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2026, 42(5): 897-905
doi: 10.11862/CJIC.20250358
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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。
PtRu/N-doped carbon nanofiber: Preparation and hydrogen evolution performance for water electrolysis
2026, 42(5): 1003-1014
doi: 10.11862/CJIC.20250238
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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.
