Login In
Browse Articles
Display Method:
Display Method: |
2026, 42(8): 1569-1581
doi: 10.11862/CJIC.20260062
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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.
