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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(10): 2051-2062
doi: 10.11862/CJIC.20260204
摘要:
尿素是重要的农用肥料与化工原料，但其传统合成工艺存在能耗高、碳排放量大等突出问题。而电催化合成尿素作为一种绿色合成路线，有助于实现碳减排与氮资源循环利用。当前电催化合成尿素仍面临反应物活化困难、C-N偶联效率低等关键挑战。金属有机框架(MOFs)凭借活性中心可调、多孔结构利于传质、配体功能可设计等独特优势，为解决上述瓶颈提供了理想的材料平台。本文系统综述了基于单金属MOFs、多元金属MOFs以及MOF基复合材料在电催化合成尿素领域的研究进展，重点围绕其结构设计策略、催化作用机制与性能优化途径进行归纳、评述。在此基础上，进一步分析了当前MOF基催化剂在C-N偶联效率、反应选择性等方面的挑战，并对其规模化应用及未来发展方向进行了展望，以期为高效尿素电合成催化剂的理性设计与开发提供参考。
尿素是重要的农用肥料与化工原料，但其传统合成工艺存在能耗高、碳排放量大等突出问题。而电催化合成尿素作为一种绿色合成路线，有助于实现碳减排与氮资源循环利用。当前电催化合成尿素仍面临反应物活化困难、C-N偶联效率低等关键挑战。金属有机框架(MOFs)凭借活性中心可调、多孔结构利于传质、配体功能可设计等独特优势，为解决上述瓶颈提供了理想的材料平台。本文系统综述了基于单金属MOFs、多元金属MOFs以及MOF基复合材料在电催化合成尿素领域的研究进展，重点围绕其结构设计策略、催化作用机制与性能优化途径进行归纳、评述。在此基础上，进一步分析了当前MOF基催化剂在C-N偶联效率、反应选择性等方面的挑战，并对其规模化应用及未来发展方向进行了展望，以期为高效尿素电合成催化剂的理性设计与开发提供参考。
2026, 42(10): 2063-2076
doi: 10.11862/CJIC.20260194
摘要:
水系锌离子电池因安全性高、成本低和环境友好等优势而受到广泛关注，但其在循环过程中易发生枝晶生长、析氢、腐蚀、界面副产物沉积及正极溶解等问题，严重制约了实际应用。电解液添加剂作为一种高效且易实施的调控策略，可通过调节Zn2+溶剂化结构、重构双电层与电极/电解液界面、诱导锌沉积取向、抑制正极溶解及缓冲界面pH波动等途径，显著提升水系锌离子电池的循环稳定性与沉积/剥离可逆性。本文系统综述了近年来电解液添加剂在水系锌离子电池中的研究进展，总结了不同类型添加剂的作用机制及构效关系，并对机理解析、长期稳定性、多组分协同及工程化应用等方面面临的挑战进行了讨论与展望。
水系锌离子电池因安全性高、成本低和环境友好等优势而受到广泛关注，但其在循环过程中易发生枝晶生长、析氢、腐蚀、界面副产物沉积及正极溶解等问题，严重制约了实际应用。电解液添加剂作为一种高效且易实施的调控策略，可通过调节Zn2+溶剂化结构、重构双电层与电极/电解液界面、诱导锌沉积取向、抑制正极溶解及缓冲界面pH波动等途径，显著提升水系锌离子电池的循环稳定性与沉积/剥离可逆性。本文系统综述了近年来电解液添加剂在水系锌离子电池中的研究进展，总结了不同类型添加剂的作用机制及构效关系，并对机理解析、长期稳定性、多组分协同及工程化应用等方面面临的挑战进行了讨论与展望。
2026, 42(10): 2077-2091
doi: 10.11862/CJIC.20260220
摘要:
以Keggin型磷钼酸(H3PMo12O40)为模板，亚乙基二膦酸四异丙酯(L)为配体，采用水浴回流法合成了4种新型稀土配合物[Ln(L)3(H2O)2](PMo12O40)·4CH3CN(Ln=Pr、Tb、Dy、Er)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、热重分析及固体紫外可见漫反射光谱对配合物进行了系统表征。单晶结构解析表明4种配合物为同构晶体，属三斜晶系P1空间群，中心稀土离子呈八配位扭曲四方反棱柱构型，与3个双齿螯合L配体和2个水分子配位，多酸阴离子作为抗衡离子，通过氢键作用被固定在晶格中。热重分析记录了配合物的质量变化过程。通过固体紫外可见漫反射光谱计算得配合物的光学带隙为2.56~2.57 eV。在配合物光催化降解罗丹明B实验中，紫外光照90 min内罗丹明B的降解率为95.21%~97.53%。活性物种捕获实验显示·OH、·O2-和h+参与光催化降解过程。太赫兹时域光谱(0.4~2.4 THz)记录到配体骨架振动及分子间弱相互作用引起的特征吸收峰。
以Keggin型磷钼酸(H3PMo12O40)为模板，亚乙基二膦酸四异丙酯(L)为配体，采用水浴回流法合成了4种新型稀土配合物[Ln(L)3(H2O)2](PMo12O40)·4CH3CN(Ln=Pr、Tb、Dy、Er)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、热重分析及固体紫外可见漫反射光谱对配合物进行了系统表征。单晶结构解析表明4种配合物为同构晶体，属三斜晶系P1空间群，中心稀土离子呈八配位扭曲四方反棱柱构型，与3个双齿螯合L配体和2个水分子配位，多酸阴离子作为抗衡离子，通过氢键作用被固定在晶格中。热重分析记录了配合物的质量变化过程。通过固体紫外可见漫反射光谱计算得配合物的光学带隙为2.56~2.57 eV。在配合物光催化降解罗丹明B实验中，紫外光照90 min内罗丹明B的降解率为95.21%~97.53%。活性物种捕获实验显示·OH、·O2-和h+参与光催化降解过程。太赫兹时域光谱(0.4~2.4 THz)记录到配体骨架振动及分子间弱相互作用引起的特征吸收峰。
2026, 42(10): 2092-2098
doi: 10.11862/CJIC.20260157
摘要:
基于水热反应法成功合成了以四(4-羧基苯基)卟啉(TCPP)为配体的谷胱甘肽(GSH)响应型纳米级金属有机框架(nMOF)材料，即Cu-TCPP-nMOF。该纳米材料由于变价金属的存在具有较强的类过氧化物酶活性，当存在H2O2时可以催化酶底物3，3′，5，5′-四甲基联苯胺(TMB)发生反应，使反应体系颜色由无色变为蓝色。此外，该纳米材料可作为GSH响应型比色纳米探针，实现对GSH的高灵敏检测。Cu-TCPP-nMOF可以与GSH发生反应，并且随着GSH的逐渐加入，TMB+H2O2反应体系的颜色逐渐变淡。GSH检测的线性范围为10~60 μmol·L-1，检测限(LOD)达到1.20 μmol·L-1。
基于水热反应法成功合成了以四(4-羧基苯基)卟啉(TCPP)为配体的谷胱甘肽(GSH)响应型纳米级金属有机框架(nMOF)材料，即Cu-TCPP-nMOF。该纳米材料由于变价金属的存在具有较强的类过氧化物酶活性，当存在H2O2时可以催化酶底物3，3′，5，5′-四甲基联苯胺(TMB)发生反应，使反应体系颜色由无色变为蓝色。此外，该纳米材料可作为GSH响应型比色纳米探针，实现对GSH的高灵敏检测。Cu-TCPP-nMOF可以与GSH发生反应，并且随着GSH的逐渐加入，TMB+H2O2反应体系的颜色逐渐变淡。GSH检测的线性范围为10~60 μmol·L-1，检测限(LOD)达到1.20 μmol·L-1。
2026, 42(10): 2099-2108
doi: 10.11862/CJIC.20260150
摘要:
以五水合硫酸铜(CuSO4·5H2O)和4，4′-联吡啶(4，4′-bipy)为原料，通过室温固相合成法制备了纳米级铜配位聚合物{[Cu(4，4′-bipy)(H2O)3(SO4)]·2H2O}n (Cu-CP)。扫描电镜结果显示，该材料呈现均匀颗粒状，尺寸分布在100~300 nm范围内。将其作为吸附剂用于吸附水溶液中的有机染料时，该材料对刚果红(CR)染料具有优异的吸附性能，吸附容量高达5 486 mg·g-1，去除率达99.50%。吸附动力学和热力学研究表明，该吸附过程符合准二级动力学模型，且为单层化学吸附。此外，采用的球磨辅助室温固相合成策略具有操作简便、无需溶剂、易于放大及产率高等优势。
以五水合硫酸铜(CuSO4·5H2O)和4，4′-联吡啶(4，4′-bipy)为原料，通过室温固相合成法制备了纳米级铜配位聚合物{[Cu(4，4′-bipy)(H2O)3(SO4)]·2H2O}n (Cu-CP)。扫描电镜结果显示，该材料呈现均匀颗粒状，尺寸分布在100~300 nm范围内。将其作为吸附剂用于吸附水溶液中的有机染料时，该材料对刚果红(CR)染料具有优异的吸附性能，吸附容量高达5 486 mg·g-1，去除率达99.50%。吸附动力学和热力学研究表明，该吸附过程符合准二级动力学模型，且为单层化学吸附。此外，采用的球磨辅助室温固相合成策略具有操作简便、无需溶剂、易于放大及产率高等优势。
2026, 42(10): 2109-2118
doi: 10.11862/CJIC.20260145
摘要:
基于聚多巴胺(PDA)仿生材料的改性作用，在碳纳米管(CNTs)表面原位生成能够螯合金属阳离子的邻苯二酚官能团。结合乙酸锰前驱体的等体积浸渍法，实现锰氧化物(MnOx)在CNTs表面的原位负载，制备了低温脱硝性能优良的MnOx/PDA@CNTs催化剂。通过N2吸附-脱附、X射线衍射、X射线光电子能谱、场发射扫描电子显微镜和脱硝性能等测试表征了所制备催化材料的微观结构与性能。利用响应面法中的中心复合设计(CCD)，分析了MnOx活性组分负载量与气体总流速之间的交互作用对催化剂脱硝率的影响，优化确定催化剂达到最佳脱硝率和最大Brunauer-Emmett-Teller (BET)比表面积时的负载量。结果显示，负载活性组分后，所制备催化剂的BET比表面积增加。催化剂中生成了MnO2、Mn2O3和MnO活性组分，其中1.40% MnOx/PDA@CNTs催化剂在测试温度范围内呈现最佳的选择性催化还原(SCR)活性，其在180℃时的脱硝率达到86.2%。响应面法优化结果显示，1.44% MnOx/PDA@CNTs催化剂获得了最佳的脱硝率(85.1%)和BET比表面积(88 m2·g-1)，基本与实验制备的1.40% MnOx/PDA@CNTs催化剂的脱硝率(86.2%)和BET比表面积(88 m2·g-1)持平。3次验证实验结果显示，1.44% MnOx/PDA@CNTs催化剂在180℃的脱硝率分别为84.6%、87.9%和86.5%，其BET比表面积分别为86、87和89 m2·g-1，基本与实验所制备的最佳1.40% MnOx/PDA@CNTs催化剂的脱硝率和BET比表面积相当，表明CCD模型有较好的预测能力。
基于聚多巴胺(PDA)仿生材料的改性作用，在碳纳米管(CNTs)表面原位生成能够螯合金属阳离子的邻苯二酚官能团。结合乙酸锰前驱体的等体积浸渍法，实现锰氧化物(MnOx)在CNTs表面的原位负载，制备了低温脱硝性能优良的MnOx/PDA@CNTs催化剂。通过N2吸附-脱附、X射线衍射、X射线光电子能谱、场发射扫描电子显微镜和脱硝性能等测试表征了所制备催化材料的微观结构与性能。利用响应面法中的中心复合设计(CCD)，分析了MnOx活性组分负载量与气体总流速之间的交互作用对催化剂脱硝率的影响，优化确定催化剂达到最佳脱硝率和最大Brunauer-Emmett-Teller (BET)比表面积时的负载量。结果显示，负载活性组分后，所制备催化剂的BET比表面积增加。催化剂中生成了MnO2、Mn2O3和MnO活性组分，其中1.40% MnOx/PDA@CNTs催化剂在测试温度范围内呈现最佳的选择性催化还原(SCR)活性，其在180℃时的脱硝率达到86.2%。响应面法优化结果显示，1.44% MnOx/PDA@CNTs催化剂获得了最佳的脱硝率(85.1%)和BET比表面积(88 m2·g-1)，基本与实验制备的1.40% MnOx/PDA@CNTs催化剂的脱硝率(86.2%)和BET比表面积(88 m2·g-1)持平。3次验证实验结果显示，1.44% MnOx/PDA@CNTs催化剂在180℃的脱硝率分别为84.6%、87.9%和86.5%，其BET比表面积分别为86、87和89 m2·g-1，基本与实验所制备的最佳1.40% MnOx/PDA@CNTs催化剂的脱硝率和BET比表面积相当，表明CCD模型有较好的预测能力。
2026, 42(10): 2119-2126
doi: 10.11862/CJIC.20260140
摘要:
以2，7-二(4-吡啶基乙烯基)芘(2，7-bpep)为主配体，分别引入对苯二甲酸(H2PTA)和庚二酸(H2GDA)作为辅助羧酸配体，在Zn(Ⅱ)离子参与下通过溶剂热法自组装构筑了2例具有光反应活性的金属有机框架材料{[Zn2(2，7-bpep)2(PTA)2]·2DMA}n(MOF1)和[Zn (2，7-bpep)(GDA)]n(MOF2)(DMA=N，N-二甲基乙酰胺)。单晶X射线衍射分析表明，这2种框架中2，7-bpep配体呈面对面有序排列，且相邻配体间烯烃双键距离满足Schmidt规则，为固态[2+2]光化学环加成反应提供了结构基础。在420 nm可见光照射下，2种MOFs均可发生[2+2]光化学环加成反应，分别转化为含对应的环丁烷衍生物的MOF1C和MOF2C。荧光性质研究表明，相较于原始MOF1和MOF2，其光反应产物MOF1C和MOF2C均表现出明显的荧光蓝移，这主要归因于环丁烷结构的形成削弱了体系的π共轭程度。上述结果表明，通过在MOFs骨架中引入光响应单元的反应构型，可实现对固态荧光发光行为的有效调控。
以2，7-二(4-吡啶基乙烯基)芘(2，7-bpep)为主配体，分别引入对苯二甲酸(H2PTA)和庚二酸(H2GDA)作为辅助羧酸配体，在Zn(Ⅱ)离子参与下通过溶剂热法自组装构筑了2例具有光反应活性的金属有机框架材料{[Zn2(2，7-bpep)2(PTA)2]·2DMA}n(MOF1)和[Zn (2，7-bpep)(GDA)]n(MOF2)(DMA=N，N-二甲基乙酰胺)。单晶X射线衍射分析表明，这2种框架中2，7-bpep配体呈面对面有序排列，且相邻配体间烯烃双键距离满足Schmidt规则，为固态[2+2]光化学环加成反应提供了结构基础。在420 nm可见光照射下，2种MOFs均可发生[2+2]光化学环加成反应，分别转化为含对应的环丁烷衍生物的MOF1C和MOF2C。荧光性质研究表明，相较于原始MOF1和MOF2，其光反应产物MOF1C和MOF2C均表现出明显的荧光蓝移，这主要归因于环丁烷结构的形成削弱了体系的π共轭程度。上述结果表明，通过在MOFs骨架中引入光响应单元的反应构型，可实现对固态荧光发光行为的有效调控。
2026, 42(10): 2127-2137
doi: 10.11862/CJIC.20260127
摘要:
以Ni-Mo双金属-氧簇为前驱体，采用原位合成策略构建了介孔碳包覆的高活性NiMoS加氢脱硫催化剂(NiMoS/C-FD)。双金属前驱体的引入及载体的结合，实现了金属活性组分在介孔碳载体中的嵌入及均匀分散。采用X射线衍射、N2吸附-脱附、扫描电子显微镜、高分辨透射电子显微镜、X射线光电子能谱等对催化剂进行系统分析，结果表明：与传统浸渍法制备的NiMoS/C-IM催化剂相比，原位合成的催化剂NiMoS/C-FD中MoS2活性相的尺寸更小、分散度更高、硫化更充分，且形成的高活性NiMoS相更多。反应评价数据表明，该催化剂表现出优异的催化性能，转化率达到93.2%，反应速率常数与转换频率分别达1.6×10-6 mol·g-1·s-1和3.3×10-3 s-1，显著优于NiMoS/C-IM。
以Ni-Mo双金属-氧簇为前驱体，采用原位合成策略构建了介孔碳包覆的高活性NiMoS加氢脱硫催化剂(NiMoS/C-FD)。双金属前驱体的引入及载体的结合，实现了金属活性组分在介孔碳载体中的嵌入及均匀分散。采用X射线衍射、N2吸附-脱附、扫描电子显微镜、高分辨透射电子显微镜、X射线光电子能谱等对催化剂进行系统分析，结果表明：与传统浸渍法制备的NiMoS/C-IM催化剂相比，原位合成的催化剂NiMoS/C-FD中MoS2活性相的尺寸更小、分散度更高、硫化更充分，且形成的高活性NiMoS相更多。反应评价数据表明，该催化剂表现出优异的催化性能，转化率达到93.2%，反应速率常数与转换频率分别达1.6×10-6 mol·g-1·s-1和3.3×10-3 s-1，显著优于NiMoS/C-IM。
2026, 42(10): 2138-2152
doi: 10.11862/CJIC.20260117
摘要:
采用简单的一步水热法制备了含有大量低配位Mo原子、不饱和S位点及富氧掺杂的MoS2纳米花催化剂，并将其应用于电催化析氢反应，同时研究了温度、原料配比对MoS2催化剂活性的影响。实验结果表明，在200℃、S与Mo的质量比(mS/mMo)为2.0的条件下制备的MoS2纳米花催化剂在0.5 mol·L-1 H2SO4电解液中展现出优异的析氢反应活性。该催化剂具有高活性比表面积、优异的本征导电性及良好的长期运行稳定性；在10 mA·cm-2的电流密度下，其过电势为258.98 mV，Tafel斜率为68.26 mV·dec-1，表明其具有快速的动力学响应能力。性能提升的根源可归结于两方面的协同效应：一方面，O原子的原位掺杂有效调控了MoS2的电子结构，提升了载流子浓度与迁移率，从而优化了本征电导率；另一方面，富缺陷结构(包括大量低配位Mo原子和不饱和S位点)显著活化了原本惰性的MoS2基面，大幅增加了可接触的催化活性位点密度，实现了对纳米花形貌、缺陷构型与电子态的多方位协同调控。光辅助能够显著加速界面电子传输动力学过程，进一步提升析氢反应性能(10 mA·cm-2处过电势降至228 mV)。
采用简单的一步水热法制备了含有大量低配位Mo原子、不饱和S位点及富氧掺杂的MoS2纳米花催化剂，并将其应用于电催化析氢反应，同时研究了温度、原料配比对MoS2催化剂活性的影响。实验结果表明，在200℃、S与Mo的质量比(mS/mMo)为2.0的条件下制备的MoS2纳米花催化剂在0.5 mol·L-1 H2SO4电解液中展现出优异的析氢反应活性。该催化剂具有高活性比表面积、优异的本征导电性及良好的长期运行稳定性；在10 mA·cm-2的电流密度下，其过电势为258.98 mV，Tafel斜率为68.26 mV·dec-1，表明其具有快速的动力学响应能力。性能提升的根源可归结于两方面的协同效应：一方面，O原子的原位掺杂有效调控了MoS2的电子结构，提升了载流子浓度与迁移率，从而优化了本征电导率；另一方面，富缺陷结构(包括大量低配位Mo原子和不饱和S位点)显著活化了原本惰性的MoS2基面，大幅增加了可接触的催化活性位点密度，实现了对纳米花形貌、缺陷构型与电子态的多方位协同调控。光辅助能够显著加速界面电子传输动力学过程，进一步提升析氢反应性能(10 mA·cm-2处过电势降至228 mV)。
2026, 42(10): 2153-2161
doi: 10.11862/CJIC.20260082
摘要:
基于咔唑和吡唑荧光团，设计并合成了一种比率荧光探针TCM，用于灵敏检测环境中的微量联氨。光谱研究表明，TCM具有超大的斯托克斯位移(241 nm)和单激发双发射的特点。TCM与联氨反应后，601 nm处的橙黄色荧光减弱，411 nm处的蓝色荧光增强，荧光强度比(F601/F411)降低了97%。通过质谱和密度泛函理论(DFT)计算验证了探针基于分子内电荷转移(ICT)效应的荧光识别机理和比率响应模式。此外，TCM表现出良好的选择性、很强的抗干扰能力、较短的响应时间(20 min)和较低的检测限(0.15 μmol·L-1)。已成功将TCM用于水样和土壤中联氨的检测，并且制备了荧光滤纸条，用于联氨的定性分析。
基于咔唑和吡唑荧光团，设计并合成了一种比率荧光探针TCM，用于灵敏检测环境中的微量联氨。光谱研究表明，TCM具有超大的斯托克斯位移(241 nm)和单激发双发射的特点。TCM与联氨反应后，601 nm处的橙黄色荧光减弱，411 nm处的蓝色荧光增强，荧光强度比(F601/F411)降低了97%。通过质谱和密度泛函理论(DFT)计算验证了探针基于分子内电荷转移(ICT)效应的荧光识别机理和比率响应模式。此外，TCM表现出良好的选择性、很强的抗干扰能力、较短的响应时间(20 min)和较低的检测限(0.15 μmol·L-1)。已成功将TCM用于水样和土壤中联氨的检测，并且制备了荧光滤纸条，用于联氨的定性分析。
2026, 42(10): 2162-2168
doi: 10.11862/CJIC.20260071
摘要:
开发了一种高性能晶态Ta基卤化物电解质材料(命名为Cs-LTOC)，并同步建立了其高效制备方法。结构分析表明，该异质相Cs-LTOC电解质主要由LiTaCl6、LiTaOCl4及Ta2O5三种物相组成。经过工艺优化，仅需在250℃下烧结3 h，所得电解质材料的离子电导率即可达9.02 mS·cm-1。将该电解质与高镍正极材料LiNi0.83Co0.12Mn0.05O2(NCM83)匹配组装全固态电池后，展现出优异的电化学性能：在0.1C (1.0C=200 mA·g-1)、0.3C、0.5C、1.0C、2.0C、3.0C和5.0C倍率下，NCM83正极的放电比容量分别达到221.7、212.1、205.9、195.2、183.1、174.8和160.8 mAh·g-1，并在5.0C倍率下循环1 900次后，容量保持率仍高达81.2%。
开发了一种高性能晶态Ta基卤化物电解质材料(命名为Cs-LTOC)，并同步建立了其高效制备方法。结构分析表明，该异质相Cs-LTOC电解质主要由LiTaCl6、LiTaOCl4及Ta2O5三种物相组成。经过工艺优化，仅需在250℃下烧结3 h，所得电解质材料的离子电导率即可达9.02 mS·cm-1。将该电解质与高镍正极材料LiNi0.83Co0.12Mn0.05O2(NCM83)匹配组装全固态电池后，展现出优异的电化学性能：在0.1C (1.0C=200 mA·g-1)、0.3C、0.5C、1.0C、2.0C、3.0C和5.0C倍率下，NCM83正极的放电比容量分别达到221.7、212.1、205.9、195.2、183.1、174.8和160.8 mAh·g-1，并在5.0C倍率下循环1 900次后，容量保持率仍高达81.2%。
2026, 42(10): 2169-2178
doi: 10.11862/CJIC.20260046
摘要:
本研究中，利用9，10-菲醌(C14H8O2，1)和菲二酚钠(C14H8O2Na2，2)分别与SiCl4、GeCl4、SnCl2和SbCl3反应，首次分离得到了由3个菲二酚根螯合的Si、Ge、Sn、Sb的八面体构型弱配位阴离子的化合物，分别为[Na(THF)3]2[Si(C14H8O2)3] (3)、[Na(THF)3]2 [Ge(C14H8O2)3] (4)、[Na(THF)3]2[Sn(C14H8O2)3] (5)、Na[Sb(C14H8O2)3] (6)。进一步利用6的阳离子交换反应，分离得到了[Li(THF)4]+与Et3NH+的三(9，10-菲二酚根)合锑(Ⅴ)酸盐(7、8)。所有产物的组成与纯度都通过1H NMR和13C NMR完成表征。通过单晶X射线衍射表征了3~5、7、8五个产物的结构。对3~5的结构分析表明，其核心结构单元[EO6](E=Si、Ge、Sn)的成键紧密，与外围Na+的作用松散，大阴离子具有显著的外向弱配位特征。7和8的单晶结构显示，其阴阳离子间处于非配位状态，因而核心单元[SbO6]呈现理想的对称构型，锑酸根阴离子表现出更优的抗阳离子干扰能力。
本研究中，利用9，10-菲醌(C14H8O2，1)和菲二酚钠(C14H8O2Na2，2)分别与SiCl4、GeCl4、SnCl2和SbCl3反应，首次分离得到了由3个菲二酚根螯合的Si、Ge、Sn、Sb的八面体构型弱配位阴离子的化合物，分别为[Na(THF)3]2[Si(C14H8O2)3] (3)、[Na(THF)3]2 [Ge(C14H8O2)3] (4)、[Na(THF)3]2[Sn(C14H8O2)3] (5)、Na[Sb(C14H8O2)3] (6)。进一步利用6的阳离子交换反应，分离得到了[Li(THF)4]+与Et3NH+的三(9，10-菲二酚根)合锑(Ⅴ)酸盐(7、8)。所有产物的组成与纯度都通过1H NMR和13C NMR完成表征。通过单晶X射线衍射表征了3~5、7、8五个产物的结构。对3~5的结构分析表明，其核心结构单元[EO6](E=Si、Ge、Sn)的成键紧密，与外围Na+的作用松散，大阴离子具有显著的外向弱配位特征。7和8的单晶结构显示，其阴阳离子间处于非配位状态，因而核心单元[SbO6]呈现理想的对称构型，锑酸根阴离子表现出更优的抗阳离子干扰能力。
2026, 42(10): 2179-2185
doi: 10.11862/CJIC.20260068
摘要:
采用溶剂热法成功合成了晶粒尺寸约为1.3 μm的Cs2PdBr6微晶，并利用飞秒瞬态吸收光谱系统研究了其光生载流子的超快动力学行为。动力学拟合结果表明，Cs2PdBr6微晶的载流子弛豫过程可分解为3个典型时间组分：首先出现一个超快衰减组分(2.1 ps)，归因于光生载流子被表面缺陷态快速捕获，该过程与材料表面丰富的缺陷密切相关；随后出现一个中间时间组分(853.8 ps)，主要对应电子-空穴对的本征辐射复合过程；与此同时，还出现一个较长寿命的慢衰减组分(4.1 ns)，可归因于缺陷相关的载流子弛豫路径，该过程有效抑制了电子-空穴对的辐射复合，并显著延长了载流子的寿命。此外，Cs2PdBr6微晶展现出良好的光催化CO2还原性能，CO和CH4的生成速率分别为14.4和1.5 μmol·g-1·h-1。
采用溶剂热法成功合成了晶粒尺寸约为1.3 μm的Cs2PdBr6微晶，并利用飞秒瞬态吸收光谱系统研究了其光生载流子的超快动力学行为。动力学拟合结果表明，Cs2PdBr6微晶的载流子弛豫过程可分解为3个典型时间组分：首先出现一个超快衰减组分(2.1 ps)，归因于光生载流子被表面缺陷态快速捕获，该过程与材料表面丰富的缺陷密切相关；随后出现一个中间时间组分(853.8 ps)，主要对应电子-空穴对的本征辐射复合过程；与此同时，还出现一个较长寿命的慢衰减组分(4.1 ns)，可归因于缺陷相关的载流子弛豫路径，该过程有效抑制了电子-空穴对的辐射复合，并显著延长了载流子的寿命。此外，Cs2PdBr6微晶展现出良好的光催化CO2还原性能，CO和CH4的生成速率分别为14.4和1.5 μmol·g-1·h-1。
2026, 42(10): 2186-2192
doi: 10.11862/CJIC.20260058
摘要:
A microporous acs-metal-organic framework (MOF) is reported as [Fe2.9Mn0.1(μ3-OH)(L)3·xGuest] (NJTU-Bai88, NJTU-Bai=Nanjing Tech University Bai′s group; H2L=bicyclo[2.2.2]octane-1, 4-dicarboxylic acid), in which potential open metal sites (OMSs) are occupied by solvent molecules with the pore size adjusted (approximately 0.47 nm by Horváth-Kawazoe model) to be close to the kinetic diameter of C3H4 (0.476 nm) and the strong adsorption sites reduced. Interestingly, NJTU-Bai88 showed a high C3H4 adsorption uptake (27.5 cm3·g-1 at 298 K and 1 kPa) and moderate adsorption enthalpy (-58.8 kJ·mol-1).
A microporous acs-metal-organic framework (MOF) is reported as [Fe2.9Mn0.1(μ3-OH)(L)3·xGuest] (NJTU-Bai88, NJTU-Bai=Nanjing Tech University Bai′s group; H2L=bicyclo[2.2.2]octane-1, 4-dicarboxylic acid), in which potential open metal sites (OMSs) are occupied by solvent molecules with the pore size adjusted (approximately 0.47 nm by Horváth-Kawazoe model) to be close to the kinetic diameter of C3H4 (0.476 nm) and the strong adsorption sites reduced. Interestingly, NJTU-Bai88 showed a high C3H4 adsorption uptake (27.5 cm3·g-1 at 298 K and 1 kPa) and moderate adsorption enthalpy (-58.8 kJ·mol-1).
2026, 42(10): 2193-2202
doi: 10.11862/CJIC.20260156
摘要:
A binder-free self-supported Mo-Ni alloy electrode was in-situ fabricated on a metallic Ti substrate through a facile one-step electrochemical deposition strategy. The microscopic morphology, crystal phase structure, and surface chemical valence state of the synthesized electrode were systematically characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), confirming the successful formation of well-integrated Mo-Ni alloy active sites on the conductive substrate. Electrochemical tests demonstrated that the optimized Mo-Ni alloy electrode delivered prominent alkaline hydrogen evolution reaction (HER) activity, with a low overpotential of 107 mV at 10 mA·cm-2. Notably, it achieved a further reduced overpotential of 95 mV in simulated seawater electrolyte. Moreover, the electrode exhibited remarkable long-term durability and robust catalytic stability under varied current density conditions.
A binder-free self-supported Mo-Ni alloy electrode was in-situ fabricated on a metallic Ti substrate through a facile one-step electrochemical deposition strategy. The microscopic morphology, crystal phase structure, and surface chemical valence state of the synthesized electrode were systematically characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), confirming the successful formation of well-integrated Mo-Ni alloy active sites on the conductive substrate. Electrochemical tests demonstrated that the optimized Mo-Ni alloy electrode delivered prominent alkaline hydrogen evolution reaction (HER) activity, with a low overpotential of 107 mV at 10 mA·cm-2. Notably, it achieved a further reduced overpotential of 95 mV in simulated seawater electrolyte. Moreover, the electrode exhibited remarkable long-term durability and robust catalytic stability under varied current density conditions.
2026, 42(10): 2203-2216
doi: 10.11862/CJIC.20260108
摘要:
PtCu 3D nanoporous conductive networks (3D NCNs) with highly interconnected and interwoven structures were synthesized via a one-pot, surfactant-free, inorganic-salt-mediated self-assembly method. The role of inorganic salt ions in the formation mechanism of 3D NCNs and their effects on the structural characteristics and catalytic properties were investigated. The obtained best Pt3Cu1/C (using carbon as the carrier) NCNs possessed a large specific surface area, abundant low-coordinated edge and corner atoms, and enhanced oxygen reduction reaction (ORR) performance due to the synergistic effect of Pt-Cu alloying. The ORR mass activity (MA) of Pt3Cu1/C was approximately 2.6 times higher than that of commercial Pt/C catalysts. Furthermore, the Pt-rich shell formed during the dealloying process contributes to the improved stability of the catalyst. After 30 000 accelerated durability test cycles, Pt3Cu1/C retained 75% of its initial electrochemical surface area (ECSA), compared with 59% for the commercial Pt/C catalyst.
PtCu 3D nanoporous conductive networks (3D NCNs) with highly interconnected and interwoven structures were synthesized via a one-pot, surfactant-free, inorganic-salt-mediated self-assembly method. The role of inorganic salt ions in the formation mechanism of 3D NCNs and their effects on the structural characteristics and catalytic properties were investigated. The obtained best Pt3Cu1/C (using carbon as the carrier) NCNs possessed a large specific surface area, abundant low-coordinated edge and corner atoms, and enhanced oxygen reduction reaction (ORR) performance due to the synergistic effect of Pt-Cu alloying. The ORR mass activity (MA) of Pt3Cu1/C was approximately 2.6 times higher than that of commercial Pt/C catalysts. Furthermore, the Pt-rich shell formed during the dealloying process contributes to the improved stability of the catalyst. After 30 000 accelerated durability test cycles, Pt3Cu1/C retained 75% of its initial electrochemical surface area (ECSA), compared with 59% for the commercial Pt/C catalyst.
2026, 42(10): 2217-2231
doi: 10.11862/CJIC.20260056
摘要:
The rare-earth (La3+, Gd3+, or Er3+)-doped NiCo2O4 catalysts were supported on nickel foam to optimize charge rearrangement and structural reconstruction, thereby improving oxygen evolution reaction (OER) performance. Notably, the incorporation of La3+ collectively modulates the electronic configuration of Ni2+ and Co3+ through lattice distortion. It strengthens metal-oxygen bonding, thereby constructing the La—O—Ni/Co structural unit, which promotes charge transfer during the OER process and enhances catalytic activity. As a result, the ultrafine seagrass-shaped La-NiCo2O4-1 exhibited excellent OER activity. In a 1 mol·L-1 KOH electrolyte, the prepared 0.25 mmol La3+ doped NiCo2O4 exhibited high OER activity with a low overpotential of 283 mV at 10 mA·cm-2, along with outstanding stability for over 75 h at the multi-step chronoamperometry curve of 50→100→150→100→50 mA·cm-2.
The rare-earth (La3+, Gd3+, or Er3+)-doped NiCo2O4 catalysts were supported on nickel foam to optimize charge rearrangement and structural reconstruction, thereby improving oxygen evolution reaction (OER) performance. Notably, the incorporation of La3+ collectively modulates the electronic configuration of Ni2+ and Co3+ through lattice distortion. It strengthens metal-oxygen bonding, thereby constructing the La—O—Ni/Co structural unit, which promotes charge transfer during the OER process and enhances catalytic activity. As a result, the ultrafine seagrass-shaped La-NiCo2O4-1 exhibited excellent OER activity. In a 1 mol·L-1 KOH electrolyte, the prepared 0.25 mmol La3+ doped NiCo2O4 exhibited high OER activity with a low overpotential of 283 mV at 10 mA·cm-2, along with outstanding stability for over 75 h at the multi-step chronoamperometry curve of 50→100→150→100→50 mA·cm-2.
2026, 42(10): 2232-2244
doi: 10.11862/CJIC.20260054
摘要:
In response to the relative scarcity of microscopic mechanism studies on electrically switched ion exchange materials in the field of ion removal, a theoretical investigation based on density functional theory was conducted to explore the adsorption and migration mechanisms of lead ions (Pb2+) at the α-Zirconium phosphate (α-ZrP)/polypyrrole (PPy) composite from an atomic scale perspective. It is found that the introduction of PPy not only enhances the structural stability of α-ZrP through a physical support effect, but more importantly, the formation of interfacial chemical bonds and the accompanying electron transfer induce the generation of an internal electric field, which confers exceptional electrochemical properties to the composite. The mechanistic analysis indicates that, within the coupled interfacial region, the synergistic interplay between multi-site “cooperative anchoring” and interfacial electronic structure regulation collectively enables the highly stable coordination of Pb2+, with an adsorption energy as high as -4.64 eV. Meanwhile, the kinetic results confirm that the pronounced electron-ion coupled transport effect in the interface effectively reduces the migration energy barrier, resulting in significantly enhanced interfacial diffusion kinetics of Pb2+ of the composite compared with those of the individual components.
In response to the relative scarcity of microscopic mechanism studies on electrically switched ion exchange materials in the field of ion removal, a theoretical investigation based on density functional theory was conducted to explore the adsorption and migration mechanisms of lead ions (Pb2+) at the α-Zirconium phosphate (α-ZrP)/polypyrrole (PPy) composite from an atomic scale perspective. It is found that the introduction of PPy not only enhances the structural stability of α-ZrP through a physical support effect, but more importantly, the formation of interfacial chemical bonds and the accompanying electron transfer induce the generation of an internal electric field, which confers exceptional electrochemical properties to the composite. The mechanistic analysis indicates that, within the coupled interfacial region, the synergistic interplay between multi-site “cooperative anchoring” and interfacial electronic structure regulation collectively enables the highly stable coordination of Pb2+, with an adsorption energy as high as -4.64 eV. Meanwhile, the kinetic results confirm that the pronounced electron-ion coupled transport effect in the interface effectively reduces the migration energy barrier, resulting in significantly enhanced interfacial diffusion kinetics of Pb2+ of the composite compared with those of the individual components.
2026, 42(10): 2245-2258
doi: 10.11862/CJIC.20260042
摘要:
Two p-sulfosulfonylcalix[4 ]arene supramolecular coordination complexes, namely, {[(CH3)4N]4[Co3(μ3-O)(H4TC4AS-SO2)]2(TDC)2·2H2O·67CH3OH}n (LLU-101) and {[(CH3)4N]2[Co3(μ4-O)(H4TC4AS-SO2)0.5(TDC)2]·32DMF}n (LLU-102) were obtained via solvothermal reactions involving a mixture of cobalt salt, p-sulfosulfonylcalix[4 ]arene (H8TC4AS-SO2) and thiophene-2,5-dicarboxylic acid (H2TDC) ligands under methanol or DMF solvents, respectively. Structural analysis revealed that solvent regulation has a significant impact on the formation of the structure. Complex LLU-101 exhibits a 2D layered structure, which can be viewed as a structure composed of trinuclear shuttlecock-like secondary building units (SBUs), {Co3-H4TC4AS-SO2}, connected by the TDC2- ligand via a single coordination mode. In this architecture, both the upper and lower rims of the main ligand coordinate to Co2+ centers. In sharp contrast, LLU-102 displays a 3D network architecture, which can be conceptualized as a structure formed by tetranuclear shuttlecock-like {Co4-H4TC4AS-SO2} SBUs, which are connected through two different coordination modes of TDC2- ligands. Within the LLU-102 framework, the main ligand exhibits two distinct coordination patterns: one involving only the lower rim attached to Co2+ ions, and the other engaging both the upper and lower rims simultaneously in coordination. Magnetic studies reveal that all the cobalt centers in both complexes exhibit antiferromagnetic interactions.
Two p-sulfosulfonylcalix[
2026, 42(5): 897-905
doi: 10.11862/CJIC.20250358
摘要:
合成了3种含吡啶基水杨醛席夫碱过渡金属配合物[Co(L)2]Cl (1)、[Ni(L)2(CH3OH)2] (2)和[Cu(L)2] (3)(HL=4-(二乙氨基)水杨醛缩2-(2-吡啶基)乙胺席夫碱)，利用红外光谱、元素分析和单晶X射线衍射等测试手段对配合物1~3进行了结构表征。采用MTT法对该系列配合物进行了体外抗肿瘤活性实验，结果表明：配体HL和配合物1对人卵巢癌细胞A2780、人非小细胞肺癌细胞A549和人三阴乳腺癌细胞MDA-MB-231的抗肿瘤活性都优于顺铂，其中，配合物1对人三阴乳腺癌细胞MDA-MB-231的抑制作用最强，其半数抑制浓度(IC50)为(7.8±0.3) μmol·L-1；细胞刮板实验表明随着配合物1浓度的增加，其对人三阴乳腺癌细胞MDA-MB-231的杀伤作用增强，其杀伤作用呈剂量依赖性。此外，还研究了配体HL和配合物1~3对金黄色葡萄球菌、大肠杆菌以及白色念珠菌的抑菌活性，结果表明：HL及其配合物1和3对金黄色葡萄球菌和白色念珠菌都有较好的抑菌活性，其中，配合物1对金黄色葡萄球菌抑菌效果达到了极度敏感；其最低抑制浓度(MIC)为0.64 mg·mL-1。
合成了3种含吡啶基水杨醛席夫碱过渡金属配合物[Co(L)2]Cl (1)、[Ni(L)2(CH3OH)2] (2)和[Cu(L)2] (3)(HL=4-(二乙氨基)水杨醛缩2-(2-吡啶基)乙胺席夫碱)，利用红外光谱、元素分析和单晶X射线衍射等测试手段对配合物1~3进行了结构表征。采用MTT法对该系列配合物进行了体外抗肿瘤活性实验，结果表明：配体HL和配合物1对人卵巢癌细胞A2780、人非小细胞肺癌细胞A549和人三阴乳腺癌细胞MDA-MB-231的抗肿瘤活性都优于顺铂，其中，配合物1对人三阴乳腺癌细胞MDA-MB-231的抑制作用最强，其半数抑制浓度(IC50)为(7.8±0.3) μmol·L-1；细胞刮板实验表明随着配合物1浓度的增加，其对人三阴乳腺癌细胞MDA-MB-231的杀伤作用增强，其杀伤作用呈剂量依赖性。此外，还研究了配体HL和配合物1~3对金黄色葡萄球菌、大肠杆菌以及白色念珠菌的抑菌活性，结果表明：HL及其配合物1和3对金黄色葡萄球菌和白色念珠菌都有较好的抑菌活性，其中，配合物1对金黄色葡萄球菌抑菌效果达到了极度敏感；其最低抑制浓度(MIC)为0.64 mg·mL-1。
2026, 42(5): 906-916
doi: 10.11862/CJIC.20250348
摘要:
以不同结构的含氮有机物为前驱体，采用无溶剂法制备了氮掺杂碳包裹Mo2N纳米颗粒，并系统探究了其析氢反应(HER)电催化性能。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼(Raman)光谱、扫描电子显微镜(SEM)及透射电子显微镜(TEM)，对材料的晶体结构、元素组成、孔结构及微观形貌进行了表征。结果表明，氮前驱体种类决定产物的晶体结构，进而显著影响HER催化性能。其中以盐酸胍为前驱体制得的MoNC-G样品的性能最优：酸性条件下，其在10 mA·cm-2的电流密度下对应的过电位为123 mV，Tafel斜率62.8 mV·dec-1；碱性条件下，对应的过电位低至76 mV，Tafel斜率为70.5 mV·dec-1。稳定性测试结果显示，MoNC-G经10 h计时电流测试后无明显电流衰减，且1 000次循环前后的线性扫描伏安法(LSV)曲线基本重合，表现出优异的长期稳定性与循环耐久性。
以不同结构的含氮有机物为前驱体，采用无溶剂法制备了氮掺杂碳包裹Mo2N纳米颗粒，并系统探究了其析氢反应(HER)电催化性能。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼(Raman)光谱、扫描电子显微镜(SEM)及透射电子显微镜(TEM)，对材料的晶体结构、元素组成、孔结构及微观形貌进行了表征。结果表明，氮前驱体种类决定产物的晶体结构，进而显著影响HER催化性能。其中以盐酸胍为前驱体制得的MoNC-G样品的性能最优：酸性条件下，其在10 mA·cm-2的电流密度下对应的过电位为123 mV，Tafel斜率62.8 mV·dec-1；碱性条件下，对应的过电位低至76 mV，Tafel斜率为70.5 mV·dec-1。稳定性测试结果显示，MoNC-G经10 h计时电流测试后无明显电流衰减，且1 000次循环前后的线性扫描伏安法(LSV)曲线基本重合，表现出优异的长期稳定性与循环耐久性。
2026, 42(5): 917-924
doi: 10.11862/CJIC.20260357
摘要:
以2，5-二溴对苯二甲酸为主配体(H2L)并引入中性含氮辅助配体1，3-二(1H-咪唑-1-基)苯(1，3-bib)、1，4-二(咪唑-1-基甲基)苯(1，4-bix)、1，4-二(1H-咪唑-1-基)丁烷(bbi)，与Zn(NO3)2·6H2O在溶剂热条件下反应，得到3种新型的配位聚合物1~3。配位聚合物{[Zn2(L)2(1，3-bib)2]·H2O}n (1)展现了一个1D双链的骨架结构。配位聚合物[Zn(L)(1，4-bix)]n (2)展现了二重穿插的2D骨架结构。每个锌离子之间通过L2-配体桥联形成1D的波浪链，链与链之间进一步通过1，4-bix配体桥联形成2D波浪状的网状结构。由于1，4-bix具有一定的柔性，2个相似的2D层状结构相互穿插，形成一个二重穿插的2D骨架结构。配位聚合物{[Zn2(L)2(bbi)2]·0.3DMF}n (3)展现了四重穿插的3D骨架结构。每个锌离子之间通过L2-配体和bbi配体连接，形成1D链状结构。链与链之间通过L2-配体连接形成2D层状结构，层与层之间进一步通过bbi配体连接形成3D的骨架结构。由于配合物骨架结构中孔道的存在，4个相同的3D骨架结构互相穿插形成一个更加复杂的四重穿插的3D骨架结构。配合物1~3均具有良好的热稳定性和可调控的荧光发射。
以2，5-二溴对苯二甲酸为主配体(H2L)并引入中性含氮辅助配体1，3-二(1H-咪唑-1-基)苯(1，3-bib)、1，4-二(咪唑-1-基甲基)苯(1，4-bix)、1，4-二(1H-咪唑-1-基)丁烷(bbi)，与Zn(NO3)2·6H2O在溶剂热条件下反应，得到3种新型的配位聚合物1~3。配位聚合物{[Zn2(L)2(1，3-bib)2]·H2O}n (1)展现了一个1D双链的骨架结构。配位聚合物[Zn(L)(1，4-bix)]n (2)展现了二重穿插的2D骨架结构。每个锌离子之间通过L2-配体桥联形成1D的波浪链，链与链之间进一步通过1，4-bix配体桥联形成2D波浪状的网状结构。由于1，4-bix具有一定的柔性，2个相似的2D层状结构相互穿插，形成一个二重穿插的2D骨架结构。配位聚合物{[Zn2(L)2(bbi)2]·0.3DMF}n (3)展现了四重穿插的3D骨架结构。每个锌离子之间通过L2-配体和bbi配体连接，形成1D链状结构。链与链之间通过L2-配体连接形成2D层状结构，层与层之间进一步通过bbi配体连接形成3D的骨架结构。由于配合物骨架结构中孔道的存在，4个相同的3D骨架结构互相穿插形成一个更加复杂的四重穿插的3D骨架结构。配合物1~3均具有良好的热稳定性和可调控的荧光发射。
2026, 42(5): 925-932
doi: 10.11862/CJIC.20250352
摘要:
基于简单水热法构筑了一种由纳米片自组装形成的三维花状δ-MnO2结构。该三维多孔结构能够捕获大量电解质离子并提高电极表面的Zn2+浓度，从而优化Zn2+传输路径并加速电极反应动力学过程。此外，花状交联结构有效提升了δ-MnO2电极的机械性能，使其在循环过程中发生缓慢的体积膨胀，结构维持稳定。基于δ-MnO2电极组装得到的水系锌离子电池(AZIBs)展现出优异的放电比容量(0.1 A·g-1下为358.2 mAh·g-1)和循环稳定性(1 000次循环后放电比容量仍保持为94.9 mAh·g-1)。
基于简单水热法构筑了一种由纳米片自组装形成的三维花状δ-MnO2结构。该三维多孔结构能够捕获大量电解质离子并提高电极表面的Zn2+浓度，从而优化Zn2+传输路径并加速电极反应动力学过程。此外，花状交联结构有效提升了δ-MnO2电极的机械性能，使其在循环过程中发生缓慢的体积膨胀，结构维持稳定。基于δ-MnO2电极组装得到的水系锌离子电池(AZIBs)展现出优异的放电比容量(0.1 A·g-1下为358.2 mAh·g-1)和循环稳定性(1 000次循环后放电比容量仍保持为94.9 mAh·g-1)。
2026, 42(5): 933-943
doi: 10.11862/CJIC.20250334
摘要:
将Ni2P/碳纳米管(CNT)复合物修饰于聚丙烯(PP)隔膜表面，构建“催化-阻隔”一体化界面，旨在加速多硫化锂(Li2Sn)的转化并抑制其穿梭效应。Ni2P/CNT优异的催化特性有效促进了Li2Sn的转化，改善了其氧化还原动力学性能，提高了活性材料的利用率，显著抑制了穿梭效应。采用Ni2P/CNT/PP隔膜的电池表现出优异的电化学性能，在1C(1C=1 675 mAh·g-1)下实现了高初始放电比容量(907 mAh·g-1)，经过800次循环后，平均每圈容量衰减率仅为0.047%，展现出良好的循环稳定性。
将Ni2P/碳纳米管(CNT)复合物修饰于聚丙烯(PP)隔膜表面，构建“催化-阻隔”一体化界面，旨在加速多硫化锂(Li2Sn)的转化并抑制其穿梭效应。Ni2P/CNT优异的催化特性有效促进了Li2Sn的转化，改善了其氧化还原动力学性能，提高了活性材料的利用率，显著抑制了穿梭效应。采用Ni2P/CNT/PP隔膜的电池表现出优异的电化学性能，在1C(1C=1 675 mAh·g-1)下实现了高初始放电比容量(907 mAh·g-1)，经过800次循环后，平均每圈容量衰减率仅为0.047%，展现出良好的循环稳定性。
2026, 42(5): 944-958
doi: 10.11862/CJIC.20250323
摘要:
针对单一电化学反应体系中活性组分利用效率受限的问题，构建了泡沫Ti/FeCo-Fe2O3-CoFe2O4/SnO2-Sb(简称为Ti/ FeCoO/SnO2-Sb)复合阳极与过氧单硫酸盐(PMS)协同作用的电化学活化体系(Ti/FeCoO/SnO2-Sb+PMS)。为突破传统SnO2-Sb阳极在界面反应动力学与服役稳定性方面的固有瓶颈，提出以FeCoO作为关键中间层与SnO2-Sb构筑分级复合电极的策略。借助Fe、Co双金属位点的协同效应重构电极界面微环境，从而实现PMS活化效率与体系稳定性的同步提升。性能评估结果表明，在Ti/FeCoO/SnO2-Sb+PMS体系中，Ti/FeCoO/SnO2-Sb对甲基橙(MO)表现出最优的去除能力与矿化水平，其化学需氧量(COD)去除率显著高于对照体系；同时，酸性条件更有利于PMS活化，从而进一步强化了MO的降解动力学性能。相较于未添加FeCoO体系(Ti/SnO2-Sb+PMS)，Ti/FeCoO/SnO2-Sb+PMS复合体系展现出更为突出的整体性能优势。在此基础上，结合电化学表征、电子顺磁共振(EPR)与密度泛函理论(DFT)计算对机理进行解析，结果表明，性能提升主要归因于复合界面有效促进了直接电子转移(DET)过程并强化了PMS的电化学活化；反应过程中，超氧阴离子自由基(·O2-)、羟基自由基(·OH)、硫酸根自由基(SO4·-)和单线态氧(1O2)协同作用，实现了MO共轭结构的高效破坏与持续深度氧化。
针对单一电化学反应体系中活性组分利用效率受限的问题，构建了泡沫Ti/FeCo-Fe2O3-CoFe2O4/SnO2-Sb(简称为Ti/ FeCoO/SnO2-Sb)复合阳极与过氧单硫酸盐(PMS)协同作用的电化学活化体系(Ti/FeCoO/SnO2-Sb+PMS)。为突破传统SnO2-Sb阳极在界面反应动力学与服役稳定性方面的固有瓶颈，提出以FeCoO作为关键中间层与SnO2-Sb构筑分级复合电极的策略。借助Fe、Co双金属位点的协同效应重构电极界面微环境，从而实现PMS活化效率与体系稳定性的同步提升。性能评估结果表明，在Ti/FeCoO/SnO2-Sb+PMS体系中，Ti/FeCoO/SnO2-Sb对甲基橙(MO)表现出最优的去除能力与矿化水平，其化学需氧量(COD)去除率显著高于对照体系；同时，酸性条件更有利于PMS活化，从而进一步强化了MO的降解动力学性能。相较于未添加FeCoO体系(Ti/SnO2-Sb+PMS)，Ti/FeCoO/SnO2-Sb+PMS复合体系展现出更为突出的整体性能优势。在此基础上，结合电化学表征、电子顺磁共振(EPR)与密度泛函理论(DFT)计算对机理进行解析，结果表明，性能提升主要归因于复合界面有效促进了直接电子转移(DET)过程并强化了PMS的电化学活化；反应过程中，超氧阴离子自由基(·O2-)、羟基自由基(·OH)、硫酸根自由基(SO4·-)和单线态氧(1O2)协同作用，实现了MO共轭结构的高效破坏与持续深度氧化。
2026, 42(5): 959-968
doi: 10.11862/CJIC.20250320
摘要:
通过简单的一步水热法合成了负载石墨烯量子点(GQDs)的SnS2复合纳米片光催化剂(GQDs/SnS2)，并系统探讨了碳源(柠檬酸钠和柠檬酸)对光催化还原Cr(Ⅵ)性能的影响。利用扫描电子显微镜、透射电子显微镜、X射线衍射、氮气吸附-脱附测试及X射线光电子能谱对材料进行了表征。结果表明，GQDs成功负载于六方相SnS2纳米片表面。其中，以柠檬酸钠为碳源制备的GQDs/SnS2在60 min内对Cr(Ⅵ)的还原率达到100%，而纯SnS2对Cr(Ⅵ)的还原率仅为56%。GQDs的引入可显著增大催化剂的比表面积，拓宽光谱吸收范围并加速光生载流子的分离，从而大幅提升其光催化还原性能。
通过简单的一步水热法合成了负载石墨烯量子点(GQDs)的SnS2复合纳米片光催化剂(GQDs/SnS2)，并系统探讨了碳源(柠檬酸钠和柠檬酸)对光催化还原Cr(Ⅵ)性能的影响。利用扫描电子显微镜、透射电子显微镜、X射线衍射、氮气吸附-脱附测试及X射线光电子能谱对材料进行了表征。结果表明，GQDs成功负载于六方相SnS2纳米片表面。其中，以柠檬酸钠为碳源制备的GQDs/SnS2在60 min内对Cr(Ⅵ)的还原率达到100%，而纯SnS2对Cr(Ⅵ)的还原率仅为56%。GQDs的引入可显著增大催化剂的比表面积，拓宽光谱吸收范围并加速光生载流子的分离，从而大幅提升其光催化还原性能。
2026, 42(5): 969-979
doi: 10.11862/CJIC.20250317
摘要:
合成了2种含噻吩基团的配体[5，5′-二(噻吩-2-基)-2，2′-联吡啶(tp-bpy-tp)和3，8-二溴-1，10-菲咯啉(tp-phen-tp)]，并分别与Co(NO3)2·6H2O和Ni(NO3)2·6H2O配位，制备了3种金属配合物([Co(tp-bpy-tp)3](NO3)2、[Ni(tp-bpy-tp)3](NO3)2和[Ni(tp-phen-tp)3](NO3)2)。在无水FeCl3催化下，通过聚合反应进一步合成了金属配位聚合物[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n。以苯酚溶液模拟酚类废水，考察了聚合物的光催化降解苯酚性能。结果表明，在氙灯光源照射2 h后，[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n对苯酚的降解率分别达到74.37%、62.98%和83.45%。
合成了2种含噻吩基团的配体[5，5′-二(噻吩-2-基)-2，2′-联吡啶(tp-bpy-tp)和3，8-二溴-1，10-菲咯啉(tp-phen-tp)]，并分别与Co(NO3)2·6H2O和Ni(NO3)2·6H2O配位，制备了3种金属配合物([Co(tp-bpy-tp)3](NO3)2、[Ni(tp-bpy-tp)3](NO3)2和[Ni(tp-phen-tp)3](NO3)2)。在无水FeCl3催化下，通过聚合反应进一步合成了金属配位聚合物[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n。以苯酚溶液模拟酚类废水，考察了聚合物的光催化降解苯酚性能。结果表明，在氙灯光源照射2 h后，[Co(tp-bpy-tp)3]n、[Ni(tp-bpy-tp)3]n和[Ni(tp-phen-tp)3]n对苯酚的降解率分别达到74.37%、62.98%和83.45%。
2026, 42(5): 980-990
doi: 10.11862/CJIC.20250304
摘要:
设计并制备了一种基于银(Ag)纳米颗粒复合的ZIF-8包覆钙钛矿纳米晶(Ag@CsPbBr3@ZIF-8)的表面增强拉曼散射(SERS)复合基底。与纯Ag基底相比，该复合基底具备良好的水稳定性，在水相中能显著增强芘分子的拉曼信号。通过光谱特征分析建立拟合方程，结果显示该复合基底对芘分子具有高灵敏检测性，检测限低至8.58 μg·L-1。加标回收率实验中，芘的回收率为97.6%~109.2%，相对标准偏差(RSD)为1.12%~7.91%，表明该基底具有良好的重复性和对芘分子检测的特异性。
设计并制备了一种基于银(Ag)纳米颗粒复合的ZIF-8包覆钙钛矿纳米晶(Ag@CsPbBr3@ZIF-8)的表面增强拉曼散射(SERS)复合基底。与纯Ag基底相比，该复合基底具备良好的水稳定性，在水相中能显著增强芘分子的拉曼信号。通过光谱特征分析建立拟合方程，结果显示该复合基底对芘分子具有高灵敏检测性，检测限低至8.58 μg·L-1。加标回收率实验中，芘的回收率为97.6%~109.2%，相对标准偏差(RSD)为1.12%~7.91%，表明该基底具有良好的重复性和对芘分子检测的特异性。
2026, 42(5): 991-1002
doi: 10.11862/CJIC.20250302
摘要:
以稀土硬脂酸盐为前驱体，乙醇-水-油酸混合试剂为溶剂，采用化学方法合成NaYF4∶Yb，Er上转换荧光微米材料；再以NaYF4∶Yb，Er为基质材料，在其表面依次键合1，4-苯二甲酸(PTA)、Eu3+离子和1，10-菲咯啉(Phen)，制备具有双重荧光性质的NaYF4∶Yb，Er-(PTA)Eu(Phen)微米复合材料。经表征发现，复合材料的形貌为表面结合了纳米球的微米棒，在波长为200~310 nm范围内和976 nm处分别产生紫外和近红外吸收，受254和980 nm光源激发分别产生616 nm红色下转换荧光和540 nm绿色上转换荧光。将微米材料、十二烷基硫酸钠与水配制成微米悬浮液，用于潜在手印的悬浮液法显现和双模式荧光增强。经过优化实验，确定手印显现的最优条件如下：NaYF4∶Yb，Er-(PTA)Eu(Phen)的质量分数为1.67%，十二烷基硫酸钠的质量分数为0.50‰，显现时间为30 s。结果表明，手印显现结合荧光增强具有较高的对比度、灵敏度和选择性，荧光增强模式对对比度的影响较大，而对灵敏度和选择性基本没有影响。
以稀土硬脂酸盐为前驱体，乙醇-水-油酸混合试剂为溶剂，采用化学方法合成NaYF4∶Yb，Er上转换荧光微米材料；再以NaYF4∶Yb，Er为基质材料，在其表面依次键合1，4-苯二甲酸(PTA)、Eu3+离子和1，10-菲咯啉(Phen)，制备具有双重荧光性质的NaYF4∶Yb，Er-(PTA)Eu(Phen)微米复合材料。经表征发现，复合材料的形貌为表面结合了纳米球的微米棒，在波长为200~310 nm范围内和976 nm处分别产生紫外和近红外吸收，受254和980 nm光源激发分别产生616 nm红色下转换荧光和540 nm绿色上转换荧光。将微米材料、十二烷基硫酸钠与水配制成微米悬浮液，用于潜在手印的悬浮液法显现和双模式荧光增强。经过优化实验，确定手印显现的最优条件如下：NaYF4∶Yb，Er-(PTA)Eu(Phen)的质量分数为1.67%，十二烷基硫酸钠的质量分数为0.50‰，显现时间为30 s。结果表明，手印显现结合荧光增强具有较高的对比度、灵敏度和选择性，荧光增强模式对对比度的影响较大，而对灵敏度和选择性基本没有影响。
2026, 42(5): 1003-1014
doi: 10.11862/CJIC.20250238
摘要:
采用静电纺丝技术制备了多孔氮掺杂碳纳米纤维(PNCNFs)，随后通过高温碳化及还原处理，成功合成了一系列PNCNFs锚定PtRu合金材料(PtRu/PNCNFs)。碳纳米纤维中氮的掺杂引入了大量的亲水性基团，能够显著增强材料与电解液之间的润湿性，有助于离子传输和整体电化学性能的进一步改善；同时PNCNFs具有较大的比表面积，PtRu合金的存在从一定程度上增加了其活性位点。此外，高温下形成的多孔结构使得PtRu合金能够均匀分散在材料表面，有利于调节材料的电子结构，促进电子转移，提升析氢反应(HER)性能。结果显示，经过500 ℃处理的PNCNFs(PtRu/PNCNFs-500)在1 mol·L-1 KOH和含1 mol·L-1 KOH的海水溶液中均表现出优异的HER性能。在电流密度为10 mA·cm-2时，PtRu/PNCNFs-500的析氢过电位分别为15.8和18.3 mV，塔菲尔(Tafel)斜率分别为20.58和20.65 mV·dec-1，性能显著优于经300、400和600 ℃处理的PNCNFs，并均展现出良好的HER稳定性。
采用静电纺丝技术制备了多孔氮掺杂碳纳米纤维(PNCNFs)，随后通过高温碳化及还原处理，成功合成了一系列PNCNFs锚定PtRu合金材料(PtRu/PNCNFs)。碳纳米纤维中氮的掺杂引入了大量的亲水性基团，能够显著增强材料与电解液之间的润湿性，有助于离子传输和整体电化学性能的进一步改善；同时PNCNFs具有较大的比表面积，PtRu合金的存在从一定程度上增加了其活性位点。此外，高温下形成的多孔结构使得PtRu合金能够均匀分散在材料表面，有利于调节材料的电子结构，促进电子转移，提升析氢反应(HER)性能。结果显示，经过500 ℃处理的PNCNFs(PtRu/PNCNFs-500)在1 mol·L-1 KOH和含1 mol·L-1 KOH的海水溶液中均表现出优异的HER性能。在电流密度为10 mA·cm-2时，PtRu/PNCNFs-500的析氢过电位分别为15.8和18.3 mV，塔菲尔(Tafel)斜率分别为20.58和20.65 mV·dec-1，性能显著优于经300、400和600 ℃处理的PNCNFs，并均展现出良好的HER稳定性。
2026, 42(5): 1015-1025
doi: 10.11862/CJIC.20250366
摘要:
Herein, ratiometric fluorescence-based carbon dots (N-CDs) with blue emission were prepared by using simple one-step hydrothermal methods from benzimidazole and L-tryptophan as precursors. Dual emission peaks were observed at 356 and 442 nm under the excitation wavelength of 303 nm. Upon addition of sulfide ions (S2-), the fluorescence intensity at 442 nm decreased significantly, while that at 356 nm increased. The F442/F356 intensity ratio (where F356 and F442 refer to the fluorescence intensity at 356 and 442 nm, respectively) exhibited a linear relationship with the concentration of S2- (0-60.0 μmol·L-1), and the detection limit was determined to be 0.076 μmol·L-1. The fluorescence detection mechanism was ascribed to the static quenching effect. Furthermore, this fluorescence probe was successfully used for the determination of S2- in real samples with satisfactory recoveries. Finally, the analytical greenness metric for sample preparation (AGREEprep) and blue applicability grade index (BAGI) tools indicated the high sustainability of this platform.
Herein, ratiometric fluorescence-based carbon dots (N-CDs) with blue emission were prepared by using simple one-step hydrothermal methods from benzimidazole and L-tryptophan as precursors. Dual emission peaks were observed at 356 and 442 nm under the excitation wavelength of 303 nm. Upon addition of sulfide ions (S2-), the fluorescence intensity at 442 nm decreased significantly, while that at 356 nm increased. The F442/F356 intensity ratio (where F356 and F442 refer to the fluorescence intensity at 356 and 442 nm, respectively) exhibited a linear relationship with the concentration of S2- (0-60.0 μmol·L-1), and the detection limit was determined to be 0.076 μmol·L-1. The fluorescence detection mechanism was ascribed to the static quenching effect. Furthermore, this fluorescence probe was successfully used for the determination of S2- in real samples with satisfactory recoveries. Finally, the analytical greenness metric for sample preparation (AGREEprep) and blue applicability grade index (BAGI) tools indicated the high sustainability of this platform.
2026, 42(5): 1026-1038
doi: 10.11862/CJIC.20250364
摘要:
To enhance the low-temperature activity and anti-sintering performance of Ni-based catalysts for CO methanation, mesoporous CeO2 supports with a confined structure were synthesized via a hydrothermal method. The effects of three Ni loading methods—incipient wetness impregnation, co-precipitation, and bis(cyclopentadienyl)nickel sublimation—on catalytic performance were systematically compared. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption test, hydrogen temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), revealed the critical influence of the loading method on Ni species dispersion, particle size, and metal-support interaction. The results indicated that all three mesoporous Ni/CeO2 catalysts exhibited excellent anti-sintering properties due to the confinement effect of the support. However, their low-temperature activities differed significantly, primarily determined by the specific state of Ni. In the NC-B catalyst prepared by bis(cyclopentadienyl)nickel sublimation, the interaction between Ni species and the support was relatively weak. After reduction, this method yielded highly dispersed metallic Ni nanoparticles, increasing the number of low-temperature active sites. Consequently, the NC-B catalyst achieved 98% CO conversion rate and 100% CH4 selectivity at 300 ℃, demonstrating the optimal low-temperature methanation performance.
To enhance the low-temperature activity and anti-sintering performance of Ni-based catalysts for CO methanation, mesoporous CeO2 supports with a confined structure were synthesized via a hydrothermal method. The effects of three Ni loading methods—incipient wetness impregnation, co-precipitation, and bis(cyclopentadienyl)nickel sublimation—on catalytic performance were systematically compared. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption test, hydrogen temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), revealed the critical influence of the loading method on Ni species dispersion, particle size, and metal-support interaction. The results indicated that all three mesoporous Ni/CeO2 catalysts exhibited excellent anti-sintering properties due to the confinement effect of the support. However, their low-temperature activities differed significantly, primarily determined by the specific state of Ni. In the NC-B catalyst prepared by bis(cyclopentadienyl)nickel sublimation, the interaction between Ni species and the support was relatively weak. After reduction, this method yielded highly dispersed metallic Ni nanoparticles, increasing the number of low-temperature active sites. Consequently, the NC-B catalyst achieved 98% CO conversion rate and 100% CH4 selectivity at 300 ℃, demonstrating the optimal low-temperature methanation performance.
Syntheses and photocatalytic CO2 reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters
2026, 42(5): 1039-1047
doi: 10.11862/CJIC.20250353
摘要:
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
2026, 42(5): 1048-1062
doi: 10.11862/CJIC.20250330
摘要:
Two complexes [Cd(L)(CH3O)(CH3COO)]·CH3OH·(CH3)2NH (C1) and [Mn(L)Cl2(CH3OH)] (C2) were synthesized by reacting a new imidazole-bearing ligand 4-(1H-imidazol-1-yl)-N′-(pyridin-2-ylmethylene)benzohydrazide (L) with cadmium and manganese salts, respectively. The ligand was characterized by 1H NMR and 13C NMR spectroscopy, while the complexes were analyzed by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, and UV-Vis spectroscopy. Complex C1 features a 1D zigzag chain structure formed by alternating connections of one ligand and one metal ion. In contrast, complex C2 exhibits a mononuclear molecular structure, where each unit consists of one ligand connected to one manganese ion. Both complexes further form a 3D structure through π-π interactions and intermolecular hydrogen bonds. Cell proliferation assays conducted on four tumor cell lines and one normal cell line revealed that both C1 and C2 exhibited significantly stronger inhibition of tumor cell growth compared to the ligand L. Notably, C1 demonstrated superior anti-proliferative activity against A549 and A2780 cells relative to cisplatin, while showing comparable cytotoxicity toward SMMC-7721 cells. Further mechanistic studies indicated that C1 induces apoptosis in both SMMC-7721 and A549 tumor cells, suppresses the invasion and migration of SMMC-7721 cells, and arrests the cell cycle at the G0/G1 phase.
Two complexes [Cd(L)(CH3O)(CH3COO)]·CH3OH·(CH3)2NH (C1) and [Mn(L)Cl2(CH3OH)] (C2) were synthesized by reacting a new imidazole-bearing ligand 4-(1H-imidazol-1-yl)-N′-(pyridin-2-ylmethylene)benzohydrazide (L) with cadmium and manganese salts, respectively. The ligand was characterized by 1H NMR and 13C NMR spectroscopy, while the complexes were analyzed by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, and UV-Vis spectroscopy. Complex C1 features a 1D zigzag chain structure formed by alternating connections of one ligand and one metal ion. In contrast, complex C2 exhibits a mononuclear molecular structure, where each unit consists of one ligand connected to one manganese ion. Both complexes further form a 3D structure through π-π interactions and intermolecular hydrogen bonds. Cell proliferation assays conducted on four tumor cell lines and one normal cell line revealed that both C1 and C2 exhibited significantly stronger inhibition of tumor cell growth compared to the ligand L. Notably, C1 demonstrated superior anti-proliferative activity against A549 and A2780 cells relative to cisplatin, while showing comparable cytotoxicity toward SMMC-7721 cells. Further mechanistic studies indicated that C1 induces apoptosis in both SMMC-7721 and A549 tumor cells, suppresses the invasion and migration of SMMC-7721 cells, and arrests the cell cycle at the G0/G1 phase.
2026, 42(5): 1063-1072
doi: 10.11862/CJIC.20250345
摘要:
Three zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers, namely [Zn(μ-cada)(bipy)(H2O)]n (1), [Zn(μ3-cada)(phen)·H2O]n (2), and [Cd(μ3-cada)(phen)]n (3), have been constructed hydrothermally at 160 ℃ using bis(4-carboxyphenyl)urea (H2cada), 2, 2′-bipyridine (bipy)/1, 10-phenanthroline (phen), and zinc and cadmium chlorides. The three complexes were fully characterized by infrared spectroscopy, element analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that complexes 1-3 form crystals in the monoclinic P21/n, monoclinic I2/a, and orthorhombic Pbcn space groups. These complexes all possess different 1D chain structures. Complexes 1 and 2 demonstrate substantial catalytic efficiency in the Knoevenagel condensation under ambient temperature conditions.
Three zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers, namely [Zn(μ-cada)(bipy)(H2O)]n (1), [Zn(μ3-cada)(phen)·H2O]n (2), and [Cd(μ3-cada)(phen)]n (3), have been constructed hydrothermally at 160 ℃ using bis(4-carboxyphenyl)urea (H2cada), 2, 2′-bipyridine (bipy)/1, 10-phenanthroline (phen), and zinc and cadmium chlorides. The three complexes were fully characterized by infrared spectroscopy, element analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that complexes 1-3 form crystals in the monoclinic P21/n, monoclinic I2/a, and orthorhombic Pbcn space groups. These complexes all possess different 1D chain structures. Complexes 1 and 2 demonstrate substantial catalytic efficiency in the Knoevenagel condensation under ambient temperature conditions.
2026, 42(5): 1073-1084
doi: 10.11862/CJIC.20250328
摘要:
To investigate the antitumor properties of copper(Ⅱ) complexes, a series of Cu(Ⅱ) complexes (C1-C3) derived from 6, 7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized. These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin. Among them, C3 had the highest antitumor activity against MDA-MB-231 cells, with a half maximal inhibitory concentration (IC50) value of 1.42 μmol·L-1. Moreover, C3 effectively inhibited the growth of 3D multicellular spheres. Mechanistically, it induced significant reactive oxygen species (ROS) generation, initiating a dual-pathway cytotoxic effect. On the one hand, it triggers endoplasmic reticulum stress and inhibits the activity of the related protein, protein disulfide isomerase (PDI). On the other hand, it induces mitochondrial dysfunction. These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.
To investigate the antitumor properties of copper(Ⅱ) complexes, a series of Cu(Ⅱ) complexes (C1-C3) derived from 6, 7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized. These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin. Among them, C3 had the highest antitumor activity against MDA-MB-231 cells, with a half maximal inhibitory concentration (IC50) value of 1.42 μmol·L-1. Moreover, C3 effectively inhibited the growth of 3D multicellular spheres. Mechanistically, it induced significant reactive oxygen species (ROS) generation, initiating a dual-pathway cytotoxic effect. On the one hand, it triggers endoplasmic reticulum stress and inhibits the activity of the related protein, protein disulfide isomerase (PDI). On the other hand, it induces mitochondrial dysfunction. These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.
2026, 42(5): 1085-1095
doi: 10.11862/CJIC.20250321
摘要:
To develop highly stable and active Ru complex catalysts for CO2 hydrogenation, we synthesized Ru complexes bearing rigid pincer-type tridentate NNN (pyrazole-pyridine-pyrazole) ligands and weakly coordinated triphenylphosphine (PPh3) ligands. The NNN ligands can strongly chelate with the Ru metal center, contributing to the overall robustness of the catalytic system. Meanwhile, PPh3 can easily dissociate to form vacant coordination sites, thereby enhancing catalytic activity. As a result, the Ru(Ⅱ)-NNN complex [Ru(L-NNN)Cl(PPh3)2]Cl (1, L-NNN=2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) was not only quite stable, but also showed high activity for CO2 hydrogenation to formate, achieving a TON of up to 150 000. In the mechanism study, based on the results of in-situ NMR, in-situ HPLC-HRMS spectra, and density functional theory calculations, it is speculated that the active intermediates with empty coordination sites are highly active species in CO2 hydrogenation.
To develop highly stable and active Ru complex catalysts for CO2 hydrogenation, we synthesized Ru complexes bearing rigid pincer-type tridentate NNN (pyrazole-pyridine-pyrazole) ligands and weakly coordinated triphenylphosphine (PPh3) ligands. The NNN ligands can strongly chelate with the Ru metal center, contributing to the overall robustness of the catalytic system. Meanwhile, PPh3 can easily dissociate to form vacant coordination sites, thereby enhancing catalytic activity. As a result, the Ru(Ⅱ)-NNN complex [Ru(L-NNN)Cl(PPh3)2]Cl (1, L-NNN=2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) was not only quite stable, but also showed high activity for CO2 hydrogenation to formate, achieving a TON of up to 150 000. In the mechanism study, based on the results of in-situ NMR, in-situ HPLC-HRMS spectra, and density functional theory calculations, it is speculated that the active intermediates with empty coordination sites are highly active species in CO2 hydrogenation.
2026, 42(5): 1096-1112
doi: 10.11862/CJIC.20250311
摘要:
Bi2O3@BiVO4 composites were synthesized using the solvothermal method with ethylene glycol as the solvent. Bi2O3 was grown on the surface of BiVO4 by regulating the reaction temperature. The adsorption performance of the composite for rhodamine B (RhB) was investigated. The results indicate that the reaction temperature significantly impacts the morphology and adsorption performance of Bi2O3@BiVO4. The Bi2O3@BiVO4 composite prepared at 180 ℃ (180-BO@BVO) consisted of nanoparticles with an average size of 7 nm, featuring a higher concentration of oxygen vacancies on the surface, but with a lower specific surface area (only 1.2 m2·g-1). 180-BO@BVO, with oxygen species adsorbed at surface oxygen vacancies carrying a negative charge, achieved an impressive RhB removal efficiency of up to 83.0% through electrostatic interaction with RhB. The adsorption process follows the Langmuir isotherm and the pseudo-second-order kinetic model, suggesting that it is predominantly governed by chemical adsorption. After five cycles of adsorption experiments, the removal efficiency of RhB by composites remained basically unchanged (more than 80%), demonstrating excellent regeneration performance.
Bi2O3@BiVO4 composites were synthesized using the solvothermal method with ethylene glycol as the solvent. Bi2O3 was grown on the surface of BiVO4 by regulating the reaction temperature. The adsorption performance of the composite for rhodamine B (RhB) was investigated. The results indicate that the reaction temperature significantly impacts the morphology and adsorption performance of Bi2O3@BiVO4. The Bi2O3@BiVO4 composite prepared at 180 ℃ (180-BO@BVO) consisted of nanoparticles with an average size of 7 nm, featuring a higher concentration of oxygen vacancies on the surface, but with a lower specific surface area (only 1.2 m2·g-1). 180-BO@BVO, with oxygen species adsorbed at surface oxygen vacancies carrying a negative charge, achieved an impressive RhB removal efficiency of up to 83.0% through electrostatic interaction with RhB. The adsorption process follows the Langmuir isotherm and the pseudo-second-order kinetic model, suggesting that it is predominantly governed by chemical adsorption. After five cycles of adsorption experiments, the removal efficiency of RhB by composites remained basically unchanged (more than 80%), demonstrating excellent regeneration performance.
2026, 42(5): 1113-1120
doi: 10.11862/CJIC.20250298
摘要:
To address the challenges of poor solubility and difficult recyclability of powdered metal-organic frameworks (MOFs), a Eu-based MOF complex, [EuNa(L)(H2O)3]·2H2O (Eu/Na-MOF), was synthesized by the hydrothermal method using 3,5-bis(3,5-dicarboxyphenyl)-1H-1,2,4-triazole (H4L) as the ligand in this study. Systematic characterization and performance evaluation revealed that the complex exhibits a unique 3D structure, high phase purity, excellent thermal stability, and outstanding luminescent properties. Furthermore, the complex was encapsulated in poly(methyl methacrylate) (PMMA) to fabricate a flexible and water-washable composite fluorescent film (Eu/Na-MOF/PMMA). Based on static and dynamic quenching mechanisms, respectively, the film enables reversible detection of tryptamine and Cr2O72- ions in aqueous solutions, demonstrating high selectivity, stability, and portability.
To address the challenges of poor solubility and difficult recyclability of powdered metal-organic frameworks (MOFs), a Eu-based MOF complex, [EuNa(L)(H2O)3]·2H2O (Eu/Na-MOF), was synthesized by the hydrothermal method using 3,5-bis(3,5-dicarboxyphenyl)-1H-1,2,4-triazole (H4L) as the ligand in this study. Systematic characterization and performance evaluation revealed that the complex exhibits a unique 3D structure, high phase purity, excellent thermal stability, and outstanding luminescent properties. Furthermore, the complex was encapsulated in poly(methyl methacrylate) (PMMA) to fabricate a flexible and water-washable composite fluorescent film (Eu/Na-MOF/PMMA). Based on static and dynamic quenching mechanisms, respectively, the film enables reversible detection of tryptamine and Cr2O72- ions in aqueous solutions, demonstrating high selectivity, stability, and portability.
