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2026, 42(4): 657-667
doi: 10.11862/CJIC.20250250
Abstract:
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
Abstract:
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
Abstract:
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。
Mixed-size MXene for the application of high-performance transparent zinc-ion hybrid supercapacitors
2026, 42(4): 703-712
doi: 10.11862/CJIC.20250331
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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.
