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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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期刊内热点文章
2026, 42(6): 1121-1130
doi: 10.11862/CJIC.20260115
摘要:
采用溶剂热法，以双烯基化合物1，5-二[(E)-2-(吡啶-4-基)乙烯基]萘(1，5-bpvn)为主配体，分别引入轴向长度不同的对苯二甲酸(H2bdc)和联苯二甲酸(4，4′-H2bpdc)作为辅助配体，构筑了2例Cd基柱层式配位聚合物[Cd2(1，5-bpvn)2(bdc)2]n (CP1)和[Cd(1，5-bpvn)(4，4′-bpdc)]n (CP2)。单晶结构分析表明，辅助配体的轴向尺寸对框架拓扑结构和穿插模式具有显著调控作用。CP1呈现典型的二重穿插网络，而CP2则形成不多见的自穿插框架。此外，CP1中1，5-bpvn配体间存在in-phase和out-of-phase两种堆积方式，相邻烯烃基团的间距和取向满足固相[2+2]光化学环加成反应的要求。在自然光照射下，CP1发生单晶到单晶转化，生成含双环丁烷二聚体的光反应产物[Cd2(tpdnpp)(bdc)2]n (CP1-C，tpdnpp=四(4-吡啶基)-1，2，11，12-二乙桥-[2.2]萘并环番)。相比之下，CP2中1，5-bpvn配体构象明显扭曲，烯烃间距较大，不满足光环加成条件。研究了CP1和CP2的荧光性质以及CP1在环加成反应前后的荧光变化。
采用溶剂热法，以双烯基化合物1，5-二[(E)-2-(吡啶-4-基)乙烯基]萘(1，5-bpvn)为主配体，分别引入轴向长度不同的对苯二甲酸(H2bdc)和联苯二甲酸(4，4′-H2bpdc)作为辅助配体，构筑了2例Cd基柱层式配位聚合物[Cd2(1，5-bpvn)2(bdc)2]n (CP1)和[Cd(1，5-bpvn)(4，4′-bpdc)]n (CP2)。单晶结构分析表明，辅助配体的轴向尺寸对框架拓扑结构和穿插模式具有显著调控作用。CP1呈现典型的二重穿插网络，而CP2则形成不多见的自穿插框架。此外，CP1中1，5-bpvn配体间存在in-phase和out-of-phase两种堆积方式，相邻烯烃基团的间距和取向满足固相[2+2]光化学环加成反应的要求。在自然光照射下，CP1发生单晶到单晶转化，生成含双环丁烷二聚体的光反应产物[Cd2(tpdnpp)(bdc)2]n (CP1-C，tpdnpp=四(4-吡啶基)-1，2，11，12-二乙桥-[2.2]萘并环番)。相比之下，CP2中1，5-bpvn配体构象明显扭曲，烯烃间距较大，不满足光环加成条件。研究了CP1和CP2的荧光性质以及CP1在环加成反应前后的荧光变化。
2026, 42(6): 1131-1145
doi: 10.11862/CJIC.20260063
摘要:
通过在多孔CaFe2O4上负载CaCO3，制备了一系列磁性多孔CaCO3/CaFe2O4复合材料(CCFO-x，x为合成时Ca(CH3COO)2·H2O与CaFe2O4的物质的量之比)。多孔CaFe2O4载体不仅使活性CaCO3有效分散，进而提供更多的可接触吸附位点，而且赋予了吸附剂一定的磁性，使其可以从溶液中快速分离。吸附实验结果表明，CCFO-x对磷酸盐的吸附量随着材料中Ca含量的增加而增加。其中，CCFO-5对磷酸盐的最大吸附量达到246 mg·g-1，远高于载体CaFe2O4(134 mg·g-1)。动力学拟合和吸附等温线结果揭示了CCFO-5对磷酸盐的吸附为单层化学吸附。并且，CCFO-5在酸性条件下仍能保持良好的磷酸盐吸附性能(pH=3.00~7.00，平衡吸附量Qe=174~144 mg·g-1)，且具有优异的抗离子干扰能力。机理分析表明，CCFO-5在吸附磷酸盐过程中存在表面质子化、静电作用、配体交换以及内层配位反应等化学过程，从而形成了稳定的Ca10(PO4)6(OH)2化合物。回收实验表明，当固液比为15 g·L-1时，1.0 mol·L-1的HCl洗脱剂对所吸附磷酸盐的富集率达到567.4%。
通过在多孔CaFe2O4上负载CaCO3，制备了一系列磁性多孔CaCO3/CaFe2O4复合材料(CCFO-x，x为合成时Ca(CH3COO)2·H2O与CaFe2O4的物质的量之比)。多孔CaFe2O4载体不仅使活性CaCO3有效分散，进而提供更多的可接触吸附位点，而且赋予了吸附剂一定的磁性，使其可以从溶液中快速分离。吸附实验结果表明，CCFO-x对磷酸盐的吸附量随着材料中Ca含量的增加而增加。其中，CCFO-5对磷酸盐的最大吸附量达到246 mg·g-1，远高于载体CaFe2O4(134 mg·g-1)。动力学拟合和吸附等温线结果揭示了CCFO-5对磷酸盐的吸附为单层化学吸附。并且，CCFO-5在酸性条件下仍能保持良好的磷酸盐吸附性能(pH=3.00~7.00，平衡吸附量Qe=174~144 mg·g-1)，且具有优异的抗离子干扰能力。机理分析表明，CCFO-5在吸附磷酸盐过程中存在表面质子化、静电作用、配体交换以及内层配位反应等化学过程，从而形成了稳定的Ca10(PO4)6(OH)2化合物。回收实验表明，当固液比为15 g·L-1时，1.0 mol·L-1的HCl洗脱剂对所吸附磷酸盐的富集率达到567.4%。
2026, 42(6): 1146-1154
doi: 10.11862/CJIC.20260053
摘要:
硼中子俘获疗法(BNCT)利用硼携带剂在中子照射下释放高能粒子，实现细胞尺度精准杀伤，但临床硼携带剂硼苯丙氨酸(BPA)和巯基十二水合十二硼酸钠(BSH)存在含硼量不足及缺乏成像等缺陷。本研究选择二十面体碳硼烷作为硼源，金纳米簇作为荧光探针骨架，将葡萄糖基团引入金纳米簇表面，构建集靶向性、富硼性与荧光成像于一体的新型硼携带剂(AuGSCB-Glu)。该硼携带剂在乳腺癌MCF-7细胞中表现出高特异性成像和高的硼摄取量，并在细胞水平显示出BNCT治疗效果。
硼中子俘获疗法(BNCT)利用硼携带剂在中子照射下释放高能粒子，实现细胞尺度精准杀伤，但临床硼携带剂硼苯丙氨酸(BPA)和巯基十二水合十二硼酸钠(BSH)存在含硼量不足及缺乏成像等缺陷。本研究选择二十面体碳硼烷作为硼源，金纳米簇作为荧光探针骨架，将葡萄糖基团引入金纳米簇表面，构建集靶向性、富硼性与荧光成像于一体的新型硼携带剂(AuGSCB-Glu)。该硼携带剂在乳腺癌MCF-7细胞中表现出高特异性成像和高的硼摄取量，并在细胞水平显示出BNCT治疗效果。
2026, 42(6): 1155-1163
doi: 10.11862/CJIC.20260018
摘要:
基于第一性原理计算对氮化物钙钛矿CeBN3(B=Ta、Nb)的电子结构、光学性质、本征点缺陷及缺陷钝化效果进行了系统分析。计算结果表明，CeTaN3和CeNbN3均为直接带隙半导体材料，带隙值分别为1.10和0.91 eV；CeTaN3存在N间隙(Ni)深能级缺陷，与之相比，CeNbN3未引入深能级缺陷，其能带附近电荷分布更局域，同时具有较低的载流子有效质量和较高的光吸收系数。此外，当碱金属(Li、Na、K、Rb、Cs)分别掺杂CeTaN3中的Ce时，Li、Na、K和Rb掺杂体系中Ni缺陷的跃迁能级均变浅，其中Rb掺杂钝化缺陷的效果最为显著，而Cs掺杂未能钝化Ni的跃迁能级。
基于第一性原理计算对氮化物钙钛矿CeBN3(B=Ta、Nb)的电子结构、光学性质、本征点缺陷及缺陷钝化效果进行了系统分析。计算结果表明，CeTaN3和CeNbN3均为直接带隙半导体材料，带隙值分别为1.10和0.91 eV；CeTaN3存在N间隙(Ni)深能级缺陷，与之相比，CeNbN3未引入深能级缺陷，其能带附近电荷分布更局域，同时具有较低的载流子有效质量和较高的光吸收系数。此外，当碱金属(Li、Na、K、Rb、Cs)分别掺杂CeTaN3中的Ce时，Li、Na、K和Rb掺杂体系中Ni缺陷的跃迁能级均变浅，其中Rb掺杂钝化缺陷的效果最为显著，而Cs掺杂未能钝化Ni的跃迁能级。
2026, 42(6): 1164-1174
doi: 10.11862/CJIC.20250378
摘要:
面向农产品中有机磷农药残留的快速检测需求，我们基于酶抑制效应构建了一种金属团簇基电化学传感器NF/KbE-CS/Au25-xAgx@G/GCE，其中，NF、KbE、CS、Au25-xAgx、G、GCE分别代表Nafion、白芸豆酯酶、壳聚糖、Au25-xAgx(PET)18纳米团簇(PET=2-苯乙硫醇)、多层石墨烯、玻碳电极。该传感器中，Au25-xAgx@G复合材料不仅为生物酶的固定提供了理想基质，更凭借其优异导电性与双金属协同电催化效应，显著促进了界面电子传输，有效放大了检测信号。此外，通过Au25-xAgx@G与KbE-CS的协同作用，实现了对丙溴磷的高灵敏检测。测试条件优化后，该传感器对KbE活性的抑制率与丙溴磷质量浓度的对数在10~2 200 μg·L-1范围内呈良好的线性关系(R2=0.988 4)，检出限低至0.064 μg·L-1。所构建的传感器表现出良好的重现性、稳定性与抗干扰能力，并成功应用于实际样品中的农药检测。
面向农产品中有机磷农药残留的快速检测需求，我们基于酶抑制效应构建了一种金属团簇基电化学传感器NF/KbE-CS/Au25-xAgx@G/GCE，其中，NF、KbE、CS、Au25-xAgx、G、GCE分别代表Nafion、白芸豆酯酶、壳聚糖、Au25-xAgx(PET)18纳米团簇(PET=2-苯乙硫醇)、多层石墨烯、玻碳电极。该传感器中，Au25-xAgx@G复合材料不仅为生物酶的固定提供了理想基质，更凭借其优异导电性与双金属协同电催化效应，显著促进了界面电子传输，有效放大了检测信号。此外，通过Au25-xAgx@G与KbE-CS的协同作用，实现了对丙溴磷的高灵敏检测。测试条件优化后，该传感器对KbE活性的抑制率与丙溴磷质量浓度的对数在10~2 200 μg·L-1范围内呈良好的线性关系(R2=0.988 4)，检出限低至0.064 μg·L-1。所构建的传感器表现出良好的重现性、稳定性与抗干扰能力，并成功应用于实际样品中的农药检测。
2026, 42(6): 1175-1189
doi: 10.11862/CJIC.20250375
摘要:
采用混配体策略，选取异烟酸(HINA)与刚性配体3，3′，5，5′-偶氮苯四羧酸(H4ABTC)与硝酸钴在水热条件下反应，成功协同组装成具有3D菱形孔道结构的金属有机框架(MOF)：[Co4(μ3-OH)2(ABTC)(INA)2(DMF)2]n (SXNU-6-Co，DMF=N，N-二甲基甲酰胺，SXNU=Shanxi Normal University)。其规整孔道内富含偶氮键和吡啶氮活性位点，结合四核金属氧簇中不同配位数Co原子的Co2+/Co3+可逆氧化还原对，协同调控了对4-氨基苯酚(4-AP)的吸附与电催化性能。基于此构建的SXNU-6-Co/GCE(GCE=玻碳电极)传感器在0.2~328 μmol·L-1范围内对4-AP展现出良好的线性响应，检出限低至10.47 nmol·L-1(S/N=3)。巨正则蒙特卡罗(GCMC)模拟结果表明，4-AP与框架中的氮原子之间存在π-π和氢键相互作用，显著增强了底物分子与框架间的相互作用。
采用混配体策略，选取异烟酸(HINA)与刚性配体3，3′，5，5′-偶氮苯四羧酸(H4ABTC)与硝酸钴在水热条件下反应，成功协同组装成具有3D菱形孔道结构的金属有机框架(MOF)：[Co4(μ3-OH)2(ABTC)(INA)2(DMF)2]n (SXNU-6-Co，DMF=N，N-二甲基甲酰胺，SXNU=Shanxi Normal University)。其规整孔道内富含偶氮键和吡啶氮活性位点，结合四核金属氧簇中不同配位数Co原子的Co2+/Co3+可逆氧化还原对，协同调控了对4-氨基苯酚(4-AP)的吸附与电催化性能。基于此构建的SXNU-6-Co/GCE(GCE=玻碳电极)传感器在0.2~328 μmol·L-1范围内对4-AP展现出良好的线性响应，检出限低至10.47 nmol·L-1(S/N=3)。巨正则蒙特卡罗(GCMC)模拟结果表明，4-AP与框架中的氮原子之间存在π-π和氢键相互作用，显著增强了底物分子与框架间的相互作用。
2026, 42(6): 1190-1202
doi: 10.11862/CJIC.20250365
摘要:
以泡沫镍(NF)为基底，并将其作为镍源，结合钼酸铵(钼源)和硫脲(硫源)，通过水热法在NF骨架上原位生长出MoS2/Ni3S2@NF(MNS@NF)复合光热材料。通过X射线衍射仪、扫描电子显微镜(SEM)和X射线光电子能谱仪对复合材料的结构和形貌进行了表征，并对复合光热材料的光吸收性能和界面蒸发性能进行了研究。结果表明，在模拟太阳光照(光照强度为1 kW·m-2)下，水热反应温度为200 ℃、反应时间为24 h的条件下合成的样品MNS@NF-200-24的光吸收率达到91.7%，其在去离子水中的界面蒸发速率达到2.846 kg·m-2·h-1，界面蒸发效率达到95.6%。此外，还测试了MNS@NF-200-24在模拟海水中的界面蒸发速率，蒸发1 h后速率达到2.360 kg·m-2·h-1，界面蒸发连续12 h后稳定在2.000 kg·m-2·h-1，宏观表面无结晶盐析出。蒸发冷凝得到的水达到世界卫生组织(WHO)与美国环境保护署(EPA)饮用水标准。
以泡沫镍(NF)为基底，并将其作为镍源，结合钼酸铵(钼源)和硫脲(硫源)，通过水热法在NF骨架上原位生长出MoS2/Ni3S2@NF(MNS@NF)复合光热材料。通过X射线衍射仪、扫描电子显微镜(SEM)和X射线光电子能谱仪对复合材料的结构和形貌进行了表征，并对复合光热材料的光吸收性能和界面蒸发性能进行了研究。结果表明，在模拟太阳光照(光照强度为1 kW·m-2)下，水热反应温度为200 ℃、反应时间为24 h的条件下合成的样品MNS@NF-200-24的光吸收率达到91.7%，其在去离子水中的界面蒸发速率达到2.846 kg·m-2·h-1，界面蒸发效率达到95.6%。此外，还测试了MNS@NF-200-24在模拟海水中的界面蒸发速率，蒸发1 h后速率达到2.360 kg·m-2·h-1，界面蒸发连续12 h后稳定在2.000 kg·m-2·h-1，宏观表面无结晶盐析出。蒸发冷凝得到的水达到世界卫生组织(WHO)与美国环境保护署(EPA)饮用水标准。
2026, 42(6): 1203-1214
doi: 10.11862/CJIC.20250370
摘要:
以杨絮(PC)为原料，采用乙醇溶剂热法对其进行预处理，再进行碳化，制备了高比表面积的杨絮衍生多孔碳(DPCC)，并研究了其对染料的吸附性能及动力学性能。通过单因素实验优化工艺参数，确定最佳预处理条件(液固比为17 mL·g-1、200 ℃处理2 h)，在此条件下制备的DPCC-10比表面积达到518 m2·g-1。结合傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、拉曼(Raman)光谱、扫描电镜(SEM)和N2吸附-脱附测试等表征手段，证实预处理过程能够有效去除木质素和半纤维素等，形成丰富的多级孔道结构。吸附实验表明，DPCC-10对亚甲蓝(MB)的最大吸附量达到385.71 mg·g-1，优于多数报道的生物质衍生吸附剂。DPCC-10对染料的吸附过程满足准二级动力学方程，表明该吸附以化学吸附为主。经过4次吸附-脱附循环后，DPCC-10对MB的吸附容量仍保持初始值的92.01%，表明材料具有优异的可再生性能。
以杨絮(PC)为原料，采用乙醇溶剂热法对其进行预处理，再进行碳化，制备了高比表面积的杨絮衍生多孔碳(DPCC)，并研究了其对染料的吸附性能及动力学性能。通过单因素实验优化工艺参数，确定最佳预处理条件(液固比为17 mL·g-1、200 ℃处理2 h)，在此条件下制备的DPCC-10比表面积达到518 m2·g-1。结合傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、拉曼(Raman)光谱、扫描电镜(SEM)和N2吸附-脱附测试等表征手段，证实预处理过程能够有效去除木质素和半纤维素等，形成丰富的多级孔道结构。吸附实验表明，DPCC-10对亚甲蓝(MB)的最大吸附量达到385.71 mg·g-1，优于多数报道的生物质衍生吸附剂。DPCC-10对染料的吸附过程满足准二级动力学方程，表明该吸附以化学吸附为主。经过4次吸附-脱附循环后，DPCC-10对MB的吸附容量仍保持初始值的92.01%，表明材料具有优异的可再生性能。
2026, 42(6): 1215-1228
doi: 10.11862/CJIC.20250368
摘要:
采用高温热聚合结合原位溶剂热法构建了Z型g-C3N4/Bi2WO6异质结光催化材料。借助X射线衍射、傅里叶变换红外光谱、扫描电子显微镜、X射线光电子能谱、紫外可见近红外漫反射光谱对异质结材料的组成、结构和光学性质进行了详细表征。结果表明，氧空位缺陷通过局域表面等离激元共振效应提高了异质结对可见光和近红外光的吸收能力；Ⅱ型异质结向Z型异质结的转变提高了光生电子-空穴对的分离效率和氧化还原能力。g-C3N4/Bi2WO6异质结在可见光和近红外光照射下降解氧氟沙星的表观速率常数分别可以达到0.045 8和0.003 8 min-1，明显高于单组分g-C3N4和Bi2WO6。同时，该异质结具有良好的循环稳定性和可重复使用性。
采用高温热聚合结合原位溶剂热法构建了Z型g-C3N4/Bi2WO6异质结光催化材料。借助X射线衍射、傅里叶变换红外光谱、扫描电子显微镜、X射线光电子能谱、紫外可见近红外漫反射光谱对异质结材料的组成、结构和光学性质进行了详细表征。结果表明，氧空位缺陷通过局域表面等离激元共振效应提高了异质结对可见光和近红外光的吸收能力；Ⅱ型异质结向Z型异质结的转变提高了光生电子-空穴对的分离效率和氧化还原能力。g-C3N4/Bi2WO6异质结在可见光和近红外光照射下降解氧氟沙星的表观速率常数分别可以达到0.045 8和0.003 8 min-1，明显高于单组分g-C3N4和Bi2WO6。同时，该异质结具有良好的循环稳定性和可重复使用性。
2026, 42(6): 1229-1236
doi: 10.11862/CJIC.20250355
摘要:
采用溶液扩散的方法分别合成了扩展式四硫富瓦烯衍生物C14H8(C3S2(S-R)2)2[R=苯基(T1)、噻吩-2-基(T2)、吡啶-2-基(T3)]与CuBr2的电荷转移复合物(T1)[Cu2Br6]·2THF、(T2)[Cu2Br6]·2THF和(T3)[Cu2Br6]。晶体结构研究表明，T12+、T22+和T32+呈现不同的分子构型，[Cu2Br6]2-呈平面构型和类八面体构型，3种复合物呈现不同的堆积结构。通过改变四硫富瓦烯衍生物的外围芳基，实现了对阴离子构型的有效调控，并且化合物T1~T3可根据阴离子构型调控自身构型。
采用溶液扩散的方法分别合成了扩展式四硫富瓦烯衍生物C14H8(C3S2(S-R)2)2[R=苯基(T1)、噻吩-2-基(T2)、吡啶-2-基(T3)]与CuBr2的电荷转移复合物(T1)[Cu2Br6]·2THF、(T2)[Cu2Br6]·2THF和(T3)[Cu2Br6]。晶体结构研究表明，T12+、T22+和T32+呈现不同的分子构型，[Cu2Br6]2-呈平面构型和类八面体构型，3种复合物呈现不同的堆积结构。通过改变四硫富瓦烯衍生物的外围芳基，实现了对阴离子构型的有效调控，并且化合物T1~T3可根据阴离子构型调控自身构型。
2026, 42(6): 1237-1246
doi: 10.11862/CJIC.20250322
摘要:
采用Sm3+与Sb3+共掺杂的策略，实现了对Cs2NaGdCl6荧光粉发光颜色从蓝光到白光的有效调控。采用微波固相法合成了一系列Cs2NaGd0.985-xCl6∶0.015Sb3+，xSm3+(x=0~0.130)荧光粉。物相分析表明，所有样品均保持纯相双钙钛矿结构，Sm3+成功融入晶格。光谱分析发现，在336 nm激发下，材料同时产生源于自陷激子(STEs)的460 nm宽带蓝光发射和Sm3+的特征发射(568、604、653 nm)，并且该体系中存在STEs向Sm3+的有效能量传递，效率达13.34%(x=0.070)。当Sm3+掺杂浓度为0.070时，荧光粉表现出最优性能，光致发光量子产率(PLQY)为35.49%，且具备良好的热稳定性，423 K下发光强度保持为室温的68.6%，热活化能为163 meV。更重要的是，通过调控Sm3+浓度，实现了发光颜色从蓝光区到白光区的连续可控变化。
采用Sm3+与Sb3+共掺杂的策略，实现了对Cs2NaGdCl6荧光粉发光颜色从蓝光到白光的有效调控。采用微波固相法合成了一系列Cs2NaGd0.985-xCl6∶0.015Sb3+，xSm3+(x=0~0.130)荧光粉。物相分析表明，所有样品均保持纯相双钙钛矿结构，Sm3+成功融入晶格。光谱分析发现，在336 nm激发下，材料同时产生源于自陷激子(STEs)的460 nm宽带蓝光发射和Sm3+的特征发射(568、604、653 nm)，并且该体系中存在STEs向Sm3+的有效能量传递，效率达13.34%(x=0.070)。当Sm3+掺杂浓度为0.070时，荧光粉表现出最优性能，光致发光量子产率(PLQY)为35.49%，且具备良好的热稳定性，423 K下发光强度保持为室温的68.6%，热活化能为163 meV。更重要的是，通过调控Sm3+浓度，实现了发光颜色从蓝光区到白光区的连续可控变化。
2026, 42(6): 1247-1260
doi: 10.11862/CJIC.20250299
摘要:
钯前驱体的化学结构及其与配体的协同作用，直接影响原位新生活性Pd(0)中心的构型，进而决定C—C偶联反应的效率，故本研究以[Pd(COD)X2](COD=1，5-环辛二烯，X=Cl、Br)为钯前驱体、有机膦(PR3)为调控配体，考察它们对C—C偶联反应催化性能的影响。通过元素分析、红外光谱、核磁共振及理论计算解析前驱体Pd(Ⅱ)中心的化学结构与溶剂稳定性，结合单晶X射线衍射分析反应后催化剂结构，研究前驱体结构在反应中的作用机制。结果表明，PR3调控的[Pd(COD)X2]/Pd(0)体系催化效率优于市售trans-[Pd(PPh3)2Cl2]，且呈现明确的配体依赖性(顺序为cis-[Pd(COD)X2]/Xantphos > cis-[Pd(COD)X2]/PPh3 > trans-[Pd(PPh3)2Cl2] > [Pd(COD)X2])及卤素依赖性([Pd(COD)Br2] > [Pd(COD)Cl2])。机理分析显示，PR3通过富电子膦与Pd(0)配位、大位阻效应抑制其团聚失活；PR3的构型调控与卤素键强协同影响Pd(0)生成：Xantphos的刚性骨架维持钯中心顺式配位，生成高活性cis-(Xantphos)-Pd(0)，暴露更多活性位点，而PPh3衍生的中间体易转化为顺反异构体混合物。此外，Pd-Br键能更低、更易断裂，促使[Pd(COD)Br2]更快生成Pd(0)，产物收率更高。
钯前驱体的化学结构及其与配体的协同作用，直接影响原位新生活性Pd(0)中心的构型，进而决定C—C偶联反应的效率，故本研究以[Pd(COD)X2](COD=1，5-环辛二烯，X=Cl、Br)为钯前驱体、有机膦(PR3)为调控配体，考察它们对C—C偶联反应催化性能的影响。通过元素分析、红外光谱、核磁共振及理论计算解析前驱体Pd(Ⅱ)中心的化学结构与溶剂稳定性，结合单晶X射线衍射分析反应后催化剂结构，研究前驱体结构在反应中的作用机制。结果表明，PR3调控的[Pd(COD)X2]/Pd(0)体系催化效率优于市售trans-[Pd(PPh3)2Cl2]，且呈现明确的配体依赖性(顺序为cis-[Pd(COD)X2]/Xantphos > cis-[Pd(COD)X2]/PPh3 > trans-[Pd(PPh3)2Cl2] > [Pd(COD)X2])及卤素依赖性([Pd(COD)Br2] > [Pd(COD)Cl2])。机理分析显示，PR3通过富电子膦与Pd(0)配位、大位阻效应抑制其团聚失活；PR3的构型调控与卤素键强协同影响Pd(0)生成：Xantphos的刚性骨架维持钯中心顺式配位，生成高活性cis-(Xantphos)-Pd(0)，暴露更多活性位点，而PPh3衍生的中间体易转化为顺反异构体混合物。此外，Pd-Br键能更低、更易断裂，促使[Pd(COD)Br2]更快生成Pd(0)，产物收率更高。
2026, 42(6): 1261-1275
doi: 10.11862/CJIC.20250329
摘要:
采用高温固相法制备了Ca0.993-yScBO4∶0.007Bi3+，yEu3+(y=0~0.100)系列荧光粉。通过在CaScBO4基质中构建高效的Bi3+→Eu3+非辐射能量传递体系，成功实现了330 nm激发下发光颜色从蓝光区[CIE色坐标：(0.153，0.050)]到橙红光区[CIE色坐标：(0.530，0.270)]的连续调谐。该荧光粉的能量传递效率最高可达71.2%，机制为电偶极-电偶极相互作用，临界距离为1.36 nm。代表性橙红光样品Ca0.893ScBO4∶0.007Bi3+, 0.100Eu3+在423 K时仍保持室温积分强度的77.7%，热猝灭活化能为0.417 eV，表现出优异的热稳定性。相较于单掺的Ca0.993ScBO4∶0.007Bi3+蓝光荧光粉，该共掺体系在维持较高量子效率与优异热稳定性的同时，实现了蓝光至橙红光的宽范围颜色调谐。
采用高温固相法制备了Ca0.993-yScBO4∶0.007Bi3+，yEu3+(y=0~0.100)系列荧光粉。通过在CaScBO4基质中构建高效的Bi3+→Eu3+非辐射能量传递体系，成功实现了330 nm激发下发光颜色从蓝光区[CIE色坐标：(0.153，0.050)]到橙红光区[CIE色坐标：(0.530，0.270)]的连续调谐。该荧光粉的能量传递效率最高可达71.2%，机制为电偶极-电偶极相互作用，临界距离为1.36 nm。代表性橙红光样品Ca0.893ScBO4∶0.007Bi3+, 0.100Eu3+在423 K时仍保持室温积分强度的77.7%，热猝灭活化能为0.417 eV，表现出优异的热稳定性。相较于单掺的Ca0.993ScBO4∶0.007Bi3+蓝光荧光粉，该共掺体系在维持较高量子效率与优异热稳定性的同时，实现了蓝光至橙红光的宽范围颜色调谐。
2026, 42(6): 1276-1288
doi: 10.11862/CJIC.20260011
摘要:
Using sodium phytate (PA) as a ligand precursor, boron-doped iron-cobalt phytate materials (B-FeCoPA) were synthesized via a one-step hydrothermal method. Boron incorporation into FeCoPA effectively modulates the local bonding environment and electronic structure through synergistic B-Fe-Co interactions, thereby facilitating electron transfer and enhancing the electrocatalytic activity for the oxygen evolution reaction (OER). The optimized B-FeCoPA exhibited an outstanding OER catalytic activity in alkaline electrolyte, achieving low overpotentials of 299 mV at 10 mA·cm-2 and 354 mV at 100 mA·cm-2, a small Tafel slope of 46 mV·dec-1, and a high Faradaic efficiency of 96%. Moreover, B-FeCoPA demonstrated good operational stability, maintaining a stable potential of approximately 1.52 V (vs RHE) at 10 mA·cm-2 over a 10-h continuous test in 1.0 mol·L-1 KOH.
Using sodium phytate (PA) as a ligand precursor, boron-doped iron-cobalt phytate materials (B-FeCoPA) were synthesized via a one-step hydrothermal method. Boron incorporation into FeCoPA effectively modulates the local bonding environment and electronic structure through synergistic B-Fe-Co interactions, thereby facilitating electron transfer and enhancing the electrocatalytic activity for the oxygen evolution reaction (OER). The optimized B-FeCoPA exhibited an outstanding OER catalytic activity in alkaline electrolyte, achieving low overpotentials of 299 mV at 10 mA·cm-2 and 354 mV at 100 mA·cm-2, a small Tafel slope of 46 mV·dec-1, and a high Faradaic efficiency of 96%. Moreover, B-FeCoPA demonstrated good operational stability, maintaining a stable potential of approximately 1.52 V (vs RHE) at 10 mA·cm-2 over a 10-h continuous test in 1.0 mol·L-1 KOH.
2026, 42(6): 1289-1298
doi: 10.11862/CJIC.20250369
摘要:
A composite catalyst (Ni-NiO@CN) with nickel-nickel oxide (Ni-NiO) loaded on two-dimensional g-C3N4 (CN) was successfully constructed by hydrothermal coupled pyrolysis. The Ni-NiO nanostructure served as the methanol oxidation reaction (MOR) active center, and the N-rich CN matrix promoted electron transfer and effectively protected the active components from shedding through physical isolation. Ni-NiO@CN-500, obtained by calcination at 500 ℃, exhibited the highest activity with the current density of 164 mA·cm-2 at 1.67 V (vs RHE) in the alkaline medium. Furthermore, the current density of Ni-NiO@CN-500 could be maintained at 154.9 mA·cm-2 (94.5% of its initial value) in the CO-saturated alkaline methanol electrolyte, significantly outperforming commercial Pt/C catalysts.
A composite catalyst (Ni-NiO@CN) with nickel-nickel oxide (Ni-NiO) loaded on two-dimensional g-C3N4 (CN) was successfully constructed by hydrothermal coupled pyrolysis. The Ni-NiO nanostructure served as the methanol oxidation reaction (MOR) active center, and the N-rich CN matrix promoted electron transfer and effectively protected the active components from shedding through physical isolation. Ni-NiO@CN-500, obtained by calcination at 500 ℃, exhibited the highest activity with the current density of 164 mA·cm-2 at 1.67 V (vs RHE) in the alkaline medium. Furthermore, the current density of Ni-NiO@CN-500 could be maintained at 154.9 mA·cm-2 (94.5% of its initial value) in the CO-saturated alkaline methanol electrolyte, significantly outperforming commercial Pt/C catalysts.
2026, 42(6): 1299-1311
doi: 10.11862/CJIC.20260362
摘要:
A highly sensitive surface-enhanced Raman scattering (SERS) substrate was constructed, which was a Cu2O-GO-AuNSts sandwich heterostructure assembled on a filter membrane, with ultrathin graphene oxide (GO) precisely embedded between the thorn-like Cu2O microcrystals and gold nanostars (AuNSts). This heterostructure achieved strong electromagnetic enhancement and rapid photogenerated charge transfer by synergistically coupling broadband light absorption, efficient molecular enrichment, and abundant plasma "hotspots". Using rhodamine 6G (R6G) as probe molecules, the substrate achieved an ultra-low detection limit of 10-13 mol·L-1, demonstrating superior SERS sensitivity. More importantly, the heterostructure concurrently exhibited significant photocatalytic performance, thereby endowing the substrate with self-cleaning functionality. Even for the highly stable and recalcitrant persistent organic pollutant (POP), 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47), the characteristic SERS fingerprint could be clearly identified at a concentration as low as 10-7 mol·L-1. UV-Vis spectroscopy analysis revealed a degradation efficiency of approximately 66% after 20 h of light irradiation. The excellent SERS property of the sandwich structure originates from the synergistic effect of local surface plasmon resonance (LSPR) effect attributed to AuNSts and the molecular enrichment effect of GO lamellae and filter membrane, while the photocatalytic activity originates from the photo-induced charge transfer mechanism within the structure.
A highly sensitive surface-enhanced Raman scattering (SERS) substrate was constructed, which was a Cu2O-GO-AuNSts sandwich heterostructure assembled on a filter membrane, with ultrathin graphene oxide (GO) precisely embedded between the thorn-like Cu2O microcrystals and gold nanostars (AuNSts). This heterostructure achieved strong electromagnetic enhancement and rapid photogenerated charge transfer by synergistically coupling broadband light absorption, efficient molecular enrichment, and abundant plasma "hotspots". Using rhodamine 6G (R6G) as probe molecules, the substrate achieved an ultra-low detection limit of 10-13 mol·L-1, demonstrating superior SERS sensitivity. More importantly, the heterostructure concurrently exhibited significant photocatalytic performance, thereby endowing the substrate with self-cleaning functionality. Even for the highly stable and recalcitrant persistent organic pollutant (POP), 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47), the characteristic SERS fingerprint could be clearly identified at a concentration as low as 10-7 mol·L-1. UV-Vis spectroscopy analysis revealed a degradation efficiency of approximately 66% after 20 h of light irradiation. The excellent SERS property of the sandwich structure originates from the synergistic effect of local surface plasmon resonance (LSPR) effect attributed to AuNSts and the molecular enrichment effect of GO lamellae and filter membrane, while the photocatalytic activity originates from the photo-induced charge transfer mechanism within the structure.
2026, 42(6): 1312-1320
doi: 10.11862/CJIC.20250354
摘要:
Two isostructural coordination polymers [Zn(L)(HCOO)]n (Zn-LFor) and [Zn(L)Cl]n (Zn-LCl) were synthesized by a hydrothermal method based on HL·NaX (HL=2-{[(pyridin-4-yl)methyl]amino}-3, 3-dimethylbutanoic acid, X-=HCOO-, Cl-). Zn-LFor and Zn-LCl belong to the orthorhombic system with space group P212121, which exhibit distorted square pyramidal structures. Interestingly, the values of the trigonality factor (τ5) are distinctively different. Zn-LCl has a τ5 value of 0.144, while the value of τ5 for Zn-LFor is only 0.089. Zn-LFor displayed an excellent fluorescence property, which can be used as a fluorescence probe to detect Cr2O72- in H2O solution with high selectivity and sensitivity, with a quenching constant (KSV) of 2.23×104 L·mol-1. The detection limit of Cr2O72- was calculated from the experimental data, and the value was 1.03 μmol·L-1.
Two isostructural coordination polymers [Zn(L)(HCOO)]n (Zn-LFor) and [Zn(L)Cl]n (Zn-LCl) were synthesized by a hydrothermal method based on HL·NaX (HL=2-{[(pyridin-4-yl)methyl]amino}-3, 3-dimethylbutanoic acid, X-=HCOO-, Cl-). Zn-LFor and Zn-LCl belong to the orthorhombic system with space group P212121, which exhibit distorted square pyramidal structures. Interestingly, the values of the trigonality factor (τ5) are distinctively different. Zn-LCl has a τ5 value of 0.144, while the value of τ5 for Zn-LFor is only 0.089. Zn-LFor displayed an excellent fluorescence property, which can be used as a fluorescence probe to detect Cr2O72- in H2O solution with high selectivity and sensitivity, with a quenching constant (KSV) of 2.23×104 L·mol-1. The detection limit of Cr2O72- was calculated from the experimental data, and the value was 1.03 μmol·L-1.
2026, 42(6): 1321-1336
doi: 10.11862/CJIC.20250333
摘要:
Two density functional theory methods were employed to evaluate the H2 storage capabilities of metallo-borospherenes TM8B6 (TM=Ni, Pd). Consequently, the superatoms Ni8B6 and Pd8B6, which accommodate 40 and 32 H2 molecules, respectively, exhibit gravimetric H2 uptake capacities of 13.134% and 6.562%, respectively. The average binding energies of Ni8B6(H2)40 and Pd8B6(H2)32 fall within the optimal range for reversible H2 storage applications. The interactions between H2 molecules and the parent structures were characterized using various wave function analysis methods. Polarization effects, alongside the Kubas mechanism, are pivotal to the adsorption of H2 on TM8B6. Moreover, the investigations examine the effect of temperature on the H2 storage capacity of TM8B6 at atmospheric pressure. Atom-centered density-matrix propagation molecular dynamics simulations confirm the reversibility of H2 adsorption and desorption cycles. The thermodynamic analyses of the desorption behavior of H2 molecules were conducted via a three-dimensional graph, plotted based on the relationship between the number of adsorbed H2 molecules and temperature as well as pressure, revealing that the majority of adsorbed H2 molecules can be released at 0.5 MPa and 358 K. Compared to the respective monomeric counterparts, the H2 storage densities of (TM8B6)2 dimers exhibit a slight reduction.
Two density functional theory methods were employed to evaluate the H2 storage capabilities of metallo-borospherenes TM8B6 (TM=Ni, Pd). Consequently, the superatoms Ni8B6 and Pd8B6, which accommodate 40 and 32 H2 molecules, respectively, exhibit gravimetric H2 uptake capacities of 13.134% and 6.562%, respectively. The average binding energies of Ni8B6(H2)40 and Pd8B6(H2)32 fall within the optimal range for reversible H2 storage applications. The interactions between H2 molecules and the parent structures were characterized using various wave function analysis methods. Polarization effects, alongside the Kubas mechanism, are pivotal to the adsorption of H2 on TM8B6. Moreover, the investigations examine the effect of temperature on the H2 storage capacity of TM8B6 at atmospheric pressure. Atom-centered density-matrix propagation molecular dynamics simulations confirm the reversibility of H2 adsorption and desorption cycles. The thermodynamic analyses of the desorption behavior of H2 molecules were conducted via a three-dimensional graph, plotted based on the relationship between the number of adsorbed H2 molecules and temperature as well as pressure, revealing that the majority of adsorbed H2 molecules can be released at 0.5 MPa and 358 K. Compared to the respective monomeric counterparts, the H2 storage densities of (TM8B6)2 dimers exhibit a slight reduction.
2026, 42(6): 1337-1344
doi: 10.11862/CJIC.20250325
摘要:
A novel viologen-based photochromic coordination polymer, namely [Zn(CV)0.5(BDC)(H2O)]·2H2O (1), has been successfully constructed via solvothermal self-assembly of Zn2+ ions with the 1, 1′-bis(2-carboxyethyl)-4, 4′-bipyridinium ((H2CV)2+) as a photo-responsive functional unit and terephthalic acid (H2BDC) as an auxiliary bridging ligand. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 1D chain-like framework. Upon light irradiation, complex 1 exhibited a distinct photo-responsive color-changing behavior, transforming from colorless to blue. The blue-colored sample gradually faded and reverted to its original colorless state upon being placed in a dark environment at room temperature, demonstrating excellent reversible photochromic properties. On the basis of its photochromic performance, the application of this complex in ink-free printing has been explored. Furthermore, complex 1 emitted blue light under UV irradiation in a dark environment, revealing favorable photoluminescent characteristics. In addition, complex 1 possessed multiple photoswitchable properties.
A novel viologen-based photochromic coordination polymer, namely [Zn(CV)0.5(BDC)(H2O)]·2H2O (1), has been successfully constructed via solvothermal self-assembly of Zn2+ ions with the 1, 1′-bis(2-carboxyethyl)-4, 4′-bipyridinium ((H2CV)2+) as a photo-responsive functional unit and terephthalic acid (H2BDC) as an auxiliary bridging ligand. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 1D chain-like framework. Upon light irradiation, complex 1 exhibited a distinct photo-responsive color-changing behavior, transforming from colorless to blue. The blue-colored sample gradually faded and reverted to its original colorless state upon being placed in a dark environment at room temperature, demonstrating excellent reversible photochromic properties. On the basis of its photochromic performance, the application of this complex in ink-free printing has been explored. Furthermore, complex 1 emitted blue light under UV irradiation in a dark environment, revealing favorable photoluminescent characteristics. In addition, complex 1 possessed multiple photoswitchable properties.
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.
