果达到了极度敏感；其最低抑制浓度(MIC)为0.64 mg·mL-1。
合成了3种含吡啶基水杨醛席夫碱过渡金属配合物[Co(L)2]Cl (1)、[Ni(L)2(CH3OH)2] (2)和[Cu(L)2] (3)(HL=4-(二乙氨基)水杨醛缩2-(2-吡啶基)乙胺席夫碱)，利用红外光谱、元素分析和单晶X射线衍射等测试手段对配合物1~3进行了结构表征。采用MTT法对该系列配合物进行了体外抗肿瘤活性实验，结果表明：配体HL和配合物1对人卵巢癌细胞A2780、人非小细胞肺癌细胞A549和人三阴乳腺癌细胞MDA-MB-231的抗肿瘤活性都优于顺铂，其中，配合物1对人三阴乳腺癌细胞MDA-MB-231的抑制作用最强，其半数抑制浓度(IC50)为(7.8±0.3) μmol·L-1；细胞刮板实验表明随着配合物1浓度的增加，其对人三阴乳腺癌细胞MDA-MB-231的杀伤作用增强，其杀伤作用呈剂量依赖性。此外，还研究了配体HL和配合物1~3对金黄色葡萄球菌、大肠杆菌以及白色念珠菌的抑菌活性，结果表明：HL及其配合物1和3对金黄色葡萄球菌和白色念珠菌都有较好的抑菌活性，其中，配合物1对金黄色葡萄球菌抑菌效果达到了极度敏感；其最低抑制浓度(MIC)为0.64 mg·mL-1。
2026, 42(5): 906-916
doi: 10.11862/CJIC.20250348
摘要:
以不同结构的含氮有机物为前驱体，采用无溶剂法制备了氮掺杂碳包裹Mo2N纳米颗粒，并系统探究了其析氢反应(HER)电催化性能。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼(Raman)光谱、扫描电子显微镜(SEM)及透射电子显微镜(TEM)，对材料的晶体结构、元素组成、孔结构及微观形貌进行了表征。结果表明，氮前驱体种类决定产物的晶体结构，进而显著影响HER催化性能。其中以盐酸胍为前驱体制得的MoNC-G样品的性能最优：酸性条件下，其在10 mA·cm-2的电流密度下对应的过电位为123 mV，Tafel斜率62.8 mV·dec-1；碱性条件下，对应的过电位低至76 mV，Tafel斜率为70.5 mV·dec-1。稳定性测试结果显示，MoNC-G经10 h计时电流测试后无明显电流衰减，且1 000次循环前后的线性扫描伏安法(LSV)曲线基本重合，表现出优异的长期稳定性与循环耐久性。
以不同结构的含氮有机物为前驱体，采用无溶剂法制备了氮掺杂碳包裹Mo2N纳米颗粒，并系统探究了其析氢反应(HER)电催化性能。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼(Raman)光谱、扫描电子显微镜(SEM)及透射电子显微镜(TEM)，对材料的晶体结构、元素组成、孔结构及微观形貌进行了表征。结果表明，氮前驱体种类决定产物的晶体结构，进而显著影响HER催化性能。其中以盐酸胍为前驱体制得的MoNC-G样品的性能最优：酸性条件下，其在10 mA·cm-2的电流密度下对应的过电位为123 mV，Tafel斜率62.8 mV·dec-1；碱性条件下，对应的过电位低至76 mV，Tafel斜率为70.5 mV·dec-1。稳定性测试结果显示，MoNC-G经10 h计时电流测试后无明显电流衰减，且1 000次循环前后的线性扫描伏安法(LSV)曲线基本重合，表现出优异的长期稳定性与循环耐久性。
2026, 42(5): 917-924
doi: 10.11862/CJIC.20260357
摘要:
以2，5-二溴对苯二甲酸为主配体(H2L)并引入中性含氮辅助配体1，3-二(1H-咪唑-1-基)苯(1，3-bib)、1，4-二(咪唑-1-基甲基)苯(1，4-bix)、1，4-二(1H-咪唑-1-基)丁烷(bbi)，与Zn(NO3)2·6H2O在溶剂热条件下反应，得到3种新型的配位聚合物1~3。配位聚合物{[Zn2(L)2(1，3-bib)2]·H2O}n (1)展现了一个1D双链的骨架结构。配位聚合物[Zn(L)(1，4-bix)]n (2)展现了二重穿插的2D骨架结构。每个锌离子之间通过L2-配体桥联形成1D的波浪链，链与链之间进一步通过1，4-bix配体桥联形成2D波浪状的网状结构。由于1，4-bix具有一定的柔性，2个相似的2D层状结构相互穿插，形成一个二重穿插的2D骨架结构。配位聚合物{[Zn2(L)2(bbi)2]·0.3DMF}n (3)展现了四重穿插的3D骨架结构。每个锌离子之间通过L2-配体和bbi配体连接，形成1D链状结构。链与链之间通过L2-配体连接形成2D层状结构，层与层之间进一步通过bbi配体连接形成3D的骨架结构。由于配合物骨架结构中孔道的存在，4个相同的3D骨架结构互相穿插形成一个更加复杂的四重穿插的3D骨架结构。配合物1~3均具有良好的热稳定性和可调控的荧光发射。
以2，5-二溴对苯二甲酸为主配体(H2L)并引入中性含氮辅助配体1，3-二(1H-咪唑-1-基)苯(1，3-bib)、1，4-二(咪唑-1-基甲基)苯(1，4-bix)、1，4-二(1H-咪唑-1-基)丁烷(bbi)，与Zn(NO3)2·6H2O在溶剂热条件下反应，得到3种新型的配位聚合物1~3。配位聚合物{[Zn2(L)2(1，3-bib)2]·H2O}n (1)展现了一个1D双链的骨架结构。配位聚合物[Zn(L)(1，4-bix)]n (2)展现了二重穿插的2D骨架结构。每个锌离子之间通过L2-配体桥联形成1D的波浪链，链与链之间进一步通过1，4-bix配体桥联形成2D波浪状的网状结构。由于1，4-bix具有一定的柔性，2个相似的2D层状结构相互穿插，形成一个二重穿插的2D骨架结构。配位聚合物{[Zn2(L)2(bbi)2]·0.3DMF}n (3)展现了四重穿插的3D骨架结构。每个锌离子之间通过L2-配体和bbi配体连接，形成1D链状结构。链与链之间通过L2-配体连接形成2D层状结构，层与层之间进一步通过bbi配体连接形成3D的骨架结构。由于配合物骨架结构中孔道的存在，4个相同的3D骨架结构互相穿插形成一个更加复杂的四重穿插的3D骨架结构。配合物1~3均具有良好的热稳定性和可调控的荧光发射。
2026, 42(5): 925-932
doi: 10.11862/CJIC.20250352
摘要:
基于简单水热法构筑了一种由纳米片自组装形成的三维花状δ-MnO2结构。该三维多孔结构能够捕获大量电解质离子并提高电极表面的Zn2+浓度，从而优化Zn2+传输路径并加速电极反应动力学过程。此外，花状交联结构有效提升了δ-MnO2电极的机械性能，使其在循环过程中发生缓慢的体积膨胀，结构维持稳定。基于δ-MnO2电极组装得到的水系锌离子电池(AZIBs)展现出优异的放电比容量(0.1 A·g-1下为358.2 mAh·g-1)和循环稳定性(1 000次循环后放电比容量仍保持为94.9 mAh·g-1)。
基于简单水热法构筑了一种由纳米片自组装形成的三维花状δ-MnO2结构。该三维多孔结构能够捕获大量电解质离子并提高电极表面的Zn2+浓度，从而优化Zn2+传输路径并加速电极反应动力学过程。此外，花状交联结构有效提升了δ-MnO2电极的机械性能，使其在循环过程中发生缓慢的体积膨胀，结构维持稳定。基于δ-MnO2电极组装得到的水系锌离子电池(AZIBs)展现出优异的放电比容量(0.1 A·g-1下为358.2 mAh·g-1)和循环稳定性(1 000次循环后放电比容量仍保持为94.9 mAh·g-1)。
2026, 42(5): 933-943
doi: 10.11862/CJIC.20250334
摘要:
将Ni2P/碳纳米管(CNT)复合物修饰于聚丙烯(PP)隔膜表面，构建“催化-阻隔”一体化界面，旨在加速多硫化锂(Li2Sn)的转化并抑制其穿梭效应。Ni2P/CNT优异的催化特性有效促进了Li2Sn的转化，改善了其氧化还原动力学性能，提高了活性材料的利用率，显著抑制了穿梭效应。采用Ni2P/CNT/PP隔膜的电池表现出优异的电化学性能，在1C(1C=1 675 mAh·g-1)下实现了高初始放电比容量(907 mAh·g-1)，经过800次循环后，平均每圈容量衰减率仅为0.047%，展现出良好的循环稳定性。
将Ni2P/碳纳米管(CNT)复合物修饰于聚丙烯(PP)隔膜表面，构建“催化-阻隔”一体化界面，旨在加速多硫化锂(Li2Sn)的转化并抑制其穿梭效应。Ni2P/CNT优异的催化特性有效促进了Li2Sn的转化，改善了其氧化还原动力学性能，提高了活性材料的利用率，显著抑制了穿梭效应。采用Ni2P/CNT/PP隔膜的电池表现出优异的电化学性能，在1C(1C=1 675 mAh·g-1)下实现了高初始放电比容量(907 mAh·g-1)，经过800次循环后，平均每圈容量衰减率仅为0.047%，展现出良好的循环稳定性。
2026, 42(5): 944-958
doi: 10.11862/CJIC.20250323
摘要:
针对单一电化学反应体系中活性组分利用效率受限的问题，构建了泡沫Ti/FeCo-Fe2O3-CoFe2O4/SnO2-Sb(简称为Ti/ FeCoO/SnO2-Sb)复合阳极与过氧单硫酸盐(PMS)协同作用的电化学活化体系(Ti/FeCoO/SnO2-Sb+PMS)。为突破传统SnO2-Sb阳极在界面反应动力学与服役稳定性方面的固有瓶颈，提出以FeCoO作为关键中间层与SnO2-Sb构筑分级复合电极的策略。借助Fe、Co双金属位点的协同效应重构电极界面微环境，从而实现PMS活化效率与体系稳定性的同步提升。性能评估结果表明，在Ti/FeCoO/SnO2-Sb+PMS体系中，Ti/FeCoO/SnO2-Sb对甲基橙(MO)表现出最优的去除能力与矿化水平，其化学需氧量(COD)去除率显著高于对照体系；同时，酸性条件更有利于PMS活化，从而进一步强化了MO的降解动力学性能。相较于未添加FeCoO体系(Ti/SnO2-Sb+PMS)，Ti/FeCoO/SnO2-Sb+PMS复合体系展现出更为突出的整体性能优势。在此基础上，结合电化学表征、电子顺磁共振(EPR)与密度泛函理论(DFT)计算对机理进行解析，结果表明，性能提升主要归因于复合界面有效促进了直接电子转移(DET)过程并强化了PMS的电化学活化；反应过程中，超氧阴离子自由基(·O2-)、羟基自由基(·OH)、硫酸根自由基(SO4·-)和单线态氧(1O2)协同作用，实现了MO共轭结构的高效破坏与持续深度氧化。
针对单一电化学反应体系中活性组分利用效率受限的问题，构建了泡沫Ti/FeCo-Fe2O3-CoFe2O4/SnO2-Sb(简称为Ti/ FeCoO/SnO2-Sb)复合阳极与过氧单硫酸盐(PMS)协同作用的电化学活化体系(Ti/FeCoO/SnO2-Sb+PMS)。为突破传统SnO2-Sb阳极在界面反应动力学与服役稳定性方面的固有瓶颈，提出以FeCoO作为关键中间层与SnO2-Sb构筑分级复合电极的策略。借助Fe、Co双金属位点的协同效应重构电极界面微环境，从而实现PMS活化效率与体系稳定性的同步提升。性能评估结果表明，在Ti/FeCoO/SnO2-Sb+PMS体系中，Ti/FeCoO/SnO2-Sb对甲基橙(MO)表现出最优的去除能力与矿化水平，其化学需氧量(COD)去除率显著高于对照体系；同时，酸性条件更有利于PMS活化，从而进一步强化了MO的降解动力学性能。相较于未添加FeCoO体系(Ti/SnO2-Sb+PMS)，Ti/FeCoO/SnO2-Sb+PMS复合体系展现出更为突出的整体性能优势。在此基础上，结合电化学表征、电子顺磁共振(EPR)与密度泛函理论(DFT)计算对机理进行解析，结果表明，性能提升主要归因于复合界面有效促进了直接电子转移(DET)过程并强化了PMS的电化学活化；反应过程中，超氧阴离子自由基(·O2-)、羟基自由基(·OH)、硫酸根自由基(SO4·-)和单线态氧(1O2)协同作用，实现了MO共轭结构的高效破坏与持续深度氧化。
2026, 42(5): 959-968
doi: 10.11862/CJIC.20250320
摘要:
通过简单的一步水热法合成了负载石墨烯量子点(GQDs)的SnS2复合纳米片光催化剂(GQDs/SnS2)，并系统探讨了碳源(柠檬酸钠和柠檬酸)对光催化还原Cr(Ⅵ)性能的影响。利用扫描电子显微镜、透射电子显微镜、X射线衍射、氮气吸附-脱附测试及X射线光电子能谱对材料进行了表征。结果表明，GQDs成功负载于六方相SnS2纳米片表面。其中，以柠檬酸钠为碳源制备的GQDs/SnS2在60 min内对Cr(Ⅵ)的还原率达到100%，而纯SnS2对Cr(Ⅵ)的还原率仅为56%。GQDs的引入可显著增大催化剂的比表面积，拓宽光谱吸收范围并加速光生载流子的分离，从而大幅提升其光催化还原性能。
通过简单的一步水热法合成了负载石墨烯量子点(GQDs)的SnS2复合纳米片光催化剂(GQDs/SnS2)，并系统探讨了碳源(柠檬酸钠和柠檬酸)对光催化还原Cr(Ⅵ)性能的影响。利用扫描电子显微镜、透射电子显微镜、X射线衍射、氮气吸附-脱附测试及X射线光电子能谱对材料进行了表征。结果表明，GQDs成功负载于六方相SnS2纳米片表面。其中，以柠檬酸钠为碳源制备的GQDs/SnS2在60 min内对Cr(Ⅵ)的还原率达到100%，而纯SnS2对Cr(Ⅵ)的还原率仅为56%。GQDs的引入可显著增大催化剂的比表面积，拓宽光谱吸收范围并加速光生载流子的分离，从而大幅提升其光催化还原性能。
2026, 42(5): 969-979
doi: 10.11862/CJIC.20250317
摘要:
合成了2种含噻吩基团的配体[5，5′-二(噻吩-2-基)-2，2′-联吡啶(tp-bpy-tp)和3，8-二溴-1，10-菲咯啉(tp-phen-tp)]，并分别与Co(NO3)2·6H2O和Ni(NO3)2·6H2O配位，制备了3种金属配合物([Co(tp-bpy-tp)3](NO3)2、[Ni(tp-bpy-tp)3](NO3)2和[Ni(tp-phen-tp)3](NO3)2)。在无水FeCl3催化下，通过聚合反应进一步合成了金属配位聚合物[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n。以苯酚溶液模拟酚类废水，考察了聚合物的光催化降解苯酚性能。结果表明，在氙灯光源照射2 h后，[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n对苯酚的降解率分别达到74.37%、62.98%和83.45%。
合成了2种含噻吩基团的配体[5，5′-二(噻吩-2-基)-2，2′-联吡啶(tp-bpy-tp)和3，8-二溴-1，10-菲咯啉(tp-phen-tp)]，并分别与Co(NO3)2·6H2O和Ni(NO3)2·6H2O配位，制备了3种金属配合物([Co(tp-bpy-tp)3](NO3)2、[Ni(tp-bpy-tp)3](NO3)2和[Ni(tp-phen-tp)3](NO3)2)。在无水FeCl3催化下，通过聚合反应进一步合成了金属配位聚合物[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n。以苯酚溶液模拟酚类废水，考察了聚合物的光催化降解苯酚性能。结果表明，在氙灯光源照射2 h后，[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n对苯酚的降解率分别达到74.37%、62.98%和83.45%。
2026, 42(5): 980-990
doi: 10.11862/CJIC.20250304
摘要:
设计并制备了一种基于银(Ag)纳米颗粒复合的ZIF-8包覆钙钛矿纳米晶(Ag@CsPbBr3@ZIF-8)的表面增强拉曼散射(SERS)复合基底。与纯Ag基底相比，该复合基底具备良好的水稳定性，在水相中能显著增强芘分子的拉曼信号。通过光谱特征分析建立拟合方程，结果显示该复合基底对芘分子具有高灵敏检测性，检测限低至8.58 μg·L-1。加标回收率实验中，芘的回收率为97.6%~109.2%，相对标准偏差(RSD)为1.12%~7.91%，表明该基底具有良好的重复性和对芘分子检测的特异性。
设计并制备了一种基于银(Ag)纳米颗粒复合的ZIF-8包覆钙钛矿纳米晶(Ag@CsPbBr3@ZIF-8)的表面增强拉曼散射(SERS)复合基底。与纯Ag基底相比，该复合基底具备良好的水稳定性，在水相中能显著增强芘分子的拉曼信号。通过光谱特征分析建立拟合方程，结果显示该复合基底对芘分子具有高灵敏检测性，检测限低至8.58 μg·L-1。加标回收率实验中，芘的回收率为97.6%~109.2%，相对标准偏差(RSD)为1.12%~7.91%，表明该基底具有良好的重复性和对芘分子检测的特异性。
2026, 42(5): 991-1002
doi: 10.11862/CJIC.20250302
摘要:
以稀土硬脂酸盐为前驱体，乙醇-水-油酸混合试剂为溶剂，采用化学方法合成NaYF4∶Yb，Er上转换荧光微米材料；再以NaYF4∶Yb，Er为基质材料，在其表面依次键合1，4-苯二甲酸(PTA)、Eu3+离子和1，10-菲咯啉(Phen)，制备具有双重荧光性质的NaYF4∶Yb，Er-(PTA)Eu(Phen)微米复合材料。经表征发现，复合材料的形貌为表面结合了纳米球的微米棒，在波长为200~310 nm范围内和976 nm处分别产生紫外和近红外吸收，受254和980 nm光源激发分别产生616 nm红色下转换荧光和540 nm绿色上转换荧光。将微米材料、十二烷基硫酸钠与水配制成微米悬浮液，用于潜在手印的悬浮液法显现和双模式荧光增强。经过优化实验，确定手印显现的最优条件如下：NaYF4∶Yb，Er-(PTA)Eu(Phen)的质量分数为1.67%，十二烷基硫酸钠的质量分数为0.50‰，显现时间为30 s。结果表明，手印显现结合荧光增强具有较高的对比度、灵敏度和选择性，荧光增强模式对对比度的影响较大，而对灵敏度和选择性基本没有影响。
以稀土硬脂酸盐为前驱体，乙醇-水-油酸混合试剂为溶剂，采用化学方法合成NaYF4∶Yb，Er上转换荧光微米材料；再以NaYF4∶Yb，Er为基质材料，在其表面依次键合1，4-苯二甲酸(PTA)、Eu3+离子和1，10-菲咯啉(Phen)，制备具有双重荧光性质的NaYF4∶Yb，Er-(PTA)Eu(Phen)微米复合材料。经表征发现，复合材料的形貌为表面结合了纳米球的微米棒，在波长为200~310 nm范围内和976 nm处分别产生紫外和近红外吸收，受254和980 nm光源激发分别产生616 nm红色下转换荧光和540 nm绿色上转换荧光。将微米材料、十二烷基硫酸钠与水配制成微米悬浮液，用于潜在手印的悬浮液法显现和双模式荧光增强。经过优化实验，确定手印显现的最优条件如下：NaYF4∶Yb，Er-(PTA)Eu(Phen)的质量分数为1.67%，十二烷基硫酸钠的质量分数为0.50‰，显现时间为30 s。结果表明，手印显现结合荧光增强具有较高的对比度、灵敏度和选择性，荧光增强模式对对比度的影响较大，而对灵敏度和选择性基本没有影响。
2026, 42(5): 1003-1014
doi: 10.11862/CJIC.20250238
摘要:
采用静电纺丝技术制备了多孔氮掺杂碳纳米纤维(PNCNFs)，随后通过高温碳化及还原处理，成功合成了一系列PNCNFs锚定PtRu合金材料(PtRu/PNCNFs)。碳纳米纤维中氮的掺杂引入了大量的亲水性基团，能够显著增强材料与电解液之间的润湿性，有助于离子传输和整体电化学性能的进一步改善；同时PNCNFs具有较大的比表面积，PtRu合金的存在从一定程度上增加了其活性位点。此外，高温下形成的多孔结构使得PtRu合金能够均匀分散在材料表面，有利于调节材料的电子结构，促进电子转移，提升析氢反应(HER)性能。结果显示，经过500 ℃处理的PNCNFs(PtRu/PNCNFs-500)在1 mol·L-1 KOH和含1 mol·L-1 KOH的海水溶液中均表现出优异的HER性能。在电流密度为10 mA·cm-2时，PtRu/PNCNFs-500的析氢过电位分别为15.8和18.3 mV，塔菲尔(Tafel)斜率分别为20.58和20.65 mV·dec-1，性能显著优于经300、400和600 ℃处理的PNCNFs，并均展现出良好的HER稳定性。
采用静电纺丝技术制备了多孔氮掺杂碳纳米纤维(PNCNFs)，随后通过高温碳化及还原处理，成功合成了一系列PNCNFs锚定PtRu合金材料(PtRu/PNCNFs)。碳纳米纤维中氮的掺杂引入了大量的亲水性基团，能够显著增强材料与电解液之间的润湿性，有助于离子传输和整体电化学性能的进一步改善；同时PNCNFs具有较大的比表面积，PtRu合金的存在从一定程度上增加了其活性位点。此外，高温下形成的多孔结构使得PtRu合金能够均匀分散在材料表面，有利于调节材料的电子结构，促进电子转移，提升析氢反应(HER)性能。结果显示，经过500 ℃处理的PNCNFs(PtRu/PNCNFs-500)在1 mol·L-1 KOH和含1 mol·L-1 KOH的海水溶液中均表现出优异的HER性能。在电流密度为10 mA·cm-2时，PtRu/PNCNFs-500的析氢过电位分别为15.8和18.3 mV，塔菲尔(Tafel)斜率分别为20.58和20.65 mV·dec-1，性能显著优于经300、400和600 ℃处理的PNCNFs，并均展现出良好的HER稳定性。
2026, 42(5): 1015-1025
doi: 10.11862/CJIC.20250366
摘要:
Herein, ratiometric fluorescence-based carbon dots (N-CDs) with blue emission were prepared by using simple one-step hydrothermal methods from benzimidazole and L-tryptophan as precursors. Dual emission peaks were observed at 356 and 442 nm under the excitation wavelength of 303 nm. Upon addition of sulfide ions (S2-), the fluorescence intensity at 442 nm decreased significantly, while that at 356 nm increased. The F442/F356 intensity ratio (where F356 and F442 refer to the fluorescence intensity at 356 and 442 nm, respectively) exhibited a linear relationship with the concentration of S2- (0-60.0 μmol·L-1), and the detection limit was determined to be 0.076 μmol·L-1. The fluorescence detection mechanism was ascribed to the static quenching effect. Furthermore, this fluorescence probe was successfully used for the determination of S2- in real samples with satisfactory recoveries. Finally, the analytical greenness metric for sample preparation (AGREEprep) and blue applicability grade index (BAGI) tools indicated the high sustainability of this platform.
Herein, ratiometric fluorescence-based carbon dots (N-CDs) with blue emission were prepared by using simple one-step hydrothermal methods from benzimidazole and L-tryptophan as precursors. Dual emission peaks were observed at 356 and 442 nm under the excitation wavelength of 303 nm. Upon addition of sulfide ions (S2-), the fluorescence intensity at 442 nm decreased significantly, while that at 356 nm increased. The F442/F356 intensity ratio (where F356 and F442 refer to the fluorescence intensity at 356 and 442 nm, respectively) exhibited a linear relationship with the concentration of S2- (0-60.0 μmol·L-1), and the detection limit was determined to be 0.076 μmol·L-1. The fluorescence detection mechanism was ascribed to the static quenching effect. Furthermore, this fluorescence probe was successfully used for the determination of S2- in real samples with satisfactory recoveries. Finally, the analytical greenness metric for sample preparation (AGREEprep) and blue applicability grade index (BAGI) tools indicated the high sustainability of this platform.
2026, 42(5): 1026-1038
doi: 10.11862/CJIC.20250364
摘要:
To enhance the low-temperature activity and anti-sintering performance of Ni-based catalysts for CO methanation, mesoporous CeO2 supports with a confined structure were synthesized via a hydrothermal method. The effects of three Ni loading methods—incipient wetness impregnation, co-precipitation, and bis(cyclopentadienyl)nickel sublimation—on catalytic performance were systematically compared. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption test, hydrogen temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), revealed the critical influence of the loading method on Ni species dispersion, particle size, and metal-support interaction. The results indicated that all three mesoporous Ni/CeO2 catalysts exhibited excellent anti-sintering properties due to the confinement effect of the support. However, their low-temperature activities differed significantly, primarily determined by the specific state of Ni. In the NC-B catalyst prepared by bis(cyclopentadienyl)nickel sublimation, the interaction between Ni species and the support was relatively weak. After reduction, this method yielded highly dispersed metallic Ni nanoparticles, increasing the number of low-temperature active sites. Consequently, the NC-B catalyst achieved 98% CO conversion rate and 100% CH4 selectivity at 300 ℃, demonstrating the optimal low-temperature methanation performance.
To enhance the low-temperature activity and anti-sintering performance of Ni-based catalysts for CO methanation, mesoporous CeO2 supports with a confined structure were synthesized via a hydrothermal method. The effects of three Ni loading methods—incipient wetness impregnation, co-precipitation, and bis(cyclopentadienyl)nickel sublimation—on catalytic performance were systematically compared. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption test, hydrogen temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), revealed the critical influence of the loading method on Ni species dispersion, particle size, and metal-support interaction. The results indicated that all three mesoporous Ni/CeO2 catalysts exhibited excellent anti-sintering properties due to the confinement effect of the support. However, their low-temperature activities differed significantly, primarily determined by the specific state of Ni. In the NC-B catalyst prepared by bis(cyclopentadienyl)nickel sublimation, the interaction between Ni species and the support was relatively weak. After reduction, this method yielded highly dispersed metallic Ni nanoparticles, increasing the number of low-temperature active sites. Consequently, the NC-B catalyst achieved 98% CO conversion rate and 100% CH4 selectivity at 300 ℃, demonstrating the optimal low-temperature methanation performance.
Syntheses and photocatalytic CO2 reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters
2026, 42(5): 1039-1047
doi: 10.11862/CJIC.20250353
摘要:
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
2026, 42(5): 1048-1062
doi: 10.11862/CJIC.20250330
摘要:
Two complexes [Cd(L)(CH3O)(CH3COO)]·CH3OH·(CH3)2NH (C1) and [Mn(L)Cl2(CH3OH)] (C2) were synthesized by reacting a new imidazole-bearing ligand 4-(1H-imidazol-1-yl)-N′-(pyridin-2-ylmethylene)benzohydrazide (L) with cadmium and manganese salts, respectively. The ligand was characterized by 1H NMR and 13C NMR spectroscopy, while the complexes were analyzed by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, and UV-Vis spectroscopy. Complex C1 features a 1D zigzag chain structure formed by alternating connections of one ligand and one metal ion. In contrast, complex C2 exhibits a mononuclear molecular structure, where each unit consists of one ligand connected to one manganese ion. Both complexes further form a 3D structure through π-π interactions and intermolecular hydrogen bonds. Cell proliferation assays conducted on four tumor cell lines and one normal cell line revealed that both C1 and C2 exhibited significantly stronger inhibition of tumor cell growth compared to the ligand L. Notably, C1 demonstrated superior anti-proliferative activity against A549 and A2780 cells relative to cisplatin, while showing comparable cytotoxicity toward SMMC-7721 cells. Further mechanistic studies indicated that C1 induces apoptosis in both SMMC-7721 and A549 tumor cells, suppresses the invasion and migration of SMMC-7721 cells, and arrests the cell cycle at the G0/G1 phase.
Two complexes [Cd(L)(CH3O)(CH3COO)]·CH3OH·(CH3)2NH (C1) and [Mn(L)Cl2(CH3OH)] (C2) were synthesized by reacting a new imidazole-bearing ligand 4-(1H-imidazol-1-yl)-N′-(pyridin-2-ylmethylene)benzohydrazide (L) with cadmium and manganese salts, respectively. The ligand was characterized by 1H NMR and 13C NMR spectroscopy, while the complexes were analyzed by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, and UV-Vis spectroscopy. Complex C1 features a 1D zigzag chain structure formed by alternating connections of one ligand and one metal ion. In contrast, complex C2 exhibits a mononuclear molecular structure, where each unit consists of one ligand connected to one manganese ion. Both complexes further form a 3D structure through π-π interactions and intermolecular hydrogen bonds. Cell proliferation assays conducted on four tumor cell lines and one normal cell line revealed that both C1 and C2 exhibited significantly stronger inhibition of tumor cell growth compared to the ligand L. Notably, C1 demonstrated superior anti-proliferative activity against A549 and A2780 cells relative to cisplatin, while showing comparable cytotoxicity toward SMMC-7721 cells. Further mechanistic studies indicated that C1 induces apoptosis in both SMMC-7721 and A549 tumor cells, suppresses the invasion and migration of SMMC-7721 cells, and arrests the cell cycle at the G0/G1 phase.
2026, 42(5): 1063-1072
doi: 10.11862/CJIC.20250345
摘要:
Three zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers, namely [Zn(μ-cada)(bipy)(H2O)]n (1), [Zn(μ3-cada)(phen)·H2O]n (2), and [Cd(μ3-cada)(phen)]n (3), have been constructed hydrothermally at 160 ℃ using bis(4-carboxyphenyl)urea (H2cada), 2, 2′-bipyridine (bipy)/1, 10-phenanthroline (phen), and zinc and cadmium chlorides. The three complexes were fully characterized by infrared spectroscopy, element analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that complexes 1-3 form crystals in the monoclinic P21/n, monoclinic I2/a, and orthorhombic Pbcn space groups. These complexes all possess different 1D chain structures. Complexes 1 and 2 demonstrate substantial catalytic efficiency in the Knoevenagel condensation under ambient temperature conditions.
Three zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers, namely [Zn(μ-cada)(bipy)(H2O)]n (1), [Zn(μ3-cada)(phen)·H2O]n (2), and [Cd(μ3-cada)(phen)]n (3), have been constructed hydrothermally at 160 ℃ using bis(4-carboxyphenyl)urea (H2cada), 2, 2′-bipyridine (bipy)/1, 10-phenanthroline (phen), and zinc and cadmium chlorides. The three complexes were fully characterized by infrared spectroscopy, element analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that complexes 1-3 form crystals in the monoclinic P21/n, monoclinic I2/a, and orthorhombic Pbcn space groups. These complexes all possess different 1D chain structures. Complexes 1 and 2 demonstrate substantial catalytic efficiency in the Knoevenagel condensation under ambient temperature conditions.
2026, 42(5): 1073-1084
doi: 10.11862/CJIC.20250328
摘要:
To investigate the antitumor properties of copper(Ⅱ) complexes, a series of Cu(Ⅱ) complexes (C1-C3) derived from 6, 7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized. These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin. Among them, C3 had the highest antitumor activity against MDA-MB-231 cells, with a half maximal inhibitory concentration (IC50) value of 1.42 μmol·L-1. Moreover, C3 effectively inhibited the growth of 3D multicellular spheres. Mechanistically, it induced significant reactive oxygen species (ROS) generation, initiating a dual-pathway cytotoxic effect. On the one hand, it triggers endoplasmic reticulum stress and inhibits the activity of the related protein, protein disulfide isomerase (PDI). On the other hand, it induces mitochondrial dysfunction. These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.
To investigate the antitumor properties of copper(Ⅱ) complexes, a series of Cu(Ⅱ) complexes (C1-C3) derived from 6, 7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized. These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin. Among them, C3 had the highest antitumor activity against MDA-MB-231 cells, with a half maximal inhibitory concentration (IC50) value of 1.42 μmol·L-1. Moreover, C3 effectively inhibited the growth of 3D multicellular spheres. Mechanistically, it induced significant reactive oxygen species (ROS) generation, initiating a dual-pathway cytotoxic effect. On the one hand, it triggers endoplasmic reticulum stress and inhibits the activity of the related protein, protein disulfide isomerase (PDI). On the other hand, it induces mitochondrial dysfunction. These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.
2026, 42(5): 1085-1095
doi: 10.11862/CJIC.20250321
摘要:
To develop highly stable and active Ru complex catalysts for CO2 hydrogenation, we synthesized Ru complexes bearing rigid pincer-type tridentate NNN (pyrazole-pyridine-pyrazole) ligands and weakly coordinated triphenylphosphine (PPh3) ligands. The NNN ligands can strongly chelate with the Ru metal center, contributing to the overall robustness of the catalytic system. Meanwhile, PPh3 can easily dissociate to form vacant coordination sites, thereby enhancing catalytic activity. As a result, the Ru(Ⅱ)-NNN complex [Ru(L-NNN)Cl(PPh3)2]Cl (1, L-NNN=2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) was not only quite stable, but also showed high activity for CO2 hydrogenation to formate, achieving a TON of up to 150 000. In the mechanism study, based on the results of in-situ NMR, in-situ HPLC-HRMS spectra, and density functional theory calculations, it is speculated that the active intermediates with empty coordination sites are highly active species in CO2 hydrogenation.
To develop highly stable and active Ru complex catalysts for CO2 hydrogenation, we synthesized Ru complexes bearing rigid pincer-type tridentate NNN (pyrazole-pyridine-pyrazole) ligands and weakly coordinated triphenylphosphine (PPh3) ligands. The NNN ligands can strongly chelate with the Ru metal center, contributing to the overall robustness of the catalytic system. Meanwhile, PPh3 can easily dissociate to form vacant coordination sites, thereby enhancing catalytic activity. As a result, the Ru(Ⅱ)-NNN complex [Ru(L-NNN)Cl(PPh3)2]Cl (1, L-NNN=2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) was not only quite stable, but also showed high activity for CO2 hydrogenation to formate, achieving a TON of up to 150 000. In the mechanism study, based on the results of in-situ NMR, in-situ HPLC-HRMS spectra, and density functional theory calculations, it is speculated that the active intermediates with empty coordination sites are highly active species in CO2 hydrogenation.
2026, 42(5): 1096-1112
doi: 10.11862/CJIC.20250311
摘要:
Bi2O3@BiVO4 composites were synthesized using the solvothermal method with ethylene glycol as the solvent. Bi2O3 was grown on the surface of BiVO4 by regulating the reaction temperature. The adsorption performance of the composite for rhodamine B (RhB) was investigated. The results indicate that the reaction temperature significantly impacts the morphology and adsorption performance of Bi2O3@BiVO4. The Bi2O3@BiVO4 composite prepared at 180 ℃ (180-BO@BVO) consisted of nanoparticles with an average size of 7 nm, featuring a higher concentration of oxygen vacancies on the surface, but with a lower specific surface area (only 1.2 m2·g-1). 180-BO@BVO, with oxygen species adsorbed at surface oxygen vacancies carrying a negative charge, achieved an impressive RhB removal efficiency of up to 83.0% through electrostatic interaction with RhB. The adsorption process follows the Langmuir isotherm and the pseudo-second-order kinetic model, suggesting that it is predominantly governed by chemical adsorption. After five cycles of adsorption experiments, the removal efficiency of RhB by composites remained basically unchanged (more than 80%), demonstrating excellent regeneration performance.
Bi2O3@BiVO4 composites were synthesized using the solvothermal method with ethylene glycol as the solvent. Bi2O3 was grown on the surface of BiVO4 by regulating the reaction temperature. The adsorption performance of the composite for rhodamine B (RhB) was investigated. The results indicate that the reaction temperature significantly impacts the morphology and adsorption performance of Bi2O3@BiVO4. The Bi2O3@BiVO4 composite prepared at 180 ℃ (180-BO@BVO) consisted of nanoparticles with an average size of 7 nm, featuring a higher concentration of oxygen vacancies on the surface, but with a lower specific surface area (only 1.2 m2·g-1). 180-BO@BVO, with oxygen species adsorbed at surface oxygen vacancies carrying a negative charge, achieved an impressive RhB removal efficiency of up to 83.0% through electrostatic interaction with RhB. The adsorption process follows the Langmuir isotherm and the pseudo-second-order kinetic model, suggesting that it is predominantly governed by chemical adsorption. After five cycles of adsorption experiments, the removal efficiency of RhB by composites remained basically unchanged (more than 80%), demonstrating excellent regeneration performance.
2026, 42(5): 1113-1120
doi: 10.11862/CJIC.20250298
摘要:
To address the challenges of poor solubility and difficult recyclability of powdered metal-organic frameworks (MOFs), a Eu-based MOF complex, [EuNa(L)(H2O)3]·2H2O (Eu/Na-MOF), was synthesized by the hydrothermal method using 3,5-bis(3,5-dicarboxyphenyl)-1H-1,2,4-triazole (H4L) as the ligand in this study. Systematic characterization and performance evaluation revealed that the complex exhibits a unique 3D structure, high phase purity, excellent thermal stability, and outstanding luminescent properties. Furthermore, the complex was encapsulated in poly(methyl methacrylate) (PMMA) to fabricate a flexible and water-washable composite fluorescent film (Eu/Na-MOF/PMMA). Based on static and dynamic quenching mechanisms, respectively, the film enables reversible detection of tryptamine and Cr2O72- ions in aqueous solutions, demonstrating high selectivity, stability, and portability.
To address the challenges of poor solubility and difficult recyclability of powdered metal-organic frameworks (MOFs), a Eu-based MOF complex, [EuNa(L)(H2O)3]·2H2O (Eu/Na-MOF), was synthesized by the hydrothermal method using 3,5-bis(3,5-dicarboxyphenyl)-1H-1,2,4-triazole (H4L) as the ligand in this study. Systematic characterization and performance evaluation revealed that the complex exhibits a unique 3D structure, high phase purity, excellent thermal stability, and outstanding luminescent properties. Furthermore, the complex was encapsulated in poly(methyl methacrylate) (PMMA) to fabricate a flexible and water-washable composite fluorescent film (Eu/Na-MOF/PMMA). Based on static and dynamic quenching mechanisms, respectively, the film enables reversible detection of tryptamine and Cr2O72- ions in aqueous solutions, demonstrating high selectivity, stability, and portability.
