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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(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.
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.
