-
-
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。
- 影响因子: 0.7
期刊内检索
期刊内热点文章
2026, 42(3): 441-452
doi: 10.11862/CJIC.20250303
摘要:
柠檬酸三丁酯(tributyl citrate，TBC)是一种低毒、相容性好、可降解的绿色环保增塑剂。与传统生产TBC所用的浓硫酸催化剂相比，杂多酸(heteropolyacid，HPA)作为固体超强酸具有不挥发、不腐蚀设备的优点，但其价格昂贵且难以回收。为实现HPA的循环利用，采用不同载体负载HPA制备的负载型催化剂具有比表面积大、易于分离的特点，在TBC绿色合成中展现出广阔的应用前景。本文综述了以金属氧化物、碳材料、分子筛、离子液体等为载体，通过表面负载、内部封装及离子键合等方式负载HPA的催化剂在催化合成TBC方面的研究进展及其在TBC生产工艺中的应用。如何增强HPA与载体之间的相互作用力是突破该类材料工业化应用瓶颈的关键问题。以金属有机框架(MOFs)和共价有机框架(COFs)为载体负载HPA所构建的新型多金属氧酸盐金属有机框架(POMOFs)和多金属氧酸盐共价有机框架(POMCOFs)，可通过内部封装有效减少HPA催化剂的流失。本文系统总结了不同载体在催化活性、构效关系及与新型工艺适配性方面的特点与局限，旨在为开发高效、稳定、环境友好的合成TBC催化剂提供参考。
柠檬酸三丁酯(tributyl citrate，TBC)是一种低毒、相容性好、可降解的绿色环保增塑剂。与传统生产TBC所用的浓硫酸催化剂相比，杂多酸(heteropolyacid，HPA)作为固体超强酸具有不挥发、不腐蚀设备的优点，但其价格昂贵且难以回收。为实现HPA的循环利用，采用不同载体负载HPA制备的负载型催化剂具有比表面积大、易于分离的特点，在TBC绿色合成中展现出广阔的应用前景。本文综述了以金属氧化物、碳材料、分子筛、离子液体等为载体，通过表面负载、内部封装及离子键合等方式负载HPA的催化剂在催化合成TBC方面的研究进展及其在TBC生产工艺中的应用。如何增强HPA与载体之间的相互作用力是突破该类材料工业化应用瓶颈的关键问题。以金属有机框架(MOFs)和共价有机框架(COFs)为载体负载HPA所构建的新型多金属氧酸盐金属有机框架(POMOFs)和多金属氧酸盐共价有机框架(POMCOFs)，可通过内部封装有效减少HPA催化剂的流失。本文系统总结了不同载体在催化活性、构效关系及与新型工艺适配性方面的特点与局限，旨在为开发高效、稳定、环境友好的合成TBC催化剂提供参考。
2026, 42(3): 453-466
doi: 10.11862/CJIC.20250295
摘要:
硫化铜(CuS)作为一种过渡金属硫族化合物，因其独特的电学和光学性质，在水体污染物去除领域展现出吸附和光催化应用的潜力。然而，CuS光生电子-空穴对复合速率高、光腐蚀稳定性差等关键缺陷限制了其实际应用。为克服这些瓶颈，离子掺杂策略被广泛用于提升CuS的光稳定性和光催化活性。本文系统综述了离子掺杂CuS纳米材料的合成方法，重点阐述了微波水热合成法的高效性与应用优势，深入分析了离子掺杂对其能带结构、缺陷态及载流子动力学的影响机制，并对2020—2025年间离子掺杂CuS在光催化与能源领域的最新研究进展进行了归纳与评述。
硫化铜(CuS)作为一种过渡金属硫族化合物，因其独特的电学和光学性质，在水体污染物去除领域展现出吸附和光催化应用的潜力。然而，CuS光生电子-空穴对复合速率高、光腐蚀稳定性差等关键缺陷限制了其实际应用。为克服这些瓶颈，离子掺杂策略被广泛用于提升CuS的光稳定性和光催化活性。本文系统综述了离子掺杂CuS纳米材料的合成方法，重点阐述了微波水热合成法的高效性与应用优势，深入分析了离子掺杂对其能带结构、缺陷态及载流子动力学的影响机制，并对2020—2025年间离子掺杂CuS在光催化与能源领域的最新研究进展进行了归纳与评述。
2026, 42(3): 467-478
doi: 10.11862/CJIC.20250347
摘要:
To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks, Pd-catalyzed one-pot reactions between pyridyl-substituted nido-carboranes and alkynes directly afford two distinct types of 2D-3D fused carboranyl polycyclic compounds: 3a-3f, 4a-4d. The structures of this series of compounds were characterized by nuclear magnetic resonance spectroscopy, single-crystal X-ray diffraction, and high-resolution mass spectrometry, and a plausible reaction mechanism was proposed. Crystal structures reveal that the multiple rings in such 2D-3D fused carboranyl polycyclic compounds exhibit a certain degree of coplanarity. Furthermore, these compounds exhibited properties distinct from those of conventional 2D polycyclic systems.
To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks, Pd-catalyzed one-pot reactions between pyridyl-substituted nido-carboranes and alkynes directly afford two distinct types of 2D-3D fused carboranyl polycyclic compounds: 3a-3f, 4a-4d. The structures of this series of compounds were characterized by nuclear magnetic resonance spectroscopy, single-crystal X-ray diffraction, and high-resolution mass spectrometry, and a plausible reaction mechanism was proposed. Crystal structures reveal that the multiple rings in such 2D-3D fused carboranyl polycyclic compounds exhibit a certain degree of coplanarity. Furthermore, these compounds exhibited properties distinct from those of conventional 2D polycyclic systems.
2026, 42(3): 593-605
doi: 10.11862/CJIC.20250278
摘要:
In this study, a nickel-based MOF {(NH2(CH3)2)2[Ni3(O)(L)3(NH(CH3)2)3]}n (Ni3-MOF), with pore sizes of approximately 1.6 nm×1.6 nm, was synthesized by reacting 4, 4′-biphenyldicarboxylic acid (H2L) with Ni(NO3)2·6H2O in an N, N-dimethylformamide (DMF) solution. The nanoscale adsorbent Ni3-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni3-MOF. It exhibited a maximum equilibrium tetracycline (TC) adsorption capacity of 358.2 mg·g-1 at its isoelectric point (pH=6.50), outperforming most reported MOF-based adsorbents. This exceptional performance is likely attributed to the well-matched pore size of Ni3-MOF-N (1.6 nm×1.6 nm) and the molecular dimensions of TC (0.8 nm×1.2 nm), combined with the presence of partial Ni(Ⅱ) sites on the surface of Ni3-MOF-N. These features collectively facilitate effective TC adsorption through a combination of pore filling, electrostatic attraction, hydrogen bonding, surface complexation, and π-π interactions. Recycling experiments demonstrated that Ni3-MOF-N possesses excellent structural stability and consistent adsorption performance.
In this study, a nickel-based MOF {(NH2(CH3)2)2[Ni3(O)(L)3(NH(CH3)2)3]}n (Ni3-MOF), with pore sizes of approximately 1.6 nm×1.6 nm, was synthesized by reacting 4, 4′-biphenyldicarboxylic acid (H2L) with Ni(NO3)2·6H2O in an N, N-dimethylformamide (DMF) solution. The nanoscale adsorbent Ni3-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni3-MOF. It exhibited a maximum equilibrium tetracycline (TC) adsorption capacity of 358.2 mg·g-1 at its isoelectric point (pH=6.50), outperforming most reported MOF-based adsorbents. This exceptional performance is likely attributed to the well-matched pore size of Ni3-MOF-N (1.6 nm×1.6 nm) and the molecular dimensions of TC (0.8 nm×1.2 nm), combined with the presence of partial Ni(Ⅱ) sites on the surface of Ni3-MOF-N. These features collectively facilitate effective TC adsorption through a combination of pore filling, electrostatic attraction, hydrogen bonding, surface complexation, and π-π interactions. Recycling experiments demonstrated that Ni3-MOF-N possesses excellent structural stability and consistent adsorption performance.
2026, 42(3): 606-616
doi: 10.11862/CJIC.20250277
摘要:
A collection of ordered-disordered Bi2WO6 homojunction catalysts was prepared in-situ through a facile one-step hydrothermal process, and their photocatalytic nitrogen fixation to synthesize ammonia performance was evaluated. Results showed that ordered-disordered Bi2WO6 (OD-2) obtained by adding 1.5 mL of ethylene glycol during preparation exhibited the optimal nitrogen fixation performance, with a nitrogen fixation rate of 114.92 μmol·g-1·h-1. However, its crystal counterpart, Bi2WO6 (BWO), lacked nitrogen-fixation activity. In-situ diffuse reflectance-Fourier transform infrared technique (DR-FTIR), electrochemical tests, and energy band structure analysis confirmed that the surface disordered structure in OD-2 not only promoted nitrogen activation but also enabled the effective separation of photogenerated electron-hole pairs at the ordered-disordered interface, facilitating the interface electrons transfer to the surface disordered structure of OD-2 and reacting with N2 adsorbed on the disordered structure, thereby promoting the smooth progress of the nitrogen fixation reaction.
A collection of ordered-disordered Bi2WO6 homojunction catalysts was prepared in-situ through a facile one-step hydrothermal process, and their photocatalytic nitrogen fixation to synthesize ammonia performance was evaluated. Results showed that ordered-disordered Bi2WO6 (OD-2) obtained by adding 1.5 mL of ethylene glycol during preparation exhibited the optimal nitrogen fixation performance, with a nitrogen fixation rate of 114.92 μmol·g-1·h-1. However, its crystal counterpart, Bi2WO6 (BWO), lacked nitrogen-fixation activity. In-situ diffuse reflectance-Fourier transform infrared technique (DR-FTIR), electrochemical tests, and energy band structure analysis confirmed that the surface disordered structure in OD-2 not only promoted nitrogen activation but also enabled the effective separation of photogenerated electron-hole pairs at the ordered-disordered interface, facilitating the interface electrons transfer to the surface disordered structure of OD-2 and reacting with N2 adsorbed on the disordered structure, thereby promoting the smooth progress of the nitrogen fixation reaction.
2026, 42(3): 617-631
doi: 10.11862/CJIC.20250265
摘要:
Two Co(Ⅱ) and Ni(Ⅱ) complexes were synthesized by synergistic coordination of 3,3-diphenylpropionic acid (HDPA) and 2,2′-bipyridylamine (PAm). The structures of complexes [Co(DPA)2(PAm)]·2H2O (1) and [Ni(DPA)2(PAm)]·2H2O (2) were determined by single-crystal X-ray diffraction, IR spectroscopy, and powder X-ray diffraction. Hirshfeld surface analysis provided quantitative insights into the intermolecular interactions within the complexes, while molecular docking studies elucidated their binding modes and affinities toward urease. Furthermore, the biological activities of both complexes were systematically evaluated through a range of assays, including DNA binding, urease inhibition, antibacterial activity, and in vitro cytotoxicity against cancer cells. Both complexes exhibited binding affinity for DNA and displayed notable urease inhibitory activity. Under in vitro conditions, both complexes showed appreciable cytotoxicity toward HepG2 cells with efficacy comparable to clinically used platinum-based anticancer agents.
Two Co(Ⅱ) and Ni(Ⅱ) complexes were synthesized by synergistic coordination of 3,3-diphenylpropionic acid (HDPA) and 2,2′-bipyridylamine (PAm). The structures of complexes [Co(DPA)2(PAm)]·2H2O (1) and [Ni(DPA)2(PAm)]·2H2O (2) were determined by single-crystal X-ray diffraction, IR spectroscopy, and powder X-ray diffraction. Hirshfeld surface analysis provided quantitative insights into the intermolecular interactions within the complexes, while molecular docking studies elucidated their binding modes and affinities toward urease. Furthermore, the biological activities of both complexes were systematically evaluated through a range of assays, including DNA binding, urease inhibition, antibacterial activity, and in vitro cytotoxicity against cancer cells. Both complexes exhibited binding affinity for DNA and displayed notable urease inhibitory activity. Under in vitro conditions, both complexes showed appreciable cytotoxicity toward HepG2 cells with efficacy comparable to clinically used platinum-based anticancer agents.
Synthesis, structure, and properties of hydrated tricyclohexyltin theophylline-7-acetic acid complex
2026, 42(3): 632-640
doi: 10.11862/CJIC.20250244
摘要:
The hydrated tricyclohexyltin theophylline-7-acetic acid (tpH) complex [Sn(C6H11)3(tp)(H2O)] was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio. The complex was characterized by IR, 1H (13C) NMR, elemental analysis, and powder X-ray diffraction, and the crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system with space group Iba2, and the central tin atom is in a five-coordinated trigonal bipyramidal configuration. Quantum chemistry ab initio calculations were performed to investigate the stability, molecular orbital energy, and frontier molecular orbital characteristics of the complex. Additionally, its thermal stability, electrochemical properties, and in vitro anticancer activity were evaluated.
The hydrated tricyclohexyltin theophylline-7-acetic acid (tpH) complex [Sn(C6H11)3(tp)(H2O)] was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio. The complex was characterized by IR, 1H (13C) NMR, elemental analysis, and powder X-ray diffraction, and the crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system with space group Iba2, and the central tin atom is in a five-coordinated trigonal bipyramidal configuration. Quantum chemistry ab initio calculations were performed to investigate the stability, molecular orbital energy, and frontier molecular orbital characteristics of the complex. Additionally, its thermal stability, electrochemical properties, and in vitro anticancer activity were evaluated.
2026, 42(3): 641-656
doi: 10.11862/CJIC.20250221
摘要:
In this study, sawdust served as a carbon source and urea as a nitrogen source to synthesize carbon- supported, nitrogen-doped TiO2 composites via a one-pot solvothermal method. The composites were characterized using FTIR, powder X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, thermogravimetry-derivative thermogravimetry, scanning electron microscopy-energy dispersive spectroscopy, and transmission electron microscopy. Results indicated that all synthesized composites exhibit the anatase phase, with those calcined at 800 ℃ demonstrating enhanced crystallinity. Nitrogen is incorporated into the TiO2 lattice, while carbon is predominantly located on the surface. Photodegradation experiments showed that 20 mg of composite N-TiO2/C-800 achieved degradation rates of 93.4% for methylene blue (20 mg·L-1, 50 mL) and 99.4% for oxytetracycline (20 mg·L-1, 50 mL) within 30 min. Free radical capture experiments indicated that h+ was the primary active species in the photocatalytic degradation process.
In this study, sawdust served as a carbon source and urea as a nitrogen source to synthesize carbon- supported, nitrogen-doped TiO2 composites via a one-pot solvothermal method. The composites were characterized using FTIR, powder X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, thermogravimetry-derivative thermogravimetry, scanning electron microscopy-energy dispersive spectroscopy, and transmission electron microscopy. Results indicated that all synthesized composites exhibit the anatase phase, with those calcined at 800 ℃ demonstrating enhanced crystallinity. Nitrogen is incorporated into the TiO2 lattice, while carbon is predominantly located on the surface. Photodegradation experiments showed that 20 mg of composite N-TiO2/C-800 achieved degradation rates of 93.4% for methylene blue (20 mg·L-1, 50 mL) and 99.4% for oxytetracycline (20 mg·L-1, 50 mL) within 30 min. Free radical capture experiments indicated that h+ was the primary active species in the photocatalytic degradation process.
2026, 42(3): 479-487
doi: 10.11862/CJIC.20250292
摘要:
采用简单的一步水热法制备了α-MnO2正极材料，并研究了制备温度对其形貌及电化学性能的影响。实验结果表明，不同合成温度制得的α-MnO2均呈现纳米线结构。比较发现，在180 ℃下制备得到的α-MnO2具有较好的电化学性能：在0.1 A·g-1的电流密度下的放电比容量达到了229.2 mAh·g-1，大于其他温度下制备的α-MnO2，且经过110次循环后，容量仍有90 mAh·g-1；在1 A·g-1的电流密度下，经过1 000次的循环后，其放电比容量仍有38 mAh·g-1；电荷转移电阻明显小于其他温度下制备的样品。
采用简单的一步水热法制备了α-MnO2正极材料，并研究了制备温度对其形貌及电化学性能的影响。实验结果表明，不同合成温度制得的α-MnO2均呈现纳米线结构。比较发现，在180 ℃下制备得到的α-MnO2具有较好的电化学性能：在0.1 A·g-1的电流密度下的放电比容量达到了229.2 mAh·g-1，大于其他温度下制备的α-MnO2，且经过110次循环后，容量仍有90 mAh·g-1；在1 A·g-1的电流密度下，经过1 000次的循环后，其放电比容量仍有38 mAh·g-1；电荷转移电阻明显小于其他温度下制备的样品。
2026, 42(3): 488-498
doi: 10.11862/CJIC.20250272
摘要:
通过氨基酸介导的自组装方法，成功制备了一种三维分级结构氮掺杂碳点/氧化亚铜(N-CDs/Cu2O)纳米复合材料。在具有不同酸度的氨基酸引导下，所形成的Cu2O呈现出不同的尺寸和结晶度。与N-CDs复合后形成的3D分级结构使该材料具有丰富的多孔结构，从而有效地促进了电解液的浸润。此外，N-CDs通过缺陷诱导和界面优化加速了离子/电子的传输。同时，由N-CDs构建的稳固异质界面抑制了充放电过程中复合物的体积膨胀。甘氨酸辅助合成的N-CDs/Cu2O复合电极在0.1 A·g-1的电流密度下，展现出高达373 mAh·g-1的优异初始放电容量，并且在100次循环后仍能保持78%的放电容量。
通过氨基酸介导的自组装方法，成功制备了一种三维分级结构氮掺杂碳点/氧化亚铜(N-CDs/Cu2O)纳米复合材料。在具有不同酸度的氨基酸引导下，所形成的Cu2O呈现出不同的尺寸和结晶度。与N-CDs复合后形成的3D分级结构使该材料具有丰富的多孔结构，从而有效地促进了电解液的浸润。此外，N-CDs通过缺陷诱导和界面优化加速了离子/电子的传输。同时，由N-CDs构建的稳固异质界面抑制了充放电过程中复合物的体积膨胀。甘氨酸辅助合成的N-CDs/Cu2O复合电极在0.1 A·g-1的电流密度下，展现出高达373 mAh·g-1的优异初始放电容量，并且在100次循环后仍能保持78%的放电容量。
2026, 42(3): 499-506
doi: 10.11862/CJIC.20250281
摘要:
以4，4′-联苯二甲酸和[1，1′-联苯]-3，4，4′-三羧酸为配体，四氯化锆为金属盐，利用溶剂法合成了羧基(—COOH)修饰的UiO-67纳米材料(UiO-67-COOH)。该材料对有机染料具有出色的吸附性能，对刚果红(CR)、甲基橙(MO)和酸性橙7(AO7)的最大吸附容量分别为698.7、295.9和200.8 mg·g-1。随着合成体系中含—COOH功能基团有机配体比例的增加，UiO-67-COOH吸附剂对3种阴离子染料的吸附效率均逐渐降低，这是由于静电作用、π-π相互作用和氢键作用、吸附空间和空间位阻协同作用的结果。
以4，4′-联苯二甲酸和[1，1′-联苯]-3，4，4′-三羧酸为配体，四氯化锆为金属盐，利用溶剂法合成了羧基(—COOH)修饰的UiO-67纳米材料(UiO-67-COOH)。该材料对有机染料具有出色的吸附性能，对刚果红(CR)、甲基橙(MO)和酸性橙7(AO7)的最大吸附容量分别为698.7、295.9和200.8 mg·g-1。随着合成体系中含—COOH功能基团有机配体比例的增加，UiO-67-COOH吸附剂对3种阴离子染料的吸附效率均逐渐降低，这是由于静电作用、π-π相互作用和氢键作用、吸附空间和空间位阻协同作用的结果。
2026, 42(3): 507-518
doi: 10.11862/CJIC.20250275
摘要:
为制备高效活化过硫酸盐降解有机污染物的环境友好型Ti基介孔催化剂，分别制备了Co和Zr掺杂的介孔TiO2催化剂(Co-TiO2、Zr-TiO2)，并探究了其在活化过硫酸钠(PDS)过程中活性物种的产生机制及对四环素(TC)降解性能的影响。结构表征结果表明，Co和Zr掺杂均显著提高了催化剂的比表面积和氧空位浓度。具体而言，Co与Ti间的电负性差异促进了电子迁移；而Zr4+因其离子半径大于Ti4+，掺杂后诱发了晶格畸变。TC降解实验显示，相较于未掺杂的TiO2/PDS体系，Co-TiO2/PDS和Zr-TiO2/PDS体系对TC的降解率在6 h内分别提升至93.1%和89.6%，反应速率常数分别为未掺杂体系的2.8倍和2.4倍。猝灭实验与电子顺磁共振(ESR)分析证实，Co-TiO2/PDS体系以羟基自由基(·OH)为主要活性物种，而Zr-TiO2/PDS体系则以单线态氧(1O2)为主要活性物种。磷酸盐(PO43-)添加实验表明，调控催化剂表面羟基可优化Co-TiO2/PDS体系的反应剂利用效率(ηRU)。结果阐明了金属掺杂对介孔TiO2活化PDS过程的差异化影响，以及其对活性物种和污染物降解性能的调控机制。
为制备高效活化过硫酸盐降解有机污染物的环境友好型Ti基介孔催化剂，分别制备了Co和Zr掺杂的介孔TiO2催化剂(Co-TiO2、Zr-TiO2)，并探究了其在活化过硫酸钠(PDS)过程中活性物种的产生机制及对四环素(TC)降解性能的影响。结构表征结果表明，Co和Zr掺杂均显著提高了催化剂的比表面积和氧空位浓度。具体而言，Co与Ti间的电负性差异促进了电子迁移；而Zr4+因其离子半径大于Ti4+，掺杂后诱发了晶格畸变。TC降解实验显示，相较于未掺杂的TiO2/PDS体系，Co-TiO2/PDS和Zr-TiO2/PDS体系对TC的降解率在6 h内分别提升至93.1%和89.6%，反应速率常数分别为未掺杂体系的2.8倍和2.4倍。猝灭实验与电子顺磁共振(ESR)分析证实，Co-TiO2/PDS体系以羟基自由基(·OH)为主要活性物种，而Zr-TiO2/PDS体系则以单线态氧(1O2)为主要活性物种。磷酸盐(PO43-)添加实验表明，调控催化剂表面羟基可优化Co-TiO2/PDS体系的反应剂利用效率(ηRU)。结果阐明了金属掺杂对介孔TiO2活化PDS过程的差异化影响，以及其对活性物种和污染物降解性能的调控机制。
2026, 42(3): 519-530
doi: 10.11862/CJIC.20250274
摘要:
为了加速锂硫(Li-S)电池的离子传输和多硫化物的转化，设计了一种兼顾亲锂性和催化活性的CeO2/g-C3N4复合材料。在g-C3N4亲锂骨架中，富氮单元作为强亲锂位点，通过与锂离子(Li+)之间的路易斯酸碱作用，有效降低了Li+迁移能垒，加速了Li+的定向传输；而Ce4+/Ce3+氧化还原对则发挥关键催化作用，能够诱导生成硫代硫酸盐，从而构建出一条可逆的硫代硫酸盐介导的多硫化物转化的新路径，显著提升多硫化物的双向转化动力学性能。因此，采用CeO2/g-C3N4修饰Li-S电池隔膜的正极侧，可有效提升多硫化物转化动力学性能，降低电荷转移电阻，进而提升电池的倍率性能和循环性能(1.0C下循环1 000圈，每圈容量衰减率仅为0.049%)。
为了加速锂硫(Li-S)电池的离子传输和多硫化物的转化，设计了一种兼顾亲锂性和催化活性的CeO2/g-C3N4复合材料。在g-C3N4亲锂骨架中，富氮单元作为强亲锂位点，通过与锂离子(Li+)之间的路易斯酸碱作用，有效降低了Li+迁移能垒，加速了Li+的定向传输；而Ce4+/Ce3+氧化还原对则发挥关键催化作用，能够诱导生成硫代硫酸盐，从而构建出一条可逆的硫代硫酸盐介导的多硫化物转化的新路径，显著提升多硫化物的双向转化动力学性能。因此，采用CeO2/g-C3N4修饰Li-S电池隔膜的正极侧，可有效提升多硫化物转化动力学性能，降低电荷转移电阻，进而提升电池的倍率性能和循环性能(1.0C下循环1 000圈，每圈容量衰减率仅为0.049%)。
2026, 42(3): 531-542
doi: 10.11862/CJIC.20250271
摘要:
通过提高银(Ⅰ)配合物的银离子含量和释放是增强其抗菌性质的有效手段，但同时可能增加潜在毒性，其粉末态也难以实用。为了解决以上挑战，我们通过3个设计策略构建了一个基于银(Ⅰ)配合物的聚乙烯醇(PVA)复合抗菌薄膜：首先以抗菌配体吲哚-3-羧酸与叔丁基乙炔银自组装配合物1，通过同时释放银离子和抗菌配体2种方式增强抗菌效果；接着引入第三抗菌源氧化石墨烯(GO)制备1@GO复合物，以抗菌性能为指标优化复配比例，持续提升抗菌性能；最后以PVA为基质制备1@GO/PVA薄膜，拓展实用性。通过红外光谱和粉末X射线衍射表征了1的结构、光稳定性和溶液稳定性。银离子释放测试表明1具有pH响应的银离子增强释放。抑菌圈测试结果表明GO(1 000 μg·mL-1)对大肠杆菌、铜绿假单胞菌、金黄色葡萄球菌和白色念珠菌的抑菌效果微弱，抑菌圈直径仅增加1.1、2.5、3.5和1.8 mm；1对4种微生物具有较好的广谱抗菌性，抑菌圈直径分别增加5.0、10.5、5.8和5.0 mm。SEM照片显示，在1@GO(质量浓度比1∶1)中1均匀分散在裸露大量尖锐边缘的GO中，其对大肠杆菌、金黄色葡萄球菌和白色念珠菌的抑菌圈直径分别增加了6.2、10.4和9.8 mm，大于1和GO单独作用时抑菌圈直径增加的代数和(6.1、9.3和6.8 mm)，成功实现了银配合物与GO协同抗菌。最小抑菌浓度(MIC)测试结果表明1对铜绿假单胞菌和金黄色葡萄球菌的抑制效果最好，MIC分别低至20和15 μg·mL-1。加入GO后1@GO(1∶1)对铜绿假单胞菌、金黄色葡萄球菌和白色念珠菌的MIC分别降低至5~10 μg·mL-1、5~10 μg·mL-1和10~15 μg·mL-1。1(0.5%)@GO(1∶1)/PVA薄膜对4种菌株均具有较好的抗菌性质，对铜绿假单胞菌的抑菌圈直径最大可达18.5 mm。
通过提高银(Ⅰ)配合物的银离子含量和释放是增强其抗菌性质的有效手段，但同时可能增加潜在毒性，其粉末态也难以实用。为了解决以上挑战，我们通过3个设计策略构建了一个基于银(Ⅰ)配合物的聚乙烯醇(PVA)复合抗菌薄膜：首先以抗菌配体吲哚-3-羧酸与叔丁基乙炔银自组装配合物1，通过同时释放银离子和抗菌配体2种方式增强抗菌效果；接着引入第三抗菌源氧化石墨烯(GO)制备1@GO复合物，以抗菌性能为指标优化复配比例，持续提升抗菌性能；最后以PVA为基质制备1@GO/PVA薄膜，拓展实用性。通过红外光谱和粉末X射线衍射表征了1的结构、光稳定性和溶液稳定性。银离子释放测试表明1具有pH响应的银离子增强释放。抑菌圈测试结果表明GO(1 000 μg·mL-1)对大肠杆菌、铜绿假单胞菌、金黄色葡萄球菌和白色念珠菌的抑菌效果微弱，抑菌圈直径仅增加1.1、2.5、3.5和1.8 mm；1对4种微生物具有较好的广谱抗菌性，抑菌圈直径分别增加5.0、10.5、5.8和5.0 mm。SEM照片显示，在1@GO(质量浓度比1∶1)中1均匀分散在裸露大量尖锐边缘的GO中，其对大肠杆菌、金黄色葡萄球菌和白色念珠菌的抑菌圈直径分别增加了6.2、10.4和9.8 mm，大于1和GO单独作用时抑菌圈直径增加的代数和(6.1、9.3和6.8 mm)，成功实现了银配合物与GO协同抗菌。最小抑菌浓度(MIC)测试结果表明1对铜绿假单胞菌和金黄色葡萄球菌的抑制效果最好，MIC分别低至20和15 μg·mL-1。加入GO后1@GO(1∶1)对铜绿假单胞菌、金黄色葡萄球菌和白色念珠菌的MIC分别降低至5~10 μg·mL-1、5~10 μg·mL-1和10~15 μg·mL-1。1(0.5%)@GO(1∶1)/PVA薄膜对4种菌株均具有较好的抗菌性质，对铜绿假单胞菌的抑菌圈直径最大可达18.5 mm。
2026, 42(3): 543-550
doi: 10.11862/CJIC.20250270
摘要:
在溶剂热合成条件下，用含有不同取代基的2个吡啶吡唑配体3，5-二甲基-4-(4-吡啶)吡唑(Hdmppz)和3，5-二乙基-4-(4-吡啶)吡唑(Hdeppz)与Cu(Ⅰ)反应，得到2例含有Cu3N6九元环的平面型三核[Cu(pz)]3配合物[Cu(dmppz)]3·H2O (1)和[Cu(deppz)]3 (2)。运用元素分析、红外光谱、单晶X射线衍射、热重分析、荧光光谱等对配体和配合物的结构与性质进行了表征和分析，探讨了配体取代基对配合物结构和性质的影响。结果表明：配合物1属于单斜晶系，P21/c空间群，a=0.746 65(5) nm，b=2.116 92(12) nm，c=2.004 46(10) nm，β=107.725(2)°；配合物2属于单斜晶系，P21/c空间群，a=1.056 74(6) nm，b=2.283 14(13) nm，c=1.535 72(9) nm，β=103.647 0(10)°。2例配合物中都存在丰富的分子内和分子间的Cu…Cu与Cu…π作用，并且甲基和乙基取代基的变化导致它们不同的结构堆积方式。配合物1和2具有较高的热稳定性与强的蓝绿色和浅绿色荧光性质，最大发射波长分别为513和550 nm。
在溶剂热合成条件下，用含有不同取代基的2个吡啶吡唑配体3，5-二甲基-4-(4-吡啶)吡唑(Hdmppz)和3，5-二乙基-4-(4-吡啶)吡唑(Hdeppz)与Cu(Ⅰ)反应，得到2例含有Cu3N6九元环的平面型三核[Cu(pz)]3配合物[Cu(dmppz)]3·H2O (1)和[Cu(deppz)]3 (2)。运用元素分析、红外光谱、单晶X射线衍射、热重分析、荧光光谱等对配体和配合物的结构与性质进行了表征和分析，探讨了配体取代基对配合物结构和性质的影响。结果表明：配合物1属于单斜晶系，P21/c空间群，a=0.746 65(5) nm，b=2.116 92(12) nm，c=2.004 46(10) nm，β=107.725(2)°；配合物2属于单斜晶系，P21/c空间群，a=1.056 74(6) nm，b=2.283 14(13) nm，c=1.535 72(9) nm，β=103.647 0(10)°。2例配合物中都存在丰富的分子内和分子间的Cu…Cu与Cu…π作用，并且甲基和乙基取代基的变化导致它们不同的结构堆积方式。配合物1和2具有较高的热稳定性与强的蓝绿色和浅绿色荧光性质，最大发射波长分别为513和550 nm。
2026, 42(3): 551-561
doi: 10.11862/CJIC.20250269
摘要:
以钛酸四丁酯(TBOT)和五水合硝酸铋(Bi(NO3)3·5H2O)为前驱体，在十二烷基磺酸钠(SDS)或油酸钠2种表面活性剂辅助下，通过水热法成功制备了由纳米片自组装形成的类球状Bi4Ti3O12光催化剂。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见吸收光谱(UV-Vis)、傅里叶变换红外光谱(FTIR)和电化学阻抗谱(EIS)对材料的结构与光电性能进行系统的表征。结果表明，表面活性剂的引入使材料带隙从2.72 eV降至2.46 eV，光吸收性能显著提升。在紫外光照射下，评估了Bi4Ti3O12对亚甲蓝(MB)、罗丹明B(RhB)和甲基橙(MO)的光催化降解性能。其中，SDS辅助制备的Bi4Ti3O12(BTO-1)对MB的降解率最高，达到98.9%；油酸钠辅助制备的Bi4Ti3O12(BTO-2)对RhB的降解率为98.5%，且在5次循环使用后均保持在96%以上。结果表明，表面化学修饰可以有效调控Bi4Ti3O12的表面电荷与疏水性，从而增强其对染料的吸附能力，由此提出了“表面修饰-吸附-光催化”协同作用机制。
以钛酸四丁酯(TBOT)和五水合硝酸铋(Bi(NO3)3·5H2O)为前驱体，在十二烷基磺酸钠(SDS)或油酸钠2种表面活性剂辅助下，通过水热法成功制备了由纳米片自组装形成的类球状Bi4Ti3O12光催化剂。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见吸收光谱(UV-Vis)、傅里叶变换红外光谱(FTIR)和电化学阻抗谱(EIS)对材料的结构与光电性能进行系统的表征。结果表明，表面活性剂的引入使材料带隙从2.72 eV降至2.46 eV，光吸收性能显著提升。在紫外光照射下，评估了Bi4Ti3O12对亚甲蓝(MB)、罗丹明B(RhB)和甲基橙(MO)的光催化降解性能。其中，SDS辅助制备的Bi4Ti3O12(BTO-1)对MB的降解率最高，达到98.9%；油酸钠辅助制备的Bi4Ti3O12(BTO-2)对RhB的降解率为98.5%，且在5次循环使用后均保持在96%以上。结果表明，表面化学修饰可以有效调控Bi4Ti3O12的表面电荷与疏水性，从而增强其对染料的吸附能力，由此提出了“表面修饰-吸附-光催化”协同作用机制。
2026, 42(3): 562-570
doi: 10.11862/CJIC.20250267
摘要:
采用锌箔原位自组装法，将水合五氧化二钒(HVO)直接生长于锌箔表面，成功制备了具有HVO保护层的锌负极(VOZn)。通过调控组装时间可精确控制保护层的厚度。该原位自组装过程有利于在保护层与锌基体之间形成紧密界面，有效抑制充放电过程中保护层的剥落。更重要的是，富含含氧官能团的HVO显著增强了负极表面的亲锌性，从而使Zn2+均匀分布，促进了锌的均匀成核与沉积。此外，该保护层可作为物理屏障，有效减少电解液中自由水与锌负极的直接接触，进而抑制副反应的发生。因此，该复合电极展现出优异的电化学性能：在0.5 mA·cm-2的电流密度下，表现出较低的滞后电压(37 mV)和长达700 h的循环寿命。基于VOZn组装的全电池在1 000次循环后，容量保持率高达71%。
采用锌箔原位自组装法，将水合五氧化二钒(HVO)直接生长于锌箔表面，成功制备了具有HVO保护层的锌负极(VOZn)。通过调控组装时间可精确控制保护层的厚度。该原位自组装过程有利于在保护层与锌基体之间形成紧密界面，有效抑制充放电过程中保护层的剥落。更重要的是，富含含氧官能团的HVO显著增强了负极表面的亲锌性，从而使Zn2+均匀分布，促进了锌的均匀成核与沉积。此外，该保护层可作为物理屏障，有效减少电解液中自由水与锌负极的直接接触，进而抑制副反应的发生。因此，该复合电极展现出优异的电化学性能：在0.5 mA·cm-2的电流密度下，表现出较低的滞后电压(37 mV)和长达700 h的循环寿命。基于VOZn组装的全电池在1 000次循环后，容量保持率高达71%。
2026, 42(3): 571-583
doi: 10.11862/CJIC.20250263
摘要:
在溶剂热合成HKUST-1的过程中添加聚乙烯吡咯烷酮(PVP)调控其晶体形貌结构，进而将其原位掺杂到聚酰亚胺(PI)中构建混合基质膜(MMMs)。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、氮气吸附-脱附测试表征HKUST-1晶体的形貌结构，通过HKUST-1的CO2吸附和MMMs的气体渗透实验，结合巨正则蒙特卡洛(GCMC)模拟探讨了HKUST-1晶体粒径对MMMs的CO2渗透性能的影响，揭示了PVP调控MMMs的CO2分离性能的机制。研究发现，基于PVP的空间位阻效应，添加PVP合成的HKUST-1晶体的平均粒径为1~3 μm，比表面积为731~1 007 m2·g-1，相较于未添加PVP合成的HKUST-1晶体的平均粒径显著减小，粒径分布变窄，比表面积增大，且暴露出更多的Cu2+金属位点与芳香环结构，这增强了HKUST-1与PI的界面相容性，以及HKUST-1与CO2的π-π相互作用与路易斯酸性作用。采用掺杂量(质量分数)为3%的K30型PVP调控的HKUST-1(K30)原位掺杂构建的MMMs的CO2渗透率和CO2/N2渗透选择性分别是142.81 Barrer[1 Barrer=7.5×10-14 cm3(STP)·cm·cm-2·s-1·Pa-1]和25.05，分别是PI膜的76倍和18倍，表明通过PVP调控HKUST-1晶体的形貌结构可有效强化MMMs的CO2分离性能。
在溶剂热合成HKUST-1的过程中添加聚乙烯吡咯烷酮(PVP)调控其晶体形貌结构，进而将其原位掺杂到聚酰亚胺(PI)中构建混合基质膜(MMMs)。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、氮气吸附-脱附测试表征HKUST-1晶体的形貌结构，通过HKUST-1的CO2吸附和MMMs的气体渗透实验，结合巨正则蒙特卡洛(GCMC)模拟探讨了HKUST-1晶体粒径对MMMs的CO2渗透性能的影响，揭示了PVP调控MMMs的CO2分离性能的机制。研究发现，基于PVP的空间位阻效应，添加PVP合成的HKUST-1晶体的平均粒径为1~3 μm，比表面积为731~1 007 m2·g-1，相较于未添加PVP合成的HKUST-1晶体的平均粒径显著减小，粒径分布变窄，比表面积增大，且暴露出更多的Cu2+金属位点与芳香环结构，这增强了HKUST-1与PI的界面相容性，以及HKUST-1与CO2的π-π相互作用与路易斯酸性作用。采用掺杂量(质量分数)为3%的K30型PVP调控的HKUST-1(K30)原位掺杂构建的MMMs的CO2渗透率和CO2/N2渗透选择性分别是142.81 Barrer[1 Barrer=7.5×10-14 cm3(STP)·cm·cm-2·s-1·Pa-1]和25.05，分别是PI膜的76倍和18倍，表明通过PVP调控HKUST-1晶体的形貌结构可有效强化MMMs的CO2分离性能。
2026, 42(3): 584-592
doi: 10.11862/CJIC.20250217
摘要:
系统研究了Bi2SeO5的拉曼光谱特性，发现其拉曼特征峰强度随纳米片厚度增加而增强，显示出明显的厚度依赖性。进一步将Bi2SeO5与典型二维半导体进行集成：以MoS2为沟道构建的背栅场效应晶体管(FET)中，Bi2SeO5凭借其优异的介电特性实现高效栅极调控，器件表现出高达106的开关比和144 mV·dec-1的低亚阈值摆幅(SS)，彰显出卓越的介电调控能力。同时，Bi2SeO5作为封装层，能够有效保护对气氛敏感的黑磷(BP)和硒化铟(InSe)，显著提升二者在空气中的稳定性。这些结果证实了Bi2SeO5与二维材料能够形成平整、紧密的界面。同时，Bi2SeO5兼具优异的介电性能以及良好的保护功能，具有双重优势。
系统研究了Bi2SeO5的拉曼光谱特性，发现其拉曼特征峰强度随纳米片厚度增加而增强，显示出明显的厚度依赖性。进一步将Bi2SeO5与典型二维半导体进行集成：以MoS2为沟道构建的背栅场效应晶体管(FET)中，Bi2SeO5凭借其优异的介电特性实现高效栅极调控，器件表现出高达106的开关比和144 mV·dec-1的低亚阈值摆幅(SS)，彰显出卓越的介电调控能力。同时，Bi2SeO5作为封装层，能够有效保护对气氛敏感的黑磷(BP)和硒化铟(InSe)，显著提升二者在空气中的稳定性。这些结果证实了Bi2SeO5与二维材料能够形成平整、紧密的界面。同时，Bi2SeO5兼具优异的介电性能以及良好的保护功能，具有双重优势。
2026, 42(1): 1-22
doi: 10.11862/CJIC.20250197
摘要:
CO2 reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure. It is an effective way to achieve energy conversion and utilization. Covalent organic frameworks (COFs) are porous crystalline materials formed by connecting organic monomers through covalent bonds. They have the characteristics of functional diversity and rich chemical properties. Their advantages, such as high porosity, a wide range of visible light absorption, and excellent charge separation efficiency, give them good potential in CO2 capture, separation, and conversion. Currently, Cu is a key metal in the catalytic CO2 reduction reaction (CO2RR) for the preparation of high-value-added chemicals. The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts. In this review, we discuss the latest advancements in this field, including the development of various Cu-based COFs and their applications as catalysts for CO2RR. Here, we mainly introduce the synthesis strategies, some important characterization information, and the applications of electrocatalytic and photocatalytic CO2 conversion using these previously reported Cu-based COFs.
CO2 reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure. It is an effective way to achieve energy conversion and utilization. Covalent organic frameworks (COFs) are porous crystalline materials formed by connecting organic monomers through covalent bonds. They have the characteristics of functional diversity and rich chemical properties. Their advantages, such as high porosity, a wide range of visible light absorption, and excellent charge separation efficiency, give them good potential in CO2 capture, separation, and conversion. Currently, Cu is a key metal in the catalytic CO2 reduction reaction (CO2RR) for the preparation of high-value-added chemicals. The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts. In this review, we discuss the latest advancements in this field, including the development of various Cu-based COFs and their applications as catalysts for CO2RR. Here, we mainly introduce the synthesis strategies, some important characterization information, and the applications of electrocatalytic and photocatalytic CO2 conversion using these previously reported Cu-based COFs.
2026, 42(1): 23-44
doi: 10.11862/CJIC.20250188
摘要:
钌合金催化剂是一类重要的催化材料，得益于其独特的电子结构和表面特性，在多相催化、电催化、光催化等众多领域备受关注。通过与其他金属元素的高效结合，可显著改善钌基催化剂的催化性能，拓宽其应用范围。尤其是在析氢反应(HER)中，钌合金催化剂凭借催化活性高、成本效益低、稳定性和耐久性好等突出优势，成为驱动绿色氢能高效转化的研究焦点，其优异性能为可持续能源技术的突破带来了新的可能。本文围绕HER钌合金催化剂，着重从制备方法、组分设计、改性手段及性能研究4个核心维度切入，深入探讨了近年来有关HER钌合金催化剂的最新进展。同时，结合行业发展趋势对未来研究方向进行前瞻性展望，旨在为高性能HER钌合金催化剂的创新设计与工程化开发提供理论支撑与参考，助力推动该领域技术的快速发展。
钌合金催化剂是一类重要的催化材料，得益于其独特的电子结构和表面特性，在多相催化、电催化、光催化等众多领域备受关注。通过与其他金属元素的高效结合，可显著改善钌基催化剂的催化性能，拓宽其应用范围。尤其是在析氢反应(HER)中，钌合金催化剂凭借催化活性高、成本效益低、稳定性和耐久性好等突出优势，成为驱动绿色氢能高效转化的研究焦点，其优异性能为可持续能源技术的突破带来了新的可能。本文围绕HER钌合金催化剂，着重从制备方法、组分设计、改性手段及性能研究4个核心维度切入，深入探讨了近年来有关HER钌合金催化剂的最新进展。同时，结合行业发展趋势对未来研究方向进行前瞻性展望，旨在为高性能HER钌合金催化剂的创新设计与工程化开发提供理论支撑与参考，助力推动该领域技术的快速发展。
2026, 42(1): 45-54
doi: 10.11862/CJIC.20250196
摘要:
Under hydrothermal and solvothermal conditions, two novel cobalt-based complexes, {[Co2(CIA)(OH)(1, 4-dtb)]·2H2O}n (HU23) and {[Co2(CIA)(OH)(1, 4-dib)]·3.5H2O·DMF}n (HU24), were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid (H3CIA) with the N-heterocyclic ligands 1, 4-di(4H-1, 2, 4-triazol-4-yl)benzene (1, 4-dtb) and 1, 4-di(1H-imidazol-1-yl)benzene (1, 4-dib), respectively, around Co2+ ions. Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24, the CIA3- anions adopt a κ7-coordination mode, bridging six Co2+ ions via their five carboxylate oxygen atoms and one ether oxygen atom. This linkage forms tetranuclear [Co4(μ3-OH)2]6+ units. These Co-oxo cluster units were interconnected by CIA3- anions to assemble into 2D kgd-type structures featuring a 3, 6-connected topology. The 2D layers were further connected by 1, 4-dtb and 1, 4-dib, resulting in 3D pillar-layered frameworks for HU23 and HU24. Notably, despite the similar configurations of 1, 4-dtb and 1, 4-dib, differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24. Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3, 10-connected net (point symbol: (410.63.82)(43)2) and a 3, 8-connected tfz-d net (point symbol: (43)2(46.618.84)), respectively. This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks. Moreover, the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light. According to the Kubelka-Munk method, their bandwidths were 2.15 and 2.08 eV, respectively, which are consistent with those of typical semiconductor materials. Variable-temperature magnetic susceptibility measurements (2-300 K) revealed significant antiferromagnetic coupling in both complexes, with their effective magnetic moments decreasing markedly as the temperature lowered.
Under hydrothermal and solvothermal conditions, two novel cobalt-based complexes, {[Co2(CIA)(OH)(1, 4-dtb)]·2H2O}n (HU23) and {[Co2(CIA)(OH)(1, 4-dib)]·3.5H2O·DMF}n (HU24), were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid (H3CIA) with the N-heterocyclic ligands 1, 4-di(4H-1, 2, 4-triazol-4-yl)benzene (1, 4-dtb) and 1, 4-di(1H-imidazol-1-yl)benzene (1, 4-dib), respectively, around Co2+ ions. Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24, the CIA3- anions adopt a κ7-coordination mode, bridging six Co2+ ions via their five carboxylate oxygen atoms and one ether oxygen atom. This linkage forms tetranuclear [Co4(μ3-OH)2]6+ units. These Co-oxo cluster units were interconnected by CIA3- anions to assemble into 2D kgd-type structures featuring a 3, 6-connected topology. The 2D layers were further connected by 1, 4-dtb and 1, 4-dib, resulting in 3D pillar-layered frameworks for HU23 and HU24. Notably, despite the similar configurations of 1, 4-dtb and 1, 4-dib, differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24. Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3, 10-connected net (point symbol: (410.63.82)(43)2) and a 3, 8-connected tfz-d net (point symbol: (43)2(46.618.84)), respectively. This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks. Moreover, the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light. According to the Kubelka-Munk method, their bandwidths were 2.15 and 2.08 eV, respectively, which are consistent with those of typical semiconductor materials. Variable-temperature magnetic susceptibility measurements (2-300 K) revealed significant antiferromagnetic coupling in both complexes, with their effective magnetic moments decreasing markedly as the temperature lowered.
2026, 42(1): 152-160
doi: 10.11862/CJIC.20250204
摘要:
Three copper(Ⅱ), nickel and cadmium(Ⅱ) complexes, namely [Cu2(μ-H2dbda)2(phen)2]·2H2O (1), [Ni(μ-H2dbda)(μ-bpb)(H2O)2]n (2), and [Cd(μ-H2dbda)(μ-bpa)]n (3), have been constructed hydrothermally using H4dbda (4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid), phen (1,10-phenanthroline), bpb (1,4-bis(pyrid-4-yl)benzene), bpa (bis(4-pyridyl)amine), and copper, nickel and cadmium chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n, tetragonal I42d, and orthorhombic P21212 space groups. The complexes exhibit molecular dimers (1) or 2D metal-organic networks (2 and 3). The catalytic performances in the Knoevenagel reaction of these complexes were investigated. Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.
Three copper(Ⅱ), nickel and cadmium(Ⅱ) complexes, namely [Cu2(μ-H2dbda)2(phen)2]·2H2O (1), [Ni(μ-H2dbda)(μ-bpb)(H2O)2]n (2), and [Cd(μ-H2dbda)(μ-bpa)]n (3), have been constructed hydrothermally using H4dbda (4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid), phen (1,10-phenanthroline), bpb (1,4-bis(pyrid-4-yl)benzene), bpa (bis(4-pyridyl)amine), and copper, nickel and cadmium chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n, tetragonal I42d, and orthorhombic P21212 space groups. The complexes exhibit molecular dimers (1) or 2D metal-organic networks (2 and 3). The catalytic performances in the Knoevenagel reaction of these complexes were investigated. Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.
2026, 42(1): 161-169
doi: 10.11862/CJIC.20250195
摘要:
The complexes 1-4 of cyclobutanocucurbit[5]uril (CyB5Q[5]) with Na+/K+ have been synthesized and characterized by single-crystal X-ray diffraction. The results show that although the inorganic salts are used when the cations are the same and the anions are different, in complex 1, Na+ closes one port of CyB5Q[5] through Na—O seven coordination bonds to form a molecular bowl; in complex 3, Na+ completely closes the two ports of CyB5Q[5] to form a molecular capsule with six Na—O coordination bonds; in complexes 2 and 4, the two ports of CyB5Q[5] are completely closed to form K—O coordinated molecular capsules, but the K+ of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated. and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.
The complexes 1-4 of cyclobutanocucurbit[5]uril (CyB5Q[5]) with Na+/K+ have been synthesized and characterized by single-crystal X-ray diffraction. The results show that although the inorganic salts are used when the cations are the same and the anions are different, in complex 1, Na+ closes one port of CyB5Q[5] through Na—O seven coordination bonds to form a molecular bowl; in complex 3, Na+ completely closes the two ports of CyB5Q[5] to form a molecular capsule with six Na—O coordination bonds; in complexes 2 and 4, the two ports of CyB5Q[5] are completely closed to form K—O coordinated molecular capsules, but the K+ of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated. and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.
2026, 42(1): 170-180
doi: 10.11862/CJIC.20250161
摘要:
Three zinc(Ⅱ), nickel(Ⅱ), and cadmium(Ⅱ) complexes, namely [Zn(μ-Htpta)(py)2]n (1), [Ni(H2biim)2(H2O)2][Ni(tpta)(H2biim)2(H2O)]2·3H2O (2), and [Cd3(μ4-tpta)2(μ-dpe)3]n (3), have been constructed hydrothermally at 160 ℃ using H3tpta ([1, 1′: 3′, 1″-terphenyl]-4, 4′, 5′-tricarboxylic acid), py (pyridine), H2biim (2, 2′-biimidazole), dpe (1, 2-di (4-pyridyl)ethylene), and zinc, nickel and cadmium chlorides, resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy, element analysis, thermogravimetric analysis, as well as structural analyses conducted via single-crystal X-ray diffraction. The findings from these single-crystal X-ray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P21/c space group (1) or triclinic system P1 space group (2 and 3), and possess 1D, 0D, and 3D structures, respectively. Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions. In addition, complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.
Three zinc(Ⅱ), nickel(Ⅱ), and cadmium(Ⅱ) complexes, namely [Zn(μ-Htpta)(py)2]n (1), [Ni(H2biim)2(H2O)2][Ni(tpta)(H2biim)2(H2O)]2·3H2O (2), and [Cd3(μ4-tpta)2(μ-dpe)3]n (3), have been constructed hydrothermally at 160 ℃ using H3tpta ([1, 1′: 3′, 1″-terphenyl]-4, 4′, 5′-tricarboxylic acid), py (pyridine), H2biim (2, 2′-biimidazole), dpe (1, 2-di (4-pyridyl)ethylene), and zinc, nickel and cadmium chlorides, resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy, element analysis, thermogravimetric analysis, as well as structural analyses conducted via single-crystal X-ray diffraction. The findings from these single-crystal X-ray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P21/c space group (1) or triclinic system P1 space group (2 and 3), and possess 1D, 0D, and 3D structures, respectively. Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions. In addition, complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.
2026, 42(1): 181-192
doi: 10.11862/CJIC.20250126
摘要:
Six new lanthanide complexes: [Ln(3,4-DEOBA)3(4,4′-DM-2,2′-bipy)]2·2C2H5OH, [Ln=Dy (1), Eu (2), Tb (3), Sm (4), Ho (5), Gd (6); 3,4-DEOBA-=3,4-diethoxybenzoate, 4,4′-DM-2,2′-bipy=4,4′-dimethyl-2,2′-bipyridine] were successfully synthesized by the volatilization of the solution at room temperature. The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology. The results showed that the complexes all have a binuclear structure, and the structures contain free ethanol molecules. Moreover, the coordination number of the central metal of each structural unit is eight. Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures. After conducting a systematic study on the luminescence properties of complexes 1-4, their emission and excitation spectra were obtained. Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms, respectively. The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system, and their corresponding luminescent regions cover the yellow light, red light, green light, and orange-red light bands, respectively. Within the temperature range of 299.15-1 300 K, the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology. The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas, 3D infrared spectroscopy, and ion fragment information detected by mass spectrometry. The specific decomposition path is as follows: firstly, free ethanol molecules and neutral ligands are removed, and finally, acidic ligands are released; the final product is the corresponding metal oxide.
Six new lanthanide complexes: [Ln(3,4-DEOBA)3(4,4′-DM-2,2′-bipy)]2·2C2H5OH, [Ln=Dy (1), Eu (2), Tb (3), Sm (4), Ho (5), Gd (6); 3,4-DEOBA-=3,4-diethoxybenzoate, 4,4′-DM-2,2′-bipy=4,4′-dimethyl-2,2′-bipyridine] were successfully synthesized by the volatilization of the solution at room temperature. The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology. The results showed that the complexes all have a binuclear structure, and the structures contain free ethanol molecules. Moreover, the coordination number of the central metal of each structural unit is eight. Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures. After conducting a systematic study on the luminescence properties of complexes 1-4, their emission and excitation spectra were obtained. Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms, respectively. The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system, and their corresponding luminescent regions cover the yellow light, red light, green light, and orange-red light bands, respectively. Within the temperature range of 299.15-1 300 K, the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology. The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas, 3D infrared spectroscopy, and ion fragment information detected by mass spectrometry. The specific decomposition path is as follows: firstly, free ethanol molecules and neutral ligands are removed, and finally, acidic ligands are released; the final product is the corresponding metal oxide.
2026, 42(1): 193-202
doi: 10.11862/CJIC.20250029
摘要:
The poor electrical conductivity of metal-organic frameworks (MOFs) limits their electrocatalytic performance in the oxygen evolution reaction (OER). In this study, a Py@Co-MOF composite material based on pyrene (Py) molecules and {[Co2(BINDI)(DMA)2]·DMA}n (Co-MOF, H4BINDI=N,N′-bis(5-isophthalic acid)naphthalenediimide, DMA=N,N-dimethylacetamide) was synthesized via a one-pot method, leveraging π-π interactions between pyrene and Co-MOF to modulate electrical conductivity. Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes, achieving an overpotential of 246 mV at a current density of 10 mA·cm-2 along with excellent stability. Density functional theory (DFT) calculations reveal that the formation of O* in the second step is the rate-determining step (RDS) during the OER process on Co-MOF, with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH* intermediate for Co sites.
The poor electrical conductivity of metal-organic frameworks (MOFs) limits their electrocatalytic performance in the oxygen evolution reaction (OER). In this study, a Py@Co-MOF composite material based on pyrene (Py) molecules and {[Co2(BINDI)(DMA)2]·DMA}n (Co-MOF, H4BINDI=N,N′-bis(5-isophthalic acid)naphthalenediimide, DMA=N,N-dimethylacetamide) was synthesized via a one-pot method, leveraging π-π interactions between pyrene and Co-MOF to modulate electrical conductivity. Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes, achieving an overpotential of 246 mV at a current density of 10 mA·cm-2 along with excellent stability. Density functional theory (DFT) calculations reveal that the formation of O* in the second step is the rate-determining step (RDS) during the OER process on Co-MOF, with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH* intermediate for Co sites.
CoMoNiO-S/nickel foam heterostructure composite for efficient oxygen evolution catalysis performance
2026, 42(1): 203-215
doi: 10.11862/CJIC.20250041
摘要:
A composite electrocatalyst, CoMoNiO-S/NF-110 (NF is nickel foam), was synthesized through electrodeposition, followed by pyrolysis and then the vulcanization process. CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets, creating a rich, heterogeneous interface that enhances the synergistic effects of each component. In an alkaline electrolyte, the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction (OER), achieving current densities of 100 and 200 mA·cm-2 with low overpotentials of 199.4 and 224.4 mV, respectively, outperforming RuO2 and several high-performance Mo and Ni-based catalysts. This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.
A composite electrocatalyst, CoMoNiO-S/NF-110 (NF is nickel foam), was synthesized through electrodeposition, followed by pyrolysis and then the vulcanization process. CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets, creating a rich, heterogeneous interface that enhances the synergistic effects of each component. In an alkaline electrolyte, the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction (OER), achieving current densities of 100 and 200 mA·cm-2 with low overpotentials of 199.4 and 224.4 mV, respectively, outperforming RuO2 and several high-performance Mo and Ni-based catalysts. This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.
2026, 42(1): 55-64
doi: 10.11862/CJIC.20250178
摘要:
使用不同金属盐(高氯酸锌、高氯酸镍)与配体2，7-萘二羧酸(H2NDA)、1，4-二(1H-咪唑-1-基)苯(1，4-DMB)反应，在溶剂热条件下成功构筑出2例具有不同性质的配位聚合物：{[Zn(NDA)(1，4-DMB)0.5(H2O)]}n (Zn-CP)和{[Ni(NDA)(1，4-DMB)(H2O)3]}n (Ni-CP)，并采取单晶X射线衍射、Hirshfeld表面分析、热重分析等手段进一步探究二者的结构、晶体内相互作用、相纯度及热稳定性。研究结果表明：2个配位聚合物均为一维链状结构，并最终都通过丰富的分子间氢键和π…π堆积相互作用形成了3D超分子结构。值得注意的是，2个配合物合成时，除金属阳离子不同外，阴离子及其余试剂和条件方法均相同，但在Zn-CP中Zn2+处于四配位的变形四面体中心，NDA2-配体中的羧基均参与配位，为一双齿桥联配体，配位聚合物最终结构为一维梯子形链；而Ni-CP中，Ni2+处于六配位的变形八面体中心，但NDA2-配体中只有一个羧基参与配位，为一单齿端基配体，因此配位聚合物仅为一维扭曲梯形链。此外，固体荧光和电催化硝酸根还原制氨性能测试结果显示，Zn-CP具有较好的荧光性质，而Ni-CP具备一定的电催化硝酸根还原制氨能力。
使用不同金属盐(高氯酸锌、高氯酸镍)与配体2，7-萘二羧酸(H2NDA)、1，4-二(1H-咪唑-1-基)苯(1，4-DMB)反应，在溶剂热条件下成功构筑出2例具有不同性质的配位聚合物：{[Zn(NDA)(1，4-DMB)0.5(H2O)]}n (Zn-CP)和{[Ni(NDA)(1，4-DMB)(H2O)3]}n (Ni-CP)，并采取单晶X射线衍射、Hirshfeld表面分析、热重分析等手段进一步探究二者的结构、晶体内相互作用、相纯度及热稳定性。研究结果表明：2个配位聚合物均为一维链状结构，并最终都通过丰富的分子间氢键和π…π堆积相互作用形成了3D超分子结构。值得注意的是，2个配合物合成时，除金属阳离子不同外，阴离子及其余试剂和条件方法均相同，但在Zn-CP中Zn2+处于四配位的变形四面体中心，NDA2-配体中的羧基均参与配位，为一双齿桥联配体，配位聚合物最终结构为一维梯子形链；而Ni-CP中，Ni2+处于六配位的变形八面体中心，但NDA2-配体中只有一个羧基参与配位，为一单齿端基配体，因此配位聚合物仅为一维扭曲梯形链。此外，固体荧光和电催化硝酸根还原制氨性能测试结果显示，Zn-CP具有较好的荧光性质，而Ni-CP具备一定的电催化硝酸根还原制氨能力。
2026, 42(1): 65-77
doi: 10.11862/CJIC.20250172
摘要:
为改善光催化剂的载流子复合效率高、光响应能力差的问题，利用碱性KOH的“剪切效应”原位合成了具有可见光响应能力的Bi12TiO20/BaTiO3复合压电-光催化剂，通过BaTiO3持有的内置电场调制Bi12TiO20的光生载流子运输行为，提升其分离效率。采用X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱、X射线光电子能谱、扫描电子显微镜对合成粉体的物相、形貌进行表征、分析，获得了Bi12TiO20/BaTiO3的时间演化过程。Bi12TiO20/BaTiO3对染料的压电-光催化降解反应速率常数为9.76×10-2 min-1，优于压电催化(2.39×10-2 min-1)和光催化(8.17×10-2 min-1)；此外，结合自由基捕获实验、电子自旋共振(ESR)技术与Bi12TiO20/BaTiO3异质结能带结构揭示了压电-光催化增强机制。
为改善光催化剂的载流子复合效率高、光响应能力差的问题，利用碱性KOH的“剪切效应”原位合成了具有可见光响应能力的Bi12TiO20/BaTiO3复合压电-光催化剂，通过BaTiO3持有的内置电场调制Bi12TiO20的光生载流子运输行为，提升其分离效率。采用X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱、X射线光电子能谱、扫描电子显微镜对合成粉体的物相、形貌进行表征、分析，获得了Bi12TiO20/BaTiO3的时间演化过程。Bi12TiO20/BaTiO3对染料的压电-光催化降解反应速率常数为9.76×10-2 min-1，优于压电催化(2.39×10-2 min-1)和光催化(8.17×10-2 min-1)；此外，结合自由基捕获实验、电子自旋共振(ESR)技术与Bi12TiO20/BaTiO3异质结能带结构揭示了压电-光催化增强机制。
2026, 42(1): 78-86
doi: 10.11862/CJIC.20250141
摘要:
通过原位反应，设计合成了2例配合物[Ni(HL1)2]·CH3CN·CH3OH (1)和[Ni(L2)2] (2)，其中H2L1=2-羟基苯甲酸(6-甲氧基-吡啶-2-基亚甲基)-肼，HL2=4-溴-2-[(6-甲氧基吡啶-2-基亚甲基)-氨基]-苯酚。单晶X射线衍射分析表明：配合物1和2均具有以二价镍离子为中心的单核零维结构。打孔抑菌圈实验数据表明，与单纯的过渡金属镍离子相比，配合物1和2表现出更强的抑菌活性。采用紫外可见光谱法、循环伏安法和荧光光谱法研究了配合物1和2与小牛胸腺DNA(CTDNA)之间的相互作用，结果表明2个配合物均通过插入作用模式与CTDNA结合。
通过原位反应，设计合成了2例配合物[Ni(HL1)2]·CH3CN·CH3OH (1)和[Ni(L2)2] (2)，其中H2L1=2-羟基苯甲酸(6-甲氧基-吡啶-2-基亚甲基)-肼，HL2=4-溴-2-[(6-甲氧基吡啶-2-基亚甲基)-氨基]-苯酚。单晶X射线衍射分析表明：配合物1和2均具有以二价镍离子为中心的单核零维结构。打孔抑菌圈实验数据表明，与单纯的过渡金属镍离子相比，配合物1和2表现出更强的抑菌活性。采用紫外可见光谱法、循环伏安法和荧光光谱法研究了配合物1和2与小牛胸腺DNA(CTDNA)之间的相互作用，结果表明2个配合物均通过插入作用模式与CTDNA结合。
2026, 42(1): 87-96
doi: 10.11862/CJIC.20250127
摘要:
选用食醋为碳源，通过直接透析法得到荧光碳量子点(vCDs)，并对其形貌、组成、结构、光谱性能进行了表征和测试。结果表明，食醋提取的vCDs溶液的质量浓度为0.006 2 g·mL-1。所制备的vCDs表现出均一的尺寸分布，平均粒径为4.05 nm。vCDs的最佳荧光发射波长为460 nm，具有良好的抗光漂白性和抗盐性。由于表面质子化引发的电子能级变化，以及vCDs对Fe3+具有高选择性荧光猝灭，使得vCDs针对pH和Fe3+表现出特异的荧光分析传感特性。此外，将vCDs与聚乙烯醇丁醛(PVB)相融合，制备出荧光薄膜。
选用食醋为碳源，通过直接透析法得到荧光碳量子点(vCDs)，并对其形貌、组成、结构、光谱性能进行了表征和测试。结果表明，食醋提取的vCDs溶液的质量浓度为0.006 2 g·mL-1。所制备的vCDs表现出均一的尺寸分布，平均粒径为4.05 nm。vCDs的最佳荧光发射波长为460 nm，具有良好的抗光漂白性和抗盐性。由于表面质子化引发的电子能级变化，以及vCDs对Fe3+具有高选择性荧光猝灭，使得vCDs针对pH和Fe3+表现出特异的荧光分析传感特性。此外，将vCDs与聚乙烯醇丁醛(PVB)相融合，制备出荧光薄膜。
2026, 42(1): 97-110
doi: 10.11862/CJIC.20250116
摘要:
采用液相还原法首先合成纳米Cu2O，再通过煅烧的方式成功制备出系列价态可调的Cu2O/CuO复合结构，并测试其在黑暗条件下的普通催化性能以及光辅助催化氨硼烷水解制氢的性能。通过X射线衍射、傅里叶红外光谱、扫描电子显微镜、透射电子显微镜、X射线光电子能谱和紫外可见分光光度计对催化剂进行系统表征。结果表明，Cu2O/CuO复合结构为类树莓状纳米空心球，其中CuO的含量随煅烧时长增加而升高，并且相较于单相Cu2O增强了对可见光的吸收与利用。复合结构在可见光辅助条件下，催化水解制氢速率最高可达150.09 mL·g-1·min-1，且反应所需活化能仅为37.1 kJ·mol-1，明显优于黑暗条件。Cu2O/CuO催化剂在催化氨硼烷水解过程中发生表面重构形成Cu/Cu2O/CuO，金属与氧化物的复合结构在可见光下提供了更加高效的活性氢产生过程，进而增强了催化活性。
采用液相还原法首先合成纳米Cu2O，再通过煅烧的方式成功制备出系列价态可调的Cu2O/CuO复合结构，并测试其在黑暗条件下的普通催化性能以及光辅助催化氨硼烷水解制氢的性能。通过X射线衍射、傅里叶红外光谱、扫描电子显微镜、透射电子显微镜、X射线光电子能谱和紫外可见分光光度计对催化剂进行系统表征。结果表明，Cu2O/CuO复合结构为类树莓状纳米空心球，其中CuO的含量随煅烧时长增加而升高，并且相较于单相Cu2O增强了对可见光的吸收与利用。复合结构在可见光辅助条件下，催化水解制氢速率最高可达150.09 mL·g-1·min-1，且反应所需活化能仅为37.1 kJ·mol-1，明显优于黑暗条件。Cu2O/CuO催化剂在催化氨硼烷水解过程中发生表面重构形成Cu/Cu2O/CuO，金属与氧化物的复合结构在可见光下提供了更加高效的活性氢产生过程，进而增强了催化活性。
2026, 42(1): 111-119
doi: 10.11862/CJIC.20250121
摘要:
以低毒的乙酸乙酯为溶剂，合成了一种含溴离子的乙烯基咪唑-三联吡啶离子液体单体(TerVi[Br])，经聚合后再通过离子交换法引入双三氟甲烷磺酰亚胺阴离子(Tf2N-)，制得疏水型的聚离子液体(PTerVi[Tf2N])。该结构中三联吡啶基团不仅可有效配位稀土Eu3+离子，还可作为“天线”基团敏化其发光，从而构建高性能稀土发光材料。系统研究聚合与离子交换顺序对发光材料结构与性能的影响发现，“先聚合后离子交换”路径所得产物(PTerVi[Tf2N]-Eu)的发光性能显著优于“先离子交换后聚合”产物(P(TerVi[Tf2N])-Eu)。结果表明，PTerVi[Tf2N]-Eu的量子产率达20.52%，高于P(TerVi[Tf2N])-Eu的15.70%，同时其Eu3+的5D0能级荧光寿命也更长。
以低毒的乙酸乙酯为溶剂，合成了一种含溴离子的乙烯基咪唑-三联吡啶离子液体单体(TerVi[Br])，经聚合后再通过离子交换法引入双三氟甲烷磺酰亚胺阴离子(Tf2N-)，制得疏水型的聚离子液体(PTerVi[Tf2N])。该结构中三联吡啶基团不仅可有效配位稀土Eu3+离子，还可作为“天线”基团敏化其发光，从而构建高性能稀土发光材料。系统研究聚合与离子交换顺序对发光材料结构与性能的影响发现，“先聚合后离子交换”路径所得产物(PTerVi[Tf2N]-Eu)的发光性能显著优于“先离子交换后聚合”产物(P(TerVi[Tf2N])-Eu)。结果表明，PTerVi[Tf2N]-Eu的量子产率达20.52%，高于P(TerVi[Tf2N])-Eu的15.70%，同时其Eu3+的5D0能级荧光寿命也更长。
2026, 42(1): 120-128
doi: 10.11862/CJIC.20250091
摘要:
采用静电吸附层层组装技术，在氨基修饰的硅片上构建了不同组装层数(n)的氧化石墨烯(GO)与金纳米棒(AuNR)复合组装体(GO/AuNR)n。系统研究了该复合组装体在催化还原4-硝基苯酚(4-NP)和光催化降解罗丹明B(RhB)反应中的性能，并评估了其作为表面增强拉曼散射(SERS)基底在检测多种污染物(如4-NP、RhB、吡啶和4-氨基苯硫酚)以及实时原位监测上述催化反应过程中的应用。结果表明，(GO/AuNR)n复合组装体相较于单一AuNR表现出更优异的催化活性和SERS增强性能，且随着组装层数的增加，其催化与SERS性能均显著提升。
采用静电吸附层层组装技术，在氨基修饰的硅片上构建了不同组装层数(n)的氧化石墨烯(GO)与金纳米棒(AuNR)复合组装体(GO/AuNR)n。系统研究了该复合组装体在催化还原4-硝基苯酚(4-NP)和光催化降解罗丹明B(RhB)反应中的性能，并评估了其作为表面增强拉曼散射(SERS)基底在检测多种污染物(如4-NP、RhB、吡啶和4-氨基苯硫酚)以及实时原位监测上述催化反应过程中的应用。结果表明，(GO/AuNR)n复合组装体相较于单一AuNR表现出更优异的催化活性和SERS增强性能，且随着组装层数的增加，其催化与SERS性能均显著提升。
2026, 42(1): 129-140
doi: 10.11862/CJIC.20250069
摘要:
基于A位点阳离子替代策略，采用高温固相反应法制备了系列Li0.5La0.5MgSrWO6∶xMn4+(LLMSW∶xMn4+)荧光粉，并对其结构和发光性能进行了系统的研究。实验结果表明，LLMSW∶xMn4+荧光粉为八面体结构，Mn4+占据八面体中心。Li+与La3+结合，形成阳离子对，平衡了格位取代时的多余电荷，实现了有效的电荷补偿，也导致了Mn4+周围局域环境发生变化，打破了发光中心的反演对称性，有利于实现2Eg→4A2g发光增强。LLMSW∶xMn4+荧光粉激发波段为270~600 nm，其激发峰分别归属于Mn→O电荷转移带(318 nm)、4A2g→4T1g(342 nm)、4A2g→2T2g(361 nm)和4A2g→4T2g(484 nm)。在332 nm紫外光激发下，其发射光谱位于650~800 nm(2Eg→4A2g)，呈深红色，峰值波长为708 nm。Mn4+最佳掺杂浓度为0.012，对应LLMSW∶0.012Mn4+荧光粉的荧光寿命为1.528 ms，内量子效率为65.74%，温度升高至423 K时，荧光强度降为室温下的53.1%，激活能为0.32 eV。采用365 nm紫外芯片封装的LED在40 mA电流激发下的光谱呈深红色，色坐标位于(0.724 0，0.269 6)，色纯度为98.1%。且其光谱与植物光敏色素(Pfr)具有很好的匹配性。
基于A位点阳离子替代策略，采用高温固相反应法制备了系列Li0.5La0.5MgSrWO6∶xMn4+(LLMSW∶xMn4+)荧光粉，并对其结构和发光性能进行了系统的研究。实验结果表明，LLMSW∶xMn4+荧光粉为八面体结构，Mn4+占据八面体中心。Li+与La3+结合，形成阳离子对，平衡了格位取代时的多余电荷，实现了有效的电荷补偿，也导致了Mn4+周围局域环境发生变化，打破了发光中心的反演对称性，有利于实现2Eg→4A2g发光增强。LLMSW∶xMn4+荧光粉激发波段为270~600 nm，其激发峰分别归属于Mn→O电荷转移带(318 nm)、4A2g→4T1g(342 nm)、4A2g→2T2g(361 nm)和4A2g→4T2g(484 nm)。在332 nm紫外光激发下，其发射光谱位于650~800 nm(2Eg→4A2g)，呈深红色，峰值波长为708 nm。Mn4+最佳掺杂浓度为0.012，对应LLMSW∶0.012Mn4+荧光粉的荧光寿命为1.528 ms，内量子效率为65.74%，温度升高至423 K时，荧光强度降为室温下的53.1%，激活能为0.32 eV。采用365 nm紫外芯片封装的LED在40 mA电流激发下的光谱呈深红色，色坐标位于(0.724 0，0.269 6)，色纯度为98.1%。且其光谱与植物光敏色素(Pfr)具有很好的匹配性。
2026, 42(1): 141-151
doi: 10.11862/CJIC.20250049
摘要:
采用硫酸铝(Al2(SO4)3)来强化硫酸(H2SO4)对混合稀土精矿中氟碳铈矿的浸取，使用三异辛胺和N1923对浸出液中的余酸和稀土元素进行分步萃取，并获得硫酸钙、冰晶石副产品及独居石精矿。结果表明，铝与氟的强配位作用不仅强化了浸取，还消除了HF的产生，有利于稀土与氟铝的分离及氟铝的综合回收利用，消除了对环境的影响。在液固比(矿浆中液体体积与固体的质量之比)为32 mL·g-1的条件下，100目的稀土混合精矿与3.0 mol·L-1 H2SO4和0.3 mol·L-1 Al2(SO4)3的混合溶液在135 ℃和200 r·min-1的搅拌条件下反应2 h时，精矿和稀土浸出率分别达到68.00%和66.91%，氟离子浸出率和萤石的分解率分别为94.42%和99.30%。采用三异辛胺萃取浸出液中的大部分余酸后，直接用N1923萃取稀土，萃取率为97.38%；用HCl反萃负载有机相中的稀土，反萃率为98.05%，反萃液中铝与稀土的质量比仅为0.008 0。萃余水相中的氟铝配合物与外加氟源反应生成冰晶石，实现了氟铝资源的回收。
采用硫酸铝(Al2(SO4)3)来强化硫酸(H2SO4)对混合稀土精矿中氟碳铈矿的浸取，使用三异辛胺和N1923对浸出液中的余酸和稀土元素进行分步萃取，并获得硫酸钙、冰晶石副产品及独居石精矿。结果表明，铝与氟的强配位作用不仅强化了浸取，还消除了HF的产生，有利于稀土与氟铝的分离及氟铝的综合回收利用，消除了对环境的影响。在液固比(矿浆中液体体积与固体的质量之比)为32 mL·g-1的条件下，100目的稀土混合精矿与3.0 mol·L-1 H2SO4和0.3 mol·L-1 Al2(SO4)3的混合溶液在135 ℃和200 r·min-1的搅拌条件下反应2 h时，精矿和稀土浸出率分别达到68.00%和66.91%，氟离子浸出率和萤石的分解率分别为94.42%和99.30%。采用三异辛胺萃取浸出液中的大部分余酸后，直接用N1923萃取稀土，萃取率为97.38%；用HCl反萃负载有机相中的稀土，反萃率为98.05%，反萃液中铝与稀土的质量比仅为0.008 0。萃余水相中的氟铝配合物与外加氟源反应生成冰晶石，实现了氟铝资源的回收。
