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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(8): 1569-1581
doi: 10.11862/CJIC.20260062
摘要:
发展快速、灵敏、高选择性的现场检测技术是保障食品安全的关键。金属有机骨架(metal-organic frameworks，MOFs)凭借高比表面积、结构可调及易于功能化等特性，在荧光传感领域展现出巨大应用潜力。然而，传统MOFs材料水稳定性较差，在含水食品基质中易发生骨架水解坍塌，极大地限制了其在实际食品检测中的应用。本文基于软硬酸碱理论、空间位阻效应、疏水功能修饰及框架互锁等关键策略，系统归纳高水稳定性MOFs的构筑方法，并深入阐述荧光猝灭、荧光开启、比率荧光等荧光传感机制。在此基础上，重点综述了水稳定性MOFs荧光传感器在食品安全领域的最新研究进展，涵盖农药残留、抗生素、重金属离子、食源性致病菌及食品新鲜度指示检测等方面。最后，基于当前研究面临的挑战，对未来发展趋势进行了展望。本综述旨在为复杂食品体系中高水稳定性MOFs荧光传感材料的制备与应用提供理论参考。
发展快速、灵敏、高选择性的现场检测技术是保障食品安全的关键。金属有机骨架(metal-organic frameworks，MOFs)凭借高比表面积、结构可调及易于功能化等特性，在荧光传感领域展现出巨大应用潜力。然而，传统MOFs材料水稳定性较差，在含水食品基质中易发生骨架水解坍塌，极大地限制了其在实际食品检测中的应用。本文基于软硬酸碱理论、空间位阻效应、疏水功能修饰及框架互锁等关键策略，系统归纳高水稳定性MOFs的构筑方法，并深入阐述荧光猝灭、荧光开启、比率荧光等荧光传感机制。在此基础上，重点综述了水稳定性MOFs荧光传感器在食品安全领域的最新研究进展，涵盖农药残留、抗生素、重金属离子、食源性致病菌及食品新鲜度指示检测等方面。最后，基于当前研究面临的挑战，对未来发展趋势进行了展望。本综述旨在为复杂食品体系中高水稳定性MOFs荧光传感材料的制备与应用提供理论参考。
2026, 42(8): 1582-1592
doi: 10.11862/CJIC.20260077
摘要:
通过静电组装方法成功构建了二维Cu-TCPP/MXene复合材料[Cu-TCPP=四羧基苯基卟啉铜]，其具有高导电网络和多孔传输通道的异质界面，有效促进了电解质离子扩散和电荷传输。在最优配比下，Cu-TCPP/MXene电极的透光率在60%以上，组装的透明超级电容器的面电容达到7.48 mF·cm-2。进一步以Cu-TCPP/MXene为正极，电沉积锌为负极，构建了非对称锌离子混合超级电容器(ZIHSC)，其电压窗口拓宽至0~1.2 V，透光率为58.9%，面电容达到10.5 mF·cm-2，能量密度达到2.1 μWh·cm-2。
通过静电组装方法成功构建了二维Cu-TCPP/MXene复合材料[Cu-TCPP=四羧基苯基卟啉铜]，其具有高导电网络和多孔传输通道的异质界面，有效促进了电解质离子扩散和电荷传输。在最优配比下，Cu-TCPP/MXene电极的透光率在60%以上，组装的透明超级电容器的面电容达到7.48 mF·cm-2。进一步以Cu-TCPP/MXene为正极，电沉积锌为负极，构建了非对称锌离子混合超级电容器(ZIHSC)，其电压窗口拓宽至0~1.2 V，透光率为58.9%，面电容达到10.5 mF·cm-2，能量密度达到2.1 μWh·cm-2。
2026, 42(8): 1593-1602
doi: 10.11862/CJIC.20260107
摘要:
合成了一种稳定、易合成的多酸(即多金属氧酸盐，简称POM)基Cu-MOF杂化物(POM-Cu-MOF)，并将其制备成碳糊电极(CPE)，记为POM-Cu-MOF-CPE。利用标准的三电极系统研究了其电化学行为。结果表明，在pH=1~4的范围内，POM-Cu-MOF-CPE的循环伏安法曲线呈现出4对可逆的氧化还原对，分别对应Cu2+/Cu+的单电子氧化还原及钼系POM中Mo6+的三步双电子、双质子氧化还原过程。与经典Keggin型POM在水溶液中的电化学性能对比可知，POM-Cu-MOF-CPE具有更宽的电化学窗口。对水中常见的污染离子(IO3-、NO2-、Cr2O72-)的电催化研究表明，POM-Cu-MOF中归属于Mo6+的4e-→6e-还原产物的阴极峰对上述水中污染物的电催化还原反应展现出优异的催化性能，检出限达到痕量检测标准。在常见的干扰物共存体系中，POM-Cu-MOF-CPE仍保持稳定的电流响应，表现出强抗干扰能力。
合成了一种稳定、易合成的多酸(即多金属氧酸盐，简称POM)基Cu-MOF杂化物(POM-Cu-MOF)，并将其制备成碳糊电极(CPE)，记为POM-Cu-MOF-CPE。利用标准的三电极系统研究了其电化学行为。结果表明，在pH=1~4的范围内，POM-Cu-MOF-CPE的循环伏安法曲线呈现出4对可逆的氧化还原对，分别对应Cu2+/Cu+的单电子氧化还原及钼系POM中Mo6+的三步双电子、双质子氧化还原过程。与经典Keggin型POM在水溶液中的电化学性能对比可知，POM-Cu-MOF-CPE具有更宽的电化学窗口。对水中常见的污染离子(IO3-、NO2-、Cr2O72-)的电催化研究表明，POM-Cu-MOF中归属于Mo6+的4e-→6e-还原产物的阴极峰对上述水中污染物的电催化还原反应展现出优异的催化性能，检出限达到痕量检测标准。在常见的干扰物共存体系中，POM-Cu-MOF-CPE仍保持稳定的电流响应，表现出强抗干扰能力。
2026, 42(8): 1603-1612
doi: 10.11862/CJIC.20260089
摘要:
采用酸碱混合配体策略，选用2，6-二[4-(1，2，4-三唑-1-基)苯乙烯基]环己酮(BTBCH)分别与对苯二甲酸(H2BDC)、间苯二甲酸(IPA)或5-甲基间苯二甲酸(H2MP)，通过溶剂热反应制备了3种新型配位聚合物[Zn(BTBCH)2(BDC)]n (1)、[Zn(BTBCH)2(IPA)]n (2)和[Zn(BTBCH)(MP)]n (3)。晶体结构分析表明化合物1和2属于一维链状结构，3的二维网状结构整齐堆积，形成隧道。3种材料在CO2环加成反应和光催化染料降解上展现出了较好的催化性能，并具有一定的重复使用性能。
采用酸碱混合配体策略，选用2，6-二[4-(1，2，4-三唑-1-基)苯乙烯基]环己酮(BTBCH)分别与对苯二甲酸(H2BDC)、间苯二甲酸(IPA)或5-甲基间苯二甲酸(H2MP)，通过溶剂热反应制备了3种新型配位聚合物[Zn(BTBCH)2(BDC)]n (1)、[Zn(BTBCH)2(IPA)]n (2)和[Zn(BTBCH)(MP)]n (3)。晶体结构分析表明化合物1和2属于一维链状结构，3的二维网状结构整齐堆积，形成隧道。3种材料在CO2环加成反应和光催化染料降解上展现出了较好的催化性能，并具有一定的重复使用性能。
2026, 42(8): 1613-1626
doi: 10.11862/CJIC.20260086
摘要:
采用原位溶剂热法合成了氮空位g-C3N4(NVCN)、Ti3C2Tx(TCT)、W18O49(WO)三者复合的CN/TCT/WO异质结材料，并对其物相组成、微观结构、光学和光电化学性质及光催化降解性能进行表征。CN/TCT/WO异质结因缺陷的表面等离激元共振效应表现出全太阳光谱吸收特性。此外，多级异质界面的形成及缺陷的局域电磁场增强效应提高了材料光生电子-空穴对的分离效率并延长了其寿命。Ⅱ型异质结以TCT为电子媒介转变为Z型异质结，提高了表面氧化还原反应的驱动力。最优的异质结在可见光照射40 min、近红外光照射180 min时，对四环素的矿化效率分别达到82.9%和72.3%，同时可以分解和矿化环丙沙星、氧氟沙星、诺氟沙星和甲硝唑等抗生素。循环实验结果证实了该异质结材料具有良好的结构稳定性和可重复使用性。
采用原位溶剂热法合成了氮空位g-C3N4(NVCN)、Ti3C2Tx(TCT)、W18O49(WO)三者复合的CN/TCT/WO异质结材料，并对其物相组成、微观结构、光学和光电化学性质及光催化降解性能进行表征。CN/TCT/WO异质结因缺陷的表面等离激元共振效应表现出全太阳光谱吸收特性。此外，多级异质界面的形成及缺陷的局域电磁场增强效应提高了材料光生电子-空穴对的分离效率并延长了其寿命。Ⅱ型异质结以TCT为电子媒介转变为Z型异质结，提高了表面氧化还原反应的驱动力。最优的异质结在可见光照射40 min、近红外光照射180 min时，对四环素的矿化效率分别达到82.9%和72.3%，同时可以分解和矿化环丙沙星、氧氟沙星、诺氟沙星和甲硝唑等抗生素。循环实验结果证实了该异质结材料具有良好的结构稳定性和可重复使用性。
2026, 42(8): 1627-1636
doi: 10.11862/CJIC.20260084
摘要:
基于肌醇中多羟基的亲锌性，将肌醇用作水系锌离子电池(AZIBs)的电解质添加剂，设计了一种由ZnSO4(ZSO)和肌醇组成的复合电解质(ZSO+肌醇)，以提高锌负极的稳定性。肌醇所含的极性羟基官能团赋予了电解质优异的亲锌性，使其能够参与Zn2+溶剂化结构重构，优化Zn2+配位环境，并有效降低电极/电解质界面自由水活度，抑制副反应发生。肌醇可优先吸附在锌负极表面，改善电解质与电极的润湿性，增强电极/电解质界面的稳定性。肌醇为Zn2+的迁移提供了丰富的活性位点，显著改善了其扩散动力学性能，并有效提高了Zn2+迁移数。因此，基于ZSO+肌醇电解质组装的Zn||Zn对称电池在1 mA·cm-2下可实现长达2 000 h的稳定循环；Zn||Cu半电池在循环1 000圈后仍能保持99.7%的平均库仑效率。此外，Zn||ZVO(Zn3V3O8)全电池表现出优异的电化学性能，循环1 000圈后仍保持72.7 mAh·g-1的放电容量。
基于肌醇中多羟基的亲锌性，将肌醇用作水系锌离子电池(AZIBs)的电解质添加剂，设计了一种由ZnSO4(ZSO)和肌醇组成的复合电解质(ZSO+肌醇)，以提高锌负极的稳定性。肌醇所含的极性羟基官能团赋予了电解质优异的亲锌性，使其能够参与Zn2+溶剂化结构重构，优化Zn2+配位环境，并有效降低电极/电解质界面自由水活度，抑制副反应发生。肌醇可优先吸附在锌负极表面，改善电解质与电极的润湿性，增强电极/电解质界面的稳定性。肌醇为Zn2+的迁移提供了丰富的活性位点，显著改善了其扩散动力学性能，并有效提高了Zn2+迁移数。因此，基于ZSO+肌醇电解质组装的Zn||Zn对称电池在1 mA·cm-2下可实现长达2 000 h的稳定循环；Zn||Cu半电池在循环1 000圈后仍能保持99.7%的平均库仑效率。此外，Zn||ZVO(Zn3V3O8)全电池表现出优异的电化学性能，循环1 000圈后仍保持72.7 mAh·g-1的放电容量。
2026, 42(8): 1637-1646
doi: 10.11862/CJIC.20260049
摘要:
本工作中，通过引入芳香磺酸配体1，5-萘二磺酸(H2NDS)作为结构导向剂，与七元瓜环(Q[7])和过渡金属离子Cu2+和Cd2+在水热条件下反应，成功制备出了2例同构的新型七元瓜环基超分子自组装体：[M(H2O)4(Q[7])](NDS)·xH2O(1：M=Cd，x=14；2：M=Cu，x=15)，并采用单晶X射线衍射、粉末X射线衍射、红外光谱、热重分析和Hirshfeld表面分析等手段对其进行了测试和表征。结果表明，2种自组装体晶体中，Q[7]均是直接与过渡金属离子配位，形成了1∶1型简单配合物Q[7]-M2+，而磺酸配体则是完全去质子化，以阴离子形式NDS2-来保持体系电荷平衡并分布在Q[7]环外侧；二者通过Q[7]外壁上的次甲基和亚甲基与NDS2-的磺酸根之间的C—H…O氢键、萘环之间的C—H…π作用形成双链型一维超分子链，并进一步通过Q[7]分子间的氢键作用形成了最终的三维超分子框架结构。Hirshfeld表面分析进一步证明了自组装体晶体中含有丰富的弱相互作用，其中氢键作用对于最终三维超分子框架结构的形成起到了主要贡献。此外，荧光测试结果还表明，自组装体1可以通过荧光猝灭的方式选择性检测水体系中的Cu2+。
本工作中，通过引入芳香磺酸配体1，5-萘二磺酸(H2NDS)作为结构导向剂，与七元瓜环(Q[7])和过渡金属离子Cu2+和Cd2+在水热条件下反应，成功制备出了2例同构的新型七元瓜环基超分子自组装体：[M(H2O)4(Q[7])](NDS)·xH2O(1：M=Cd，x=14；2：M=Cu，x=15)，并采用单晶X射线衍射、粉末X射线衍射、红外光谱、热重分析和Hirshfeld表面分析等手段对其进行了测试和表征。结果表明，2种自组装体晶体中，Q[7]均是直接与过渡金属离子配位，形成了1∶1型简单配合物Q[7]-M2+，而磺酸配体则是完全去质子化，以阴离子形式NDS2-来保持体系电荷平衡并分布在Q[7]环外侧；二者通过Q[7]外壁上的次甲基和亚甲基与NDS2-的磺酸根之间的C—H…O氢键、萘环之间的C—H…π作用形成双链型一维超分子链，并进一步通过Q[7]分子间的氢键作用形成了最终的三维超分子框架结构。Hirshfeld表面分析进一步证明了自组装体晶体中含有丰富的弱相互作用，其中氢键作用对于最终三维超分子框架结构的形成起到了主要贡献。此外，荧光测试结果还表明，自组装体1可以通过荧光猝灭的方式选择性检测水体系中的Cu2+。
2026, 42(8): 1647-1657
doi: 10.11862/CJIC.20260041
摘要:
针对O3型Na0.86Ni1/3Fe1/3Mn1/3O2正极材料在充放电过程中易发生有害相变等问题，采用Ti4+/P5+双位点协同掺杂策略，旨在提升其结构稳定性。通过溶胶-凝胶法协同高温固相法，合成了Na0.82Ni1/3Fe1/3Mn1/3Ti0.02P0.01O2(NFMTP)材料。电化学测试表明，NFMTP正极在1C(160 mA·g-1)倍率下循环200次后，容量保持率高达80.1%，高于原始NFM(45.4%)。在10C高倍率下，NFMTP仍能提供111.6 mAh·g-1的可逆容量。机理研究表明，Ti占据Na位点以及P占据过渡金属(TM)层四面体间隙位点的协同作用，有效强化了TM—O键，抑制了有害相变，加速了Na+扩散，共同提升了材料的综合电化学性能。
针对O3型Na0.86Ni1/3Fe1/3Mn1/3O2正极材料在充放电过程中易发生有害相变等问题，采用Ti4+/P5+双位点协同掺杂策略，旨在提升其结构稳定性。通过溶胶-凝胶法协同高温固相法，合成了Na0.82Ni1/3Fe1/3Mn1/3Ti0.02P0.01O2(NFMTP)材料。电化学测试表明，NFMTP正极在1C(160 mA·g-1)倍率下循环200次后，容量保持率高达80.1%，高于原始NFM(45.4%)。在10C高倍率下，NFMTP仍能提供111.6 mAh·g-1的可逆容量。机理研究表明，Ti占据Na位点以及P占据过渡金属(TM)层四面体间隙位点的协同作用，有效强化了TM—O键，抑制了有害相变，加速了Na+扩散，共同提升了材料的综合电化学性能。
2026, 42(8): 1658-1668
doi: 10.11862/CJIC.20260009
摘要:
基于第一性原理，系统研究了系列钒酸盐晶体K3RE(VO4)2(RE=Sc、Y、La、Lu)的电子结构与光学性质。计算结果表明，该系列化合物均属于三方晶系，空间群为P3m1，具有彼此不共顶点的[VO4]四面体和[REO6]八面体构成的层状结构。能带计算表明该类材料均为间接带隙，带隙分布在3.286~3.701 eV之间。结合态密度中不同轨道分布与Mulliken布居和电子局域函数(ELF)分析可知，体系内部存在强共价的[VO4]3-基团与弱共价的离子性K/RE骨架。在光学性质方面，K3Sc(VO4)2、K3Y(VO4)2和K3La(VO4)2的双折射率(Δn)受阳离子尺寸效应调控，随离子半径增大而减小。然而，K3Lu(VO4)2因Lu3+特有的镧系收缩效应打破了这一常规尺寸演化趋势。镧系收缩效应通过优化晶格空间占位，调控基团畸变与空间取向的平衡，实现了“适度的低畸变+高一致性排列”的相干叠加，从而使其在1 064 nm处表现出异常高且不寻常的巨大、宏观的双折射率(Δn=0.250)。定量关联分析与相对电子密度各向异性(REDA)理论进一步证实，Δn与[VO4]3-阴离子簇的几何畸变度(Δd)及其REDA之间存在极强的线性相关，明确了[VO4]四面体是光学各向异性的绝对主导来源。
基于第一性原理，系统研究了系列钒酸盐晶体K3RE(VO4)2(RE=Sc、Y、La、Lu)的电子结构与光学性质。计算结果表明，该系列化合物均属于三方晶系，空间群为P3m1，具有彼此不共顶点的[VO4]四面体和[REO6]八面体构成的层状结构。能带计算表明该类材料均为间接带隙，带隙分布在3.286~3.701 eV之间。结合态密度中不同轨道分布与Mulliken布居和电子局域函数(ELF)分析可知，体系内部存在强共价的[VO4]3-基团与弱共价的离子性K/RE骨架。在光学性质方面，K3Sc(VO4)2、K3Y(VO4)2和K3La(VO4)2的双折射率(Δn)受阳离子尺寸效应调控，随离子半径增大而减小。然而，K3Lu(VO4)2因Lu3+特有的镧系收缩效应打破了这一常规尺寸演化趋势。镧系收缩效应通过优化晶格空间占位，调控基团畸变与空间取向的平衡，实现了“适度的低畸变+高一致性排列”的相干叠加，从而使其在1 064 nm处表现出异常高且不寻常的巨大、宏观的双折射率(Δn=0.250)。定量关联分析与相对电子密度各向异性(REDA)理论进一步证实，Δn与[VO4]3-阴离子簇的几何畸变度(Δd)及其REDA之间存在极强的线性相关，明确了[VO4]四面体是光学各向异性的绝对主导来源。
2026, 42(8): 1669-1684
doi: 10.11862/CJIC.20260002
摘要:
利用微胶囊化技术以海藻酸钠(SA)为包材将纳米氢氧化镧(n-LH)制成SA/n-LH复合微球，并探究了接收距离、针头内径、电压、进样速度、SA质量浓度、LaCl3质量浓度、交联时间及n-LH与SA的质量比(rm)等电喷雾法工艺参数对SA/n-LH微球粒径及形貌的影响，进一步探讨了SA/n-LH微球的磷吸附容量及相关机制。结果表明，随着针头内径的增大、电压的减小、SA质量浓度的增大或rm的增大，SA/n-LH复合微球的粒径增大。但当电压为15 kV时微球粒径不均一，SA质量浓度与n-LH含量过大则会轻微影响微球形貌。当初始磷溶液的pH为2.0时SA/n-LH微球的磷吸附容量达到最大值，并且随着pH的增加磷吸附容量显著降低，随着rm的增大磷吸附容量显著增大，其中pH为2.0、rm为2.0时磷吸附容量为111.05 mg·g-1。SA/n-LH微球的磷吸附过程更符合准二级动力学模型和Langmuir等温吸附模型，其磷吸附速率明显慢于n-LH，表明具有缓释效果。
利用微胶囊化技术以海藻酸钠(SA)为包材将纳米氢氧化镧(n-LH)制成SA/n-LH复合微球，并探究了接收距离、针头内径、电压、进样速度、SA质量浓度、LaCl3质量浓度、交联时间及n-LH与SA的质量比(rm)等电喷雾法工艺参数对SA/n-LH微球粒径及形貌的影响，进一步探讨了SA/n-LH微球的磷吸附容量及相关机制。结果表明，随着针头内径的增大、电压的减小、SA质量浓度的增大或rm的增大，SA/n-LH复合微球的粒径增大。但当电压为15 kV时微球粒径不均一，SA质量浓度与n-LH含量过大则会轻微影响微球形貌。当初始磷溶液的pH为2.0时SA/n-LH微球的磷吸附容量达到最大值，并且随着pH的增加磷吸附容量显著降低，随着rm的增大磷吸附容量显著增大，其中pH为2.0、rm为2.0时磷吸附容量为111.05 mg·g-1。SA/n-LH微球的磷吸附过程更符合准二级动力学模型和Langmuir等温吸附模型，其磷吸附速率明显慢于n-LH，表明具有缓释效果。
2026, 42(8): 1685-1698
doi: 10.11862/CJIC.20250343
摘要:
提出了一种基于成分特征的级联机器学习策略，用于同步预测Eu2+掺杂白磷钙矿型荧光粉的发射半高宽(FWHM)与热稳定性(TS)。通过比较决策树回归(DTR)、梯度提升回归树(GBR)、装袋法(Bagging)、随机森林回归(RFR)、极限梯度提升法(XGBoosting)和自适应提升法(AdaBoosting)六种模型算法，发现AdaBoosting模型在级联预测中表现最优，其预测FWHM和TS的测试集决定系数(R2)分别达到0.951和0.852。为验证模型可靠性，我们成功合成了Ca9Y(PO4)7∶0.08Eu2+荧光粉，发现其FWHM与TS的预测值与实验值高度吻合，误差分别仅为2.57%和1.19%。结构精修与高斯拟合表明该荧光粉中Eu2+占据4个不同格位，共同贡献于青色发射；能级分析进一步揭示其TS主要受限于Eu2+的5d能级与导带底之间较小的能隙所导致的自电离效应。最后，基于该青色荧光粉封装的白光LED器件展现了优异的性能(显色指数Ra=92.6，相关色温CCT=4 266 K)，证明了其实际应用潜力。
提出了一种基于成分特征的级联机器学习策略，用于同步预测Eu2+掺杂白磷钙矿型荧光粉的发射半高宽(FWHM)与热稳定性(TS)。通过比较决策树回归(DTR)、梯度提升回归树(GBR)、装袋法(Bagging)、随机森林回归(RFR)、极限梯度提升法(XGBoosting)和自适应提升法(AdaBoosting)六种模型算法，发现AdaBoosting模型在级联预测中表现最优，其预测FWHM和TS的测试集决定系数(R2)分别达到0.951和0.852。为验证模型可靠性，我们成功合成了Ca9Y(PO4)7∶0.08Eu2+荧光粉，发现其FWHM与TS的预测值与实验值高度吻合，误差分别仅为2.57%和1.19%。结构精修与高斯拟合表明该荧光粉中Eu2+占据4个不同格位，共同贡献于青色发射；能级分析进一步揭示其TS主要受限于Eu2+的5d能级与导带底之间较小的能隙所导致的自电离效应。最后，基于该青色荧光粉封装的白光LED器件展现了优异的性能(显色指数Ra=92.6，相关色温CCT=4 266 K)，证明了其实际应用潜力。
2026, 42(8): 1699-1711
doi: 10.11862/CJIC.20250284
摘要:
设计并构建了一种基于ZnO与Bi4NbO8Cl(BNC)的Ⅱ型异质结复合催化剂(ZnO/BNC)，旨在通过异质结界面工程有效促进载流子分离，提升催化活性。采用优化的浸渍煅烧法成功制备了ZnO/BNC，并利用多种表征手段系统研究了其晶体结构、能带结构和压电性能。结果表明，ZnO与BNC间形成的Ⅱ型能带排列以及界面处自发产生的内建电场协同作用，显著促进了压电激发下电子-空穴对的分离与迁移。在超声驱动下，优化样品ZnO/BNC-2在90 min内对甲基橙(MO)的降解率达到87%，其压电催化降解反应速率常数约为纯BNC的7.3倍、纯ZnO的5.4倍，展现出了优异的压电催化性能。
设计并构建了一种基于ZnO与Bi4NbO8Cl(BNC)的Ⅱ型异质结复合催化剂(ZnO/BNC)，旨在通过异质结界面工程有效促进载流子分离，提升催化活性。采用优化的浸渍煅烧法成功制备了ZnO/BNC，并利用多种表征手段系统研究了其晶体结构、能带结构和压电性能。结果表明，ZnO与BNC间形成的Ⅱ型能带排列以及界面处自发产生的内建电场协同作用，显著促进了压电激发下电子-空穴对的分离与迁移。在超声驱动下，优化样品ZnO/BNC-2在90 min内对甲基橙(MO)的降解率达到87%，其压电催化降解反应速率常数约为纯BNC的7.3倍、纯ZnO的5.4倍，展现出了优异的压电催化性能。
2026, 42(8): 1712-1722
doi: 10.11862/CJIC.20260136
摘要:
Three new 3-pyridazinyl-substituted triaryltriazoles, 4-(4-R-phenyl)-3-(2-pyridyl)-5-(3-pyridazinyl)-1,2,4-triazole (L1: R=OCH3; L2: R=H; L3: R=F) and their Cu(Ⅱ) complexes, trans-[Cu(L1)2(NO3)2]·H2O (1), trans-[Cu(L2)2(NO3)2] (2) and trans-[Cu(L3)2(H2O)2](NO3)2 (3), have been synthesized and characterized by FTIR, 1H NMR, elemental analysis and single crystal X-ray crystallography. Crystal structure analyses reveal that the supramolecular trimer (L1)3 and complex 3 crystallize in the triclinic P1 space group, the ligand L2 and complexes 1 and 2 belong to the monoclinic P21/c space group, while the ligand L3 crystallizes in the monoclinic P21/n space group. There is a hydrogen-bonded trimer (L1)3 in the asymmetric unit of the ligand L1. In the complexes 1-3, there is a distorted [CuN4O2] octahedron with two NO3- ions located in the axial positions in 1 and 2, whereas the two water molecules occupy the axial sites in 3. In the equatorial plane of 1-3, each L ligand adopts a chelating bidentate mode to bind the Cu(Ⅱ) ion through the pyridyl N atom and one triazole N atom, leaving the pyridazinyl group uncoordinated. The intermolecular interactions in the free ligands and the complexes have been explored by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main intermolecular interactions are H…H and C…H/H…C contacts in (L1)3, H…H and N…H/H…N contacts in L2, H…H, N…H/H…N and C…H/H…C in L3, H…H and O…H/H…O contacts in both 1 and 2, H…H, N…H/H…N and O…H/H…O contacts in 3.
Three new 3-pyridazinyl-substituted triaryltriazoles, 4-(4-R-phenyl)-3-(2-pyridyl)-5-(3-pyridazinyl)-1,2,4-triazole (L1: R=OCH3; L2: R=H; L3: R=F) and their Cu(Ⅱ) complexes, trans-[Cu(L1)2(NO3)2]·H2O (1), trans-[Cu(L2)2(NO3)2] (2) and trans-[Cu(L3)2(H2O)2](NO3)2 (3), have been synthesized and characterized by FTIR, 1H NMR, elemental analysis and single crystal X-ray crystallography. Crystal structure analyses reveal that the supramolecular trimer (L1)3 and complex 3 crystallize in the triclinic P1 space group, the ligand L2 and complexes 1 and 2 belong to the monoclinic P21/c space group, while the ligand L3 crystallizes in the monoclinic P21/n space group. There is a hydrogen-bonded trimer (L1)3 in the asymmetric unit of the ligand L1. In the complexes 1-3, there is a distorted [CuN4O2] octahedron with two NO3- ions located in the axial positions in 1 and 2, whereas the two water molecules occupy the axial sites in 3. In the equatorial plane of 1-3, each L ligand adopts a chelating bidentate mode to bind the Cu(Ⅱ) ion through the pyridyl N atom and one triazole N atom, leaving the pyridazinyl group uncoordinated. The intermolecular interactions in the free ligands and the complexes have been explored by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main intermolecular interactions are H…H and C…H/H…C contacts in (L1)3, H…H and N…H/H…N contacts in L2, H…H, N…H/H…N and C…H/H…C in L3, H…H and O…H/H…O contacts in both 1 and 2, H…H, N…H/H…N and O…H/H…O contacts in 3.
2026, 42(8): 1723-1732
doi: 10.11862/CJIC.20260103
摘要:
A heterometallic Mn/Ti cluster formulated as [Ti3Mn2(Sal)8(Phen)(CH3CN)(H2O)] (1) was solvothermally synthesized via the reaction of manganese acetate with a titanate precursor, using salicylic acid (H2Sal) and 1, 10-phenanthroline (Phen) as organic ligands. By carefully tuning the reaction parameters and eliminating Phen from the reaction system, a structurally distinct heterometallic Mn/Ti cluster, [Ti4Mn4(Sal)12(CH3CN)2]·(CH3CN)4 (2), was further isolated. The molecular structures of both complexes 1 and 2 were unambiguously established by elemental analysis, Fourier-transform infrared (FTIR) spectra, and single-crystal X-ray diffraction. Spectroscopic measurements demonstrated that both complexes feature prominent light absorption in the visible region, with the calculated optical band gaps of 1.93 eV for complex 1 and 2.15 eV for complex 2, respectively. Photocatalytic investigations revealed that complexes 1 and 2 exhibited efficient catalytic activity toward CO2 reduction, affording CO as the exclusive carbon-containing product, with corresponding CO evolution rates of 7.21 and 14.39 μmol·g-1·h-1, respectively.
A heterometallic Mn/Ti cluster formulated as [Ti3Mn2(Sal)8(Phen)(CH3CN)(H2O)] (1) was solvothermally synthesized via the reaction of manganese acetate with a titanate precursor, using salicylic acid (H2Sal) and 1, 10-phenanthroline (Phen) as organic ligands. By carefully tuning the reaction parameters and eliminating Phen from the reaction system, a structurally distinct heterometallic Mn/Ti cluster, [Ti4Mn4(Sal)12(CH3CN)2]·(CH3CN)4 (2), was further isolated. The molecular structures of both complexes 1 and 2 were unambiguously established by elemental analysis, Fourier-transform infrared (FTIR) spectra, and single-crystal X-ray diffraction. Spectroscopic measurements demonstrated that both complexes feature prominent light absorption in the visible region, with the calculated optical band gaps of 1.93 eV for complex 1 and 2.15 eV for complex 2, respectively. Photocatalytic investigations revealed that complexes 1 and 2 exhibited efficient catalytic activity toward CO2 reduction, affording CO as the exclusive carbon-containing product, with corresponding CO evolution rates of 7.21 and 14.39 μmol·g-1·h-1, respectively.
2026, 42(8): 1733-1750
doi: 10.11862/CJIC.20260055
摘要:
Aiming at the problem of water pollution, a broad-spectrum response composite material CQDs/PW12/CdS modified by carbon quantum dots (CQDs) was prepared via a microwave-assisted hydrothermal method using glucose as the carbon source, cadmium sulfide (CdS) and phosphotungstic acid (PW12) as precursors. The photocatalytic mechanism of CQDs/PW12/CdS is more inclined towards the Z-scheme heterojunction. The optimized CQDs/PW12/CdS heterojunction composites achieved 93.01% photodegradation efficiency of rhodamine B (RhB) at 120 min of simulated sunlight irradiation, and they also exhibited a favorable degrading effect on common dyes and antibiotics in water. Using lactic acid as the sacrificial reagent, the photocatalytic hydrogen production activity of the developed photocatalyst was evaluated under simulated sunlight irradiation. According to the experimental results, after 8 h of irradiation, the CQDs/PW12/CdS composite material showed the highest H2 production rate (12.34 mmol·g-1), which was six times that of the monomer CdS (2.05 mmol·g-1). The enhancement of photocatalytic activity is attributed to the effective separation of photogenerated charges caused by the anisotropic junctions in the CQDs/PW12/CdS system.
Aiming at the problem of water pollution, a broad-spectrum response composite material CQDs/PW12/CdS modified by carbon quantum dots (CQDs) was prepared via a microwave-assisted hydrothermal method using glucose as the carbon source, cadmium sulfide (CdS) and phosphotungstic acid (PW12) as precursors. The photocatalytic mechanism of CQDs/PW12/CdS is more inclined towards the Z-scheme heterojunction. The optimized CQDs/PW12/CdS heterojunction composites achieved 93.01% photodegradation efficiency of rhodamine B (RhB) at 120 min of simulated sunlight irradiation, and they also exhibited a favorable degrading effect on common dyes and antibiotics in water. Using lactic acid as the sacrificial reagent, the photocatalytic hydrogen production activity of the developed photocatalyst was evaluated under simulated sunlight irradiation. According to the experimental results, after 8 h of irradiation, the CQDs/PW12/CdS composite material showed the highest H2 production rate (12.34 mmol·g-1), which was six times that of the monomer CdS (2.05 mmol·g-1). The enhancement of photocatalytic activity is attributed to the effective separation of photogenerated charges caused by the anisotropic junctions in the CQDs/PW12/CdS system.
2026, 42(8): 1751-1762
doi: 10.11862/CJIC.20260039
摘要:
A new cadmium-based coordination polymer (CP) with 1D structure, [Cd(4-DTBPT)(DMF)2(H2O)2](C10H4O8)·4-DTBPT·3H2O (Cd-CP), where 4-DTBPT=2,7-di(4H-1,2,4-triazol-4yl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H, 7H)-tetraone, DMF=N,N-dimethylformamide, C10H4O82-=2,5-dicarboxyterephthalate, which originates from the decomposition of N,N′-bis(glycinyl)pyromellitic diimide (BGPD), was firstly synthesized via the interaction of 4-DTBPT, BGPD, and Cd(NO3)2·4H2O, and characterized by IR spectrum, thermogravimetric analysis and single-crystal X-ray diffraction. In Cd-CP, 4-DTBPT ligands linked adjacent Cd(Ⅱ) ions to produce a 1D chain structure. The C10H4O82- anion and the free 4-DTBPT ligands are respectively embedded between 1D chains through electrostatic force and hydrogen bonds, forming a 3D network structure. When Cd-CP was employed as the cathode material of lithium-ion batteries (LIBs), it delivered the first discharge specific capacity of 78.3 mAh·g-1 at 0.05 A·g-1 along with the Coulombic efficiency of close to 100%, and a higher cycle stability with the capacity retention of 85.7% after 100 cycles.
A new cadmium-based coordination polymer (CP) with 1D structure, [Cd(4-DTBPT)(DMF)2(H2O)2](C10H4O8)·4-DTBPT·3H2O (Cd-CP), where 4-DTBPT=2,7-di(4H-1,2,4-triazol-4yl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H, 7H)-tetraone, DMF=N,N-dimethylformamide, C10H4O82-=2,5-dicarboxyterephthalate, which originates from the decomposition of N,N′-bis(glycinyl)pyromellitic diimide (BGPD), was firstly synthesized via the interaction of 4-DTBPT, BGPD, and Cd(NO3)2·4H2O, and characterized by IR spectrum, thermogravimetric analysis and single-crystal X-ray diffraction. In Cd-CP, 4-DTBPT ligands linked adjacent Cd(Ⅱ) ions to produce a 1D chain structure. The C10H4O82- anion and the free 4-DTBPT ligands are respectively embedded between 1D chains through electrostatic force and hydrogen bonds, forming a 3D network structure. When Cd-CP was employed as the cathode material of lithium-ion batteries (LIBs), it delivered the first discharge specific capacity of 78.3 mAh·g-1 at 0.05 A·g-1 along with the Coulombic efficiency of close to 100%, and a higher cycle stability with the capacity retention of 85.7% after 100 cycles.
2026, 42(8): 1763-1778
doi: 10.11862/CJIC.20250359
摘要:
Two novel Cd-based metal-organic frameworks (Cd-MOFs), {[Cd2(DCODBC)(phen)2]·3H2O}n (1) and {[Cd5(DCOTBC)5(H2O)8]·2H2O}n (2), were synthesized by solvothermal method, where H4DCODBC=4,4′-oxydibenzene-1,2-dicarboxylic acid, phen=1,10-phenanthroline, and H5DCOTBC=4-[(3,4-dicarboxyphenyl)oxy]benzene-1,2,3-tricarboxylic acid. The structures of compounds 1 and 2 were determined using single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. 1 is a 2D planar structure, and 2 is a 3D grid structure. The DCODBC4- ligand adopts the μ6-к2∶к2∶к2∶к2∶к1∶к1 mode in 1 and the DCOTBC5- ligand adopts the μ9-к2∶к2∶к1∶к1∶к1∶к1∶к1∶к1∶к1 mode in 2. To evaluate their optical performance, the photoluminescent properties of 1 and 2 were analyzed. 1 responded well to nitrobenzene [NB, detection limit (LOD)=0.043 8 μmol·L-1], while 2 responded well to 2,4,6-trinitrophenol (TNP, LOD=0.257 μmol·L-1). Interestingly, 1 and 2 responded well to tetracycline (TC) and fluazinam (FLU); the LODs were all in the μmol·L-1 range. The fluorescence quenching mechanisms of 1 and 2 were discussed. To further evaluate the detection capability of 1 and 2 for FLU in real samples, we conducted a spike recovery experiment using apple peels as the matrix. The recovery rate for 1 ranged from 98.78% to 99.75%, and that for 2 ranged from 98.76% to 99.27%.
Two novel Cd-based metal-organic frameworks (Cd-MOFs), {[Cd2(DCODBC)(phen)2]·3H2O}n (1) and {[Cd5(DCOTBC)5(H2O)8]·2H2O}n (2), were synthesized by solvothermal method, where H4DCODBC=4,4′-oxydibenzene-1,2-dicarboxylic acid, phen=1,10-phenanthroline, and H5DCOTBC=4-[(3,4-dicarboxyphenyl)oxy]benzene-1,2,3-tricarboxylic acid. The structures of compounds 1 and 2 were determined using single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. 1 is a 2D planar structure, and 2 is a 3D grid structure. The DCODBC4- ligand adopts the μ6-к2∶к2∶к2∶к2∶к1∶к1 mode in 1 and the DCOTBC5- ligand adopts the μ9-к2∶к2∶к1∶к1∶к1∶к1∶к1∶к1∶к1 mode in 2. To evaluate their optical performance, the photoluminescent properties of 1 and 2 were analyzed. 1 responded well to nitrobenzene [NB, detection limit (LOD)=0.043 8 μmol·L-1], while 2 responded well to 2,4,6-trinitrophenol (TNP, LOD=0.257 μmol·L-1). Interestingly, 1 and 2 responded well to tetracycline (TC) and fluazinam (FLU); the LODs were all in the μmol·L-1 range. The fluorescence quenching mechanisms of 1 and 2 were discussed. To further evaluate the detection capability of 1 and 2 for FLU in real samples, we conducted a spike recovery experiment using apple peels as the matrix. The recovery rate for 1 ranged from 98.78% to 99.75%, and that for 2 ranged from 98.76% to 99.27%.
2026, 42(8): 1779-1791
doi: 10.11862/CJIC.20260142
摘要:
The double perovskite oxide La0.6Sr1.4Ni0.4Co1.6O6 (LSNC) was synthesized using a simple sol-gel method, followed by physical mixing with S/N co-doped graphene (S/NG) to prepare LSNC@S/NG, thereby achieving excellent electrical conductivity and abundant active sites. When the mass fraction of S/NG was 15%, LSNC@S/NG-15% exhibited the largest specific surface area (11 m2·g-1) and electrochemical double-layer capacitance (71.14 mF·cm-2), which were significantly superior to those of the pristine perovskite. In linear sweep voltammetry (LSV) tests, this optimized composite demonstrated the best electrocatalytic activity for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), achieving high anodic and cathodic current densities of 356.0 mA·cm-2 (termination potential: 1.97 V) and 300.4 mA·cm-2 (termination potential: 0.37 V), respectively. This remarkable enhancement in performance is attributed to the strong synergistic effect between the catalytically active LSNC particles and the highly conductive, defect-rich S/NG support, which facilitates rapid charge transfer and provides a larger density of accessible active sites.
The double perovskite oxide La0.6Sr1.4Ni0.4Co1.6O6 (LSNC) was synthesized using a simple sol-gel method, followed by physical mixing with S/N co-doped graphene (S/NG) to prepare LSNC@S/NG, thereby achieving excellent electrical conductivity and abundant active sites. When the mass fraction of S/NG was 15%, LSNC@S/NG-15% exhibited the largest specific surface area (11 m2·g-1) and electrochemical double-layer capacitance (71.14 mF·cm-2), which were significantly superior to those of the pristine perovskite. In linear sweep voltammetry (LSV) tests, this optimized composite demonstrated the best electrocatalytic activity for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), achieving high anodic and cathodic current densities of 356.0 mA·cm-2 (termination potential: 1.97 V) and 300.4 mA·cm-2 (termination potential: 0.37 V), respectively. This remarkable enhancement in performance is attributed to the strong synergistic effect between the catalytically active LSNC particles and the highly conductive, defect-rich S/NG support, which facilitates rapid charge transfer and provides a larger density of accessible active sites.
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.
