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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(4): 657-667
doi: 10.11862/CJIC.20250250
摘要:
金属有机框架(metal-organic frameworks，MOFs)是一类由有机配体和金属离子/金属簇组成的结晶多孔材料，其独特的物理、化学和生物学特征使其成为优秀的药物递送载体平台，在脑胶质瘤的治疗中发挥着重要作用。本文综述了基于不同种类MOFs在胶质瘤治疗中的最新研究进展，重点介绍了其在促进药物穿透血脑屏障(blood-brain barrier，BBB)、实现靶向递送、药物控释以及多种药物联合治疗等方面的应用，以期为MOFs在胶质瘤治疗中的进一步应用与推广提供参考。
金属有机框架(metal-organic frameworks，MOFs)是一类由有机配体和金属离子/金属簇组成的结晶多孔材料，其独特的物理、化学和生物学特征使其成为优秀的药物递送载体平台，在脑胶质瘤的治疗中发挥着重要作用。本文综述了基于不同种类MOFs在胶质瘤治疗中的最新研究进展，重点介绍了其在促进药物穿透血脑屏障(blood-brain barrier，BBB)、实现靶向递送、药物控释以及多种药物联合治疗等方面的应用，以期为MOFs在胶质瘤治疗中的进一步应用与推广提供参考。
2026, 42(4): 668-692
doi: 10.11862/CJIC.20250319
摘要:
随着新能源汽车与电子产品的快速发展，储能设备对电池正极材料的能量密度提出了更高要求。富锂锰基正极材料(xLi2MnO3·(1-x)LiTMO2，TM=Ni、Co、Mn)因其独特的阴离子氧化还原特性，以及由高Mn含量带来的高比容量和低成本优势，备受关注，已成为发展高能量密度电池的关键正极材料之一。然而，其合成过程中不同反应物间的相变过程及元素价态变化尚未完全阐明，且合成工艺对材料的首圈库仑效率、倍率性能及电压衰减特性等电化学性能的影响也缺乏系统性研究。为实现富锂锰基正极材料的可控制备，本文从材料的特殊结构与反应机制出发，梳理了常用合成方法及其特点，系统阐述了合成过程中不同反应物与反应条件、前驱体与锂源种类、过渡金属与锂源配比、烧结氧分压及烧结工艺对材料性能的影响，并综合分析了材料形成过程中的锂化演变、物相变化、元素价态变化及缺陷对其物理化学性质与电化学性能的作用机制。通过调控合成反应条件可以分散材料中的Li2MnO3晶畴，从而减轻因晶格氧析出导致的容量损失，减少合成过程中产生的缺陷，在确保材料结构稳定性的同时拓宽锂离子扩散通道。最后，本文对富锂锰基正极材料合成过程的研究进行了总结与展望。
随着新能源汽车与电子产品的快速发展，储能设备对电池正极材料的能量密度提出了更高要求。富锂锰基正极材料(xLi2MnO3·(1-x)LiTMO2，TM=Ni、Co、Mn)因其独特的阴离子氧化还原特性，以及由高Mn含量带来的高比容量和低成本优势，备受关注，已成为发展高能量密度电池的关键正极材料之一。然而，其合成过程中不同反应物间的相变过程及元素价态变化尚未完全阐明，且合成工艺对材料的首圈库仑效率、倍率性能及电压衰减特性等电化学性能的影响也缺乏系统性研究。为实现富锂锰基正极材料的可控制备，本文从材料的特殊结构与反应机制出发，梳理了常用合成方法及其特点，系统阐述了合成过程中不同反应物与反应条件、前驱体与锂源种类、过渡金属与锂源配比、烧结氧分压及烧结工艺对材料性能的影响，并综合分析了材料形成过程中的锂化演变、物相变化、元素价态变化及缺陷对其物理化学性质与电化学性能的作用机制。通过调控合成反应条件可以分散材料中的Li2MnO3晶畴，从而减轻因晶格氧析出导致的容量损失，减少合成过程中产生的缺陷，在确保材料结构稳定性的同时拓宽锂离子扩散通道。最后，本文对富锂锰基正极材料合成过程的研究进行了总结与展望。
2026, 42(4): 693-702
doi: 10.11862/CJIC.20250350
摘要:
针对新型质子导电材料在环境适应性与稳定性方面的需求，以2，5-二溴对苯二甲酸(H2BDC-Br2)为前驱体，采用溶剂热法构筑了三维离子型氢键有机框架(iHOF 1)。利用单晶X射线衍射、粉末X射线衍射、电化学阻抗谱及固态荧光光谱等表征技术，系统研究了其晶体结构、材料稳定性、质子传导行为及荧光性质。结构解析表明，iHOF 1结晶于单斜晶系C2/c空间群，其三维框架由HBDC-Br2-与(Me2NH2)+通过强分子间氢键和静电相互作用稳定构筑。电导性能测试显示，其质子电导率表现出显著的温湿度依赖性，在100 ℃、相对湿度(RH)98%条件下可达1.72×10-3 S·cm-1。不同湿度下的活化能分析(68%：Ea=0.44 eV，98%：Ea=0.41 eV)证实，质子传输遵循Grotthuss跳跃机制，框架内由亲水性羧基、溴原子及(Me2NH2)+构成的连续氢键网络是质子快速传导的关键。稳定性研究表明，该材料具有优异的热稳定性(分解温度：230 ℃)与化学稳定性(水浸泡及电化学测试后结构保持完整)。此外，该材料在324 nm光激发下于432 nm处呈现单色性良好的蓝光发射，源于芳香基团的π→π*跃迁。
针对新型质子导电材料在环境适应性与稳定性方面的需求，以2，5-二溴对苯二甲酸(H2BDC-Br2)为前驱体，采用溶剂热法构筑了三维离子型氢键有机框架(iHOF 1)。利用单晶X射线衍射、粉末X射线衍射、电化学阻抗谱及固态荧光光谱等表征技术，系统研究了其晶体结构、材料稳定性、质子传导行为及荧光性质。结构解析表明，iHOF 1结晶于单斜晶系C2/c空间群，其三维框架由HBDC-Br2-与(Me2NH2)+通过强分子间氢键和静电相互作用稳定构筑。电导性能测试显示，其质子电导率表现出显著的温湿度依赖性，在100 ℃、相对湿度(RH)98%条件下可达1.72×10-3 S·cm-1。不同湿度下的活化能分析(68%：Ea=0.44 eV，98%：Ea=0.41 eV)证实，质子传输遵循Grotthuss跳跃机制，框架内由亲水性羧基、溴原子及(Me2NH2)+构成的连续氢键网络是质子快速传导的关键。稳定性研究表明，该材料具有优异的热稳定性(分解温度：230 ℃)与化学稳定性(水浸泡及电化学测试后结构保持完整)。此外，该材料在324 nm光激发下于432 nm处呈现单色性良好的蓝光发射，源于芳香基团的π→π*跃迁。
2026, 42(4): 703-712
doi: 10.11862/CJIC.20250331
摘要:
通过原位刻蚀和机械剥离法制备了大尺寸Ti3C2Tx MXene纳米片(L-MXene，平均横向尺寸约为3.5 μm)，并进一步通过超声破碎获得小尺寸MXene纳米片(S-MXene，平均横向尺寸约为0.2 μm)。通过调控不同尺寸MXene片层的混合比例，构建了L-MXene/S-MXene复合材料，以优化片层堆叠结构、缩短离子传输路径。基于L-MXene/S-MXene透明电极组装的透明锌离子混合超级电容器(ZHSCs)的面积比电容达到8.34 mF·cm-2，透光率为64.7%，且在180°弯曲状态下容量保持率为93.9%。
通过原位刻蚀和机械剥离法制备了大尺寸Ti3C2Tx MXene纳米片(L-MXene，平均横向尺寸约为3.5 μm)，并进一步通过超声破碎获得小尺寸MXene纳米片(S-MXene，平均横向尺寸约为0.2 μm)。通过调控不同尺寸MXene片层的混合比例，构建了L-MXene/S-MXene复合材料，以优化片层堆叠结构、缩短离子传输路径。基于L-MXene/S-MXene透明电极组装的透明锌离子混合超级电容器(ZHSCs)的面积比电容达到8.34 mF·cm-2，透光率为64.7%，且在180°弯曲状态下容量保持率为93.9%。
2026, 42(4): 713-721
doi: 10.11862/CJIC.20250318
摘要:
为钝化二维钙钛矿晶体中的缺陷并改善晶体质量，将氯苯添加到(PMA)2PbBr4钙钛矿前驱体中(PMA+=C6H5CH2NH3+)，并通过冷却控温结晶法制备大尺寸高质量的钙钛矿单晶。采用粉末X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱和稳态-瞬态荧光光谱对钙钛矿晶体的结构、形貌和光学特性进行系统的表征测试。研究结果表明，添加浓度为0.38 mol·L-1的氯苯，能够有效调控晶体生长速率，增强结晶取向并钝化表、界面缺陷，显著抑制光生载流子的非辐射复合。此外，利用氯苯添加剂能够调控阳离子堆叠效应诱导改变晶体的微观应变，从而影响电子-声子耦合作用，改善材料的光电子特性。优化后晶体的双光致发光峰强度显著增强，0.38 mol·L-1氯苯钝化晶体的低能发射峰出现红移且半高宽减小，这表明氯苯添加剂能有效缓解晶体表面和内部的畸变应力。
为钝化二维钙钛矿晶体中的缺陷并改善晶体质量，将氯苯添加到(PMA)2PbBr4钙钛矿前驱体中(PMA+=C6H5CH2NH3+)，并通过冷却控温结晶法制备大尺寸高质量的钙钛矿单晶。采用粉末X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱和稳态-瞬态荧光光谱对钙钛矿晶体的结构、形貌和光学特性进行系统的表征测试。研究结果表明，添加浓度为0.38 mol·L-1的氯苯，能够有效调控晶体生长速率，增强结晶取向并钝化表、界面缺陷，显著抑制光生载流子的非辐射复合。此外，利用氯苯添加剂能够调控阳离子堆叠效应诱导改变晶体的微观应变，从而影响电子-声子耦合作用，改善材料的光电子特性。优化后晶体的双光致发光峰强度显著增强，0.38 mol·L-1氯苯钝化晶体的低能发射峰出现红移且半高宽减小，这表明氯苯添加剂能有效缓解晶体表面和内部的畸变应力。
2026, 42(4): 722-736
doi: 10.11862/CJIC.20250312
摘要:
通过烯烃聚合方法制备了一系列卟啉基离子聚合物IP1、IP2和IP1-M(M=Zn、Mg、Ni)，并采用傅里叶变换红外光谱(FTIR)、热重分析(TGA)、扫描电子显微镜(SEM)、能谱(EDS)面扫、比表面积与孔隙率分析、X射线光电子能谱(XPS)对其进行了系统表征。将所制备材料应用于催化CO2与环氧化物的环加成反应，结果表明，这些材料在低温常压条件下均表现出良好的催化性能。其中，Zn2+与卟啉配位的IP1-Zn催化活性最优，在无溶剂、80 ℃、5 h和101 kPa CO2的反应条件下，能以94.1%的产率将环氧氯丙烷转化为对应的环状碳酸酯，并展现出一定的底物普适性。同时，IP1-Zn表现出优异的循环稳定性，重复使用8次后催化产率仍保持在90%以上。
通过烯烃聚合方法制备了一系列卟啉基离子聚合物IP1、IP2和IP1-M(M=Zn、Mg、Ni)，并采用傅里叶变换红外光谱(FTIR)、热重分析(TGA)、扫描电子显微镜(SEM)、能谱(EDS)面扫、比表面积与孔隙率分析、X射线光电子能谱(XPS)对其进行了系统表征。将所制备材料应用于催化CO2与环氧化物的环加成反应，结果表明，这些材料在低温常压条件下均表现出良好的催化性能。其中，Zn2+与卟啉配位的IP1-Zn催化活性最优，在无溶剂、80 ℃、5 h和101 kPa CO2的反应条件下，能以94.1%的产率将环氧氯丙烷转化为对应的环状碳酸酯，并展现出一定的底物普适性。同时，IP1-Zn表现出优异的循环稳定性，重复使用8次后催化产率仍保持在90%以上。
2026, 42(4): 737-746
doi: 10.11862/CJIC.20250305
摘要:
以羧甲基纤维素钠(CMC)为前驱体，制备了铁(Fe)、氮(N)共掺杂碳基催化剂(180FeNC-2)。结果表明，对CMC进行预脱氧处理可诱导其糖苷键断裂，这有利于提高其与含N前驱体共同碳化所得产物的N掺杂量，同时能够促进其转化为规整的薄层碳片，从而构建多层次介孔结构，增强催化反应中的物质传输与活性位点的暴露。180FeNC-2在碱性电解液中的氧还原半波电位为0.887 V(vs RHE)，电化学活性表面积为11.26 mF·cm-2，电荷传输电阻为81 Ω，催化活性优于由未经预脱氧处理的CMC所制的催化剂(0FeNC-2)，并与Pt/C催化剂相当，展现出优异的稳定性和耐甲醇性能。基于180FeNC-2组装的锌-空气电池的开路电压为1.478 V，最大功率密度达到162 mW·cm-2，在10 mA·cm-2的电流密度下可于1.25 V的电压下稳定放电。
以羧甲基纤维素钠(CMC)为前驱体，制备了铁(Fe)、氮(N)共掺杂碳基催化剂(180FeNC-2)。结果表明，对CMC进行预脱氧处理可诱导其糖苷键断裂，这有利于提高其与含N前驱体共同碳化所得产物的N掺杂量，同时能够促进其转化为规整的薄层碳片，从而构建多层次介孔结构，增强催化反应中的物质传输与活性位点的暴露。180FeNC-2在碱性电解液中的氧还原半波电位为0.887 V(vs RHE)，电化学活性表面积为11.26 mF·cm-2，电荷传输电阻为81 Ω，催化活性优于由未经预脱氧处理的CMC所制的催化剂(0FeNC-2)，并与Pt/C催化剂相当，展现出优异的稳定性和耐甲醇性能。基于180FeNC-2组装的锌-空气电池的开路电压为1.478 V，最大功率密度达到162 mW·cm-2，在10 mA·cm-2的电流密度下可于1.25 V的电压下稳定放电。
2026, 42(4): 747-759
doi: 10.11862/CJIC.20250286
摘要:
针对异质结光催化剂中界面电荷传输效率低以及粉体催化剂难以回收的问题，我们成功构建了基于聚多巴胺(PDA)电子桥的S型异质结光催化剂。通过静电自组装法在PDA修饰的石墨相氮化碳(g-C3N4)表面负载Bi4Ti3O12，制备了粉体材料g-C3N4@PDA-Bi4Ti3O12(CN@PDA-BTO)。光催化降解、荧光光谱和电化学测试表明，PDA作为电子传输“桥梁”有效增强了界面接触与电荷分离效率。在可见光照射下，最佳样品CN@PDA-BTO-20复合材料对亚甲蓝(MB)和盐酸四环素(TCH)的降解效率分别高达98.2%(60 min)和81.1%(90 min)，其表观反应速率常数显著优于单一组分及二元复合材料。为进一步解决粉体催化剂的回收难题，将CN@PDA-BTO-20负载于聚乙烯醇(PVA)水凝胶网络中，制得CN@PDA-BTO-PVA柔性薄膜。该薄膜在5次循环使用后，对MB与TCH的降解效率仍分别保持在77.5%和71.6%，表现出优异的稳定性和可重复使用性。
针对异质结光催化剂中界面电荷传输效率低以及粉体催化剂难以回收的问题，我们成功构建了基于聚多巴胺(PDA)电子桥的S型异质结光催化剂。通过静电自组装法在PDA修饰的石墨相氮化碳(g-C3N4)表面负载Bi4Ti3O12，制备了粉体材料g-C3N4@PDA-Bi4Ti3O12(CN@PDA-BTO)。光催化降解、荧光光谱和电化学测试表明，PDA作为电子传输“桥梁”有效增强了界面接触与电荷分离效率。在可见光照射下，最佳样品CN@PDA-BTO-20复合材料对亚甲蓝(MB)和盐酸四环素(TCH)的降解效率分别高达98.2%(60 min)和81.1%(90 min)，其表观反应速率常数显著优于单一组分及二元复合材料。为进一步解决粉体催化剂的回收难题，将CN@PDA-BTO-20负载于聚乙烯醇(PVA)水凝胶网络中，制得CN@PDA-BTO-PVA柔性薄膜。该薄膜在5次循环使用后，对MB与TCH的降解效率仍分别保持在77.5%和71.6%，表现出优异的稳定性和可重复使用性。
2026, 42(4): 760-772
doi: 10.11862/CJIC.20250273
摘要:
采用原位静电自组装法，再经单宁酸溶液蚀刻，构建了用于负载锂硫电池中活性物质硫的MXene Ti3C2Tx/中空ZIF-67(HMZ)载体。中空ZIF-67能够有效抑制MXene Ti3C2Tx的不可逆堆叠趋势，并通过Ti和Co元素共同化学吸附锂多硫化物，抑制穿梭效应，同时还能通过物理作用限制锂多硫化物，缓解膨胀效应。结果表明，单宁酸溶液蚀刻5 min形成的HMZ-5经载硫后在1C下能够提供615.1 mAh·g-1的比容量，且在700次的循环过程中具有0.055%的低容量衰减率。
采用原位静电自组装法，再经单宁酸溶液蚀刻，构建了用于负载锂硫电池中活性物质硫的MXene Ti3C2Tx/中空ZIF-67(HMZ)载体。中空ZIF-67能够有效抑制MXene Ti3C2Tx的不可逆堆叠趋势，并通过Ti和Co元素共同化学吸附锂多硫化物，抑制穿梭效应，同时还能通过物理作用限制锂多硫化物，缓解膨胀效应。结果表明，单宁酸溶液蚀刻5 min形成的HMZ-5经载硫后在1C下能够提供615.1 mAh·g-1的比容量，且在700次的循环过程中具有0.055%的低容量衰减率。
2026, 42(4): 773-788
doi: 10.11862/CJIC.20250251
摘要:
探究了Ba、Bi化学计量比对晶体结构、形貌及催化性能的调控机制。利用粉末X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱、扫描电子显微镜等表征手段，结合碱性环境下的“剪切效应”研究了Bi12TiO20/BaTiO3的结构转变过程，并探究其催化性能影响。研究结果表明，Bi12TiO20/BaTiO3经历了“化学键重组-晶体生成-长大-Ostwald熟化”过程，其在超声振动、光照、超声振动和光照条件下降解染料的反应速率常数k分别达2.05×10-2、1.06×10-1、1.47×10-1 min-1，展现出良好的压电-光催化协同效果，这主要归因于形成的Bi12TiO20/BaTiO3异质结为光生载流子的运输提供了新通道和BaTiO3建立的内建电场为载流子分离提供了新动力。
探究了Ba、Bi化学计量比对晶体结构、形貌及催化性能的调控机制。利用粉末X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱、扫描电子显微镜等表征手段，结合碱性环境下的“剪切效应”研究了Bi12TiO20/BaTiO3的结构转变过程，并探究其催化性能影响。研究结果表明，Bi12TiO20/BaTiO3经历了“化学键重组-晶体生成-长大-Ostwald熟化”过程，其在超声振动、光照、超声振动和光照条件下降解染料的反应速率常数k分别达2.05×10-2、1.06×10-1、1.47×10-1 min-1，展现出良好的压电-光催化协同效果，这主要归因于形成的Bi12TiO20/BaTiO3异质结为光生载流子的运输提供了新通道和BaTiO3建立的内建电场为载流子分离提供了新动力。
2026, 42(4): 789-807
doi: 10.11862/CJIC.20250208
摘要:
采用一步溶剂热法结合多元表面修饰工艺，以四氧化三铁(Fe3O4)和还原氧化石墨烯(rGO)为核，表面接枝盐酸多巴胺(DA)、十二烷基苯磺酸钠(SDBS)和十六十八烷基二甲基羟丙基磺基甜菜碱(HSB1618)制备双亲性磁性复合材料Fe3O4/rGO/PDA(聚多巴胺)/SDBS/HSB(FGPSH)。系统研究了该材料对水体中聚氯乙烯(PVC)和聚对苯二甲酸乙二醇酯(PET)微塑料(MPs)的吸附行为。结果表明，FGPSH呈纳米多孔球状结构，平均粒径为426.15 nm，平均孔径为33.02 nm。材料表现出优异的超顺磁性，饱和磁化强度高达44.15 emu·g-1，可通过外加磁场实现快速固液分离。多层表面修饰使FGPSH兼具亲水性和疏水性，并使其在水体中保持高分散性的同时，为不同极性MPs匹配吸附位点，呈现出广谱且高效的选择性吸附行为。在优化条件下(PVC和PET的初始质量浓度均为25 mg·L-1，溶液pH均为9.0，FGPSH用量分别优化为0.50和0.40 g·L-1，吸附时间分别为30和80 min)，FGPSH对PVC和PET的吸附率分别达到97.58%和95.30%，对应吸附容量分别为48.75和60.33 mg·g-1，且经过5次吸附-脱附循环后仍能保持85%以上的吸附率。吸附热力学与动力学研究表明，FGPSH对亲水性PVC的吸附行为符合准二级动力学模型和Freundlich等温吸附模型，而对疏水性PET的吸附则遵循Langmuir模型，表明其对不同极性微塑料的吸附机制存在显著差异。
采用一步溶剂热法结合多元表面修饰工艺，以四氧化三铁(Fe3O4)和还原氧化石墨烯(rGO)为核，表面接枝盐酸多巴胺(DA)、十二烷基苯磺酸钠(SDBS)和十六十八烷基二甲基羟丙基磺基甜菜碱(HSB1618)制备双亲性磁性复合材料Fe3O4/rGO/PDA(聚多巴胺)/SDBS/HSB(FGPSH)。系统研究了该材料对水体中聚氯乙烯(PVC)和聚对苯二甲酸乙二醇酯(PET)微塑料(MPs)的吸附行为。结果表明，FGPSH呈纳米多孔球状结构，平均粒径为426.15 nm，平均孔径为33.02 nm。材料表现出优异的超顺磁性，饱和磁化强度高达44.15 emu·g-1，可通过外加磁场实现快速固液分离。多层表面修饰使FGPSH兼具亲水性和疏水性，并使其在水体中保持高分散性的同时，为不同极性MPs匹配吸附位点，呈现出广谱且高效的选择性吸附行为。在优化条件下(PVC和PET的初始质量浓度均为25 mg·L-1，溶液pH均为9.0，FGPSH用量分别优化为0.50和0.40 g·L-1，吸附时间分别为30和80 min)，FGPSH对PVC和PET的吸附率分别达到97.58%和95.30%，对应吸附容量分别为48.75和60.33 mg·g-1，且经过5次吸附-脱附循环后仍能保持85%以上的吸附率。吸附热力学与动力学研究表明，FGPSH对亲水性PVC的吸附行为符合准二级动力学模型和Freundlich等温吸附模型，而对疏水性PET的吸附则遵循Langmuir模型，表明其对不同极性微塑料的吸附机制存在显著差异。
2026, 42(4): 808-816
doi: 10.11862/CJIC.20260012
摘要:
5, 5′-dithiobis(2-nitrobenzoic acid) (H2DTNB) was employed as the second ligand to react with cucurbit[6]uril (Q[6]) and Cd(NO3)2, and it was deprotonated or transformed into HDTNB-, TNB2- and NSB2- (H2TNB=5, 5′-thiobis(2-nitrobenzoic acid), H2NSB=2-nitro-5-sulfobenzoic acid) under different conditions to afford three novel supramolecular assemblies with the formulas of [Cd(H2O)4(Q[6])](HDTNB)2·3H2O (1), [Cd(H2O)6]2(TNB)2·Q[6]·4H2O (2) and [Cd(H2O)5(NSB)]2·Q[6] (3). Singe-crystal diffraction (SC-XRD) analysis revealed that assembly 1 is constructed from 2D [Cd(H2O)4(Q[6])]2+ supramolecular layers and HDTNB- supra molecular layers, the structure of assembly 2 is comprised of the 2D {[Cd(H2O)6]2·Q[6]}4+ supramolecular layers and 1D TNB2- supramolecular chains, while assembly 3 is built from the 3D Q[6] frameworks with [Cd(H2O)5(NSB)] supramolecular chains filled in the pores. Meanwhile, the noncovalent interactions between the ligands HDTNB-/TNB2-/NSB2- and the outer-surface of Q[6] molecules contributed greatly to the formation of the supramolecular architecture of assemblies 1-3.
5, 5′-dithiobis(2-nitrobenzoic acid) (H2DTNB) was employed as the second ligand to react with cucurbit[6]uril (Q[6]) and Cd(NO3)2, and it was deprotonated or transformed into HDTNB-, TNB2- and NSB2- (H2TNB=5, 5′-thiobis(2-nitrobenzoic acid), H2NSB=2-nitro-5-sulfobenzoic acid) under different conditions to afford three novel supramolecular assemblies with the formulas of [Cd(H2O)4(Q[6])](HDTNB)2·3H2O (1), [Cd(H2O)6]2(TNB)2·Q[6]·4H2O (2) and [Cd(H2O)5(NSB)]2·Q[6] (3). Singe-crystal diffraction (SC-XRD) analysis revealed that assembly 1 is constructed from 2D [Cd(H2O)4(Q[6])]2+ supramolecular layers and HDTNB- supra molecular layers, the structure of assembly 2 is comprised of the 2D {[Cd(H2O)6]2·Q[6]}4+ supramolecular layers and 1D TNB2- supramolecular chains, while assembly 3 is built from the 3D Q[6] frameworks with [Cd(H2O)5(NSB)] supramolecular chains filled in the pores. Meanwhile, the noncovalent interactions between the ligands HDTNB-/TNB2-/NSB2- and the outer-surface of Q[6] molecules contributed greatly to the formation of the supramolecular architecture of assemblies 1-3.
2026, 42(4): 817-825
doi: 10.11862/CJIC.20250376
摘要:
Two [FeFe]-hydrogenase compounds with 2-cyanobenzyl groups, {Fe2[(SCH2CH3)(SR)](CO)6} (1 or 1′, which are the crystalline states from petroleum ether and dichloromethane solution, respectively) and {Fe2[(SCH2CH3)(SR)](CO)5(PPh3)} (2) (R=2-cyanobenzyl), were synthesized and characterized by infrared spectroscopy, UV-Vis spectroscopy, single-crystal diffraction, powder X-ray diffraction, etc. Their performances as photocatalysts for H2 production through water splitting were evaluated. The results showed that 316.8 μmol of H2 was produced on compound 1 after 3 h of illumination, with a catalytic efficiency of 25.1 μmol·mg-1·h-1 and a turnover number (TON) of 36.8. The replacement of carbonyl with PPh3 could significantly improve the catalytic performance of the complex, and 705.0 μmol of H2 was produced on 2 after 3 h of illumination, with a catalytic efficiency of 37.9 μmol·mg-1·h-1 and a TON of 81.8.
Two [FeFe]-hydrogenase compounds with 2-cyanobenzyl groups, {Fe2[(SCH2CH3)(SR)](CO)6} (1 or 1′, which are the crystalline states from petroleum ether and dichloromethane solution, respectively) and {Fe2[(SCH2CH3)(SR)](CO)5(PPh3)} (2) (R=2-cyanobenzyl), were synthesized and characterized by infrared spectroscopy, UV-Vis spectroscopy, single-crystal diffraction, powder X-ray diffraction, etc. Their performances as photocatalysts for H2 production through water splitting were evaluated. The results showed that 316.8 μmol of H2 was produced on compound 1 after 3 h of illumination, with a catalytic efficiency of 25.1 μmol·mg-1·h-1 and a turnover number (TON) of 36.8. The replacement of carbonyl with PPh3 could significantly improve the catalytic performance of the complex, and 705.0 μmol of H2 was produced on 2 after 3 h of illumination, with a catalytic efficiency of 37.9 μmol·mg-1·h-1 and a TON of 81.8.
2026, 42(4): 826-842
doi: 10.11862/CJIC.20250332
摘要:
A metal-organic framework/inorganic composite (ZIF-8@AMP) was synthesized by the in situ introduction of the active component ammonium phosphomolybdate (AMP) during the ambient solution-phase synthesis of the metal-organic framework (ZIF-8). The structure and properties of the composite were characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). Its adsorption performance for Rb+ and Cs+ in water was investigated. Results indicate that ZIF-8@AMP exhibited adsorption efficiencies of 93.5% and 95.6% for Rb+ and Cs+ within 30 min, with maximum adsorption capacities of 92.7 and 104.5 mg·g-1, respectively. After five adsorption-desorption cycles, it maintained high adsorption capacity and achieved over 84.9% adsorption efficiency for Rb+ and Cs+ in actual brine samples. The adsorption of ZIF-8@AMP for Rb+ and Cs+ follows pseudo-second-order kinetics and the Langmuir adsorption isotherm, indicating an endothermic, entropy-increasing, and spontaneous process. The adsorption mechanism involves electrostatic attraction and ion exchange between ZIF-8@AMP and Rb+ and Cs+.
A metal-organic framework/inorganic composite (ZIF-8@AMP) was synthesized by the in situ introduction of the active component ammonium phosphomolybdate (AMP) during the ambient solution-phase synthesis of the metal-organic framework (ZIF-8). The structure and properties of the composite were characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). Its adsorption performance for Rb+ and Cs+ in water was investigated. Results indicate that ZIF-8@AMP exhibited adsorption efficiencies of 93.5% and 95.6% for Rb+ and Cs+ within 30 min, with maximum adsorption capacities of 92.7 and 104.5 mg·g-1, respectively. After five adsorption-desorption cycles, it maintained high adsorption capacity and achieved over 84.9% adsorption efficiency for Rb+ and Cs+ in actual brine samples. The adsorption of ZIF-8@AMP for Rb+ and Cs+ follows pseudo-second-order kinetics and the Langmuir adsorption isotherm, indicating an endothermic, entropy-increasing, and spontaneous process. The adsorption mechanism involves electrostatic attraction and ion exchange between ZIF-8@AMP and Rb+ and Cs+.
2026, 42(4): 843-860
doi: 10.11862/CJIC.20250301
摘要:
To overcome the limitations of traditional photocatalysts, such as inefficient separation of charge carriers and poor visible-light absorption, S-scheme g-C3N4/TiO2 heterojunction photocatalysts were synthesized via a combined method of thermal polymerization, hydrothermal synthesis, and calcination. The crystal structures, morphological features, and optical properties of the composites were systematically characterized, and their photocatalytic performance was evaluated through tetracycline (TC) degradation and hydrogen evolution experiments. Trapping experiments and electron paramagnetic resonance (EPR) measurements were conducted to elucidate the reaction mechanisms. The results demonstrate that the S-scheme heterojunction effectively extends the visible-light absorption range and facilitates the efficient separation of photogenerated electron-hole pairs. Under optimal conditions, the composite achieved a TC degradation rate of 94.5% and a hydrogen evolution rate of 329.1 μmol·h-1·g-1 after 8 h of irradiation, both values being significantly higher than those of pristine g-C3N4 or TiO2. Moreover, the S-scheme g-C3N4/TiO2 heterojunction retained high photocatalytic activity over five consecutive cycles, confirming its excellent stability. Mechanistic investigations revealed that the S-scheme heterojunction maintained strong redox capacities, with superoxide radicals (·O2-), hydroxyl radicals (·OH), electrons (e-), and holes (h+) serving as the primary active species responsible for TC degradation and H2 production.
To overcome the limitations of traditional photocatalysts, such as inefficient separation of charge carriers and poor visible-light absorption, S-scheme g-C3N4/TiO2 heterojunction photocatalysts were synthesized via a combined method of thermal polymerization, hydrothermal synthesis, and calcination. The crystal structures, morphological features, and optical properties of the composites were systematically characterized, and their photocatalytic performance was evaluated through tetracycline (TC) degradation and hydrogen evolution experiments. Trapping experiments and electron paramagnetic resonance (EPR) measurements were conducted to elucidate the reaction mechanisms. The results demonstrate that the S-scheme heterojunction effectively extends the visible-light absorption range and facilitates the efficient separation of photogenerated electron-hole pairs. Under optimal conditions, the composite achieved a TC degradation rate of 94.5% and a hydrogen evolution rate of 329.1 μmol·h-1·g-1 after 8 h of irradiation, both values being significantly higher than those of pristine g-C3N4 or TiO2. Moreover, the S-scheme g-C3N4/TiO2 heterojunction retained high photocatalytic activity over five consecutive cycles, confirming its excellent stability. Mechanistic investigations revealed that the S-scheme heterojunction maintained strong redox capacities, with superoxide radicals (·O2-), hydroxyl radicals (·OH), electrons (e-), and holes (h+) serving as the primary active species responsible for TC degradation and H2 production.
2026, 42(4): 861-871
doi: 10.11862/CJIC.20250294
摘要:
A metal-organic framework {[Zn(L)0.5(1,2,4,5-tpb)0.5]·DMF·3H2O}n (1) was synthesized by solvothermal reaction, where H4L=5,5′-(ethane-1,2-diyl)diisophthalic acid, and 1,2,4,5-tpb=1,2,4,5-tetra(pyridin-4-yl)benzene. The analysis of the single crystal structure indicates that L4- and 1,2,4,5-tpb are connected with Zn(Ⅱ) to form a 2D layered structure, and the layers are linked by 1,2,4,5-tpb to form a 3D structure. 1 can be used as a highly selective fluorescent probe for the detection of 2,4-dinitrophenylhydrazine (DNP) and tetracycline (TET), and the detection limits were 0.013 and 0.31 μmol·L-1, respectively. 1 was applied successfully to the determination of TET content in the Yanhe River water sample.
A metal-organic framework {[Zn(L)0.5(1,2,4,5-tpb)0.5]·DMF·3H2O}n (1) was synthesized by solvothermal reaction, where H4L=5,5′-(ethane-1,2-diyl)diisophthalic acid, and 1,2,4,5-tpb=1,2,4,5-tetra(pyridin-4-yl)benzene. The analysis of the single crystal structure indicates that L4- and 1,2,4,5-tpb are connected with Zn(Ⅱ) to form a 2D layered structure, and the layers are linked by 1,2,4,5-tpb to form a 3D structure. 1 can be used as a highly selective fluorescent probe for the detection of 2,4-dinitrophenylhydrazine (DNP) and tetracycline (TET), and the detection limits were 0.013 and 0.31 μmol·L-1, respectively. 1 was applied successfully to the determination of TET content in the Yanhe River water sample.
2026, 42(4): 872-882
doi: 10.11862/CJIC.20250287
摘要:
Based on 4′-(1H-tetrazol-5-yl)-[1, 1′-biphenyl]-2, 4, 6-tricarboxylic acid (H4bta) ligand, zinc metal-organic framework (Zn-MOF): {[Zn2(bta)(bpy)2(H2O)]·1.5H2O}n (bpy=2, 2′-bipyridine) was designed and synthesized by hydrothermal method. Its structure was characterized by elemental analysis, IR spectra, X-ray single crystal diffraction, etc. The asymmetric unit of Zn-MOF contains two crystallographically independent Zn2+ ions. Through the connection of Zn2+ ions via H4bta, a 1D double-layer network structure is formed. Adjacent double-layer networks further form a 2D supramolecular network through hydrogen bonding. Notably, Zn-MOF exhibited excellent fluorescence properties and could efficiently and sensitively detect various water pollutants: 4-nitrophenol (4-NP), Cu2+, and pyrimethanil (Pth). Additionally, the mechanism of fluorescence sensing was investigated.
Based on 4′-(1H-tetrazol-5-yl)-[1, 1′-biphenyl]-2, 4, 6-tricarboxylic acid (H4bta) ligand, zinc metal-organic framework (Zn-MOF): {[Zn2(bta)(bpy)2(H2O)]·1.5H2O}n (bpy=2, 2′-bipyridine) was designed and synthesized by hydrothermal method. Its structure was characterized by elemental analysis, IR spectra, X-ray single crystal diffraction, etc. The asymmetric unit of Zn-MOF contains two crystallographically independent Zn2+ ions. Through the connection of Zn2+ ions via H4bta, a 1D double-layer network structure is formed. Adjacent double-layer networks further form a 2D supramolecular network through hydrogen bonding. Notably, Zn-MOF exhibited excellent fluorescence properties and could efficiently and sensitively detect various water pollutants: 4-nitrophenol (4-NP), Cu2+, and pyrimethanil (Pth). Additionally, the mechanism of fluorescence sensing was investigated.
2026, 42(4): 883-896
doi: 10.11862/CJIC.20250248
摘要:
The ionothermal reaction between CuCl2, 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (BBTZ), and (NH4)6Mo7O24 in 1-ethyl-3-methylimidazolium bromide ((Emim)Br) led to a new octamolybdate-based coordination polymer (Emim)2[Cu(BBTZ)2(β-Mo8O26)] (Mo8-CP). Mo8-CP was characterized by elemental analysis, thermogravimetry, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. In Mo8-CP, structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain. These chains are further bridged by (β-Mo8O26)4- to construct a 3D coordination polymer. Notably, (Emim)+ acts as a structure-directing agent, occupying the channels of the 3D coordination polymer. Based on this unique structure, the ion exchange properties of Mo8-CP toward rare-earth ions were investigated. It has been found that the luminescent color of the material can be successfully regulated by introducing Eu3+ or Tb3+ through ion exchange.
The ionothermal reaction between CuCl2, 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (BBTZ), and (NH4)6Mo7O24 in 1-ethyl-3-methylimidazolium bromide ((Emim)Br) led to a new octamolybdate-based coordination polymer (Emim)2[Cu(BBTZ)2(β-Mo8O26)] (Mo8-CP). Mo8-CP was characterized by elemental analysis, thermogravimetry, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. In Mo8-CP, structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain. These chains are further bridged by (β-Mo8O26)4- to construct a 3D coordination polymer. Notably, (Emim)+ acts as a structure-directing agent, occupying the channels of the 3D coordination polymer. Based on this unique structure, the ion exchange properties of Mo8-CP toward rare-earth ions were investigated. It has been found that the luminescent color of the material can be successfully regulated by introducing Eu3+ or Tb3+ through ion exchange.
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。
