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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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2025, 41(9): 1689-1701
doi: 10.11862/CJIC.20250007
摘要:
含氟钙钛矿及其衍生物因其优异的物理和化学性质在新能源、光电器件、催化及磁性材料等领域获得了广泛关注。这类材料的合成方法是该研究领域的核心之一。合成路径的选择和优化直接影响材料的结构、性能、形貌以及在实际应用中的表现。目前, 含氟钙钛矿及其衍生物的合成方法主要包括传统的固相合成法、沉淀法、水热/溶剂热法、以及新兴的软化学合成法、沉积法等, 然而这些合成方法还没有系统的概述。因此, 本文综述了该系列化合物的合成方法, 总结了目前面临的挑战并对未来发展方向进行了展望, 期望以此推动该领域更深入、广泛的研究。
含氟钙钛矿及其衍生物因其优异的物理和化学性质在新能源、光电器件、催化及磁性材料等领域获得了广泛关注。这类材料的合成方法是该研究领域的核心之一。合成路径的选择和优化直接影响材料的结构、性能、形貌以及在实际应用中的表现。目前, 含氟钙钛矿及其衍生物的合成方法主要包括传统的固相合成法、沉淀法、水热/溶剂热法、以及新兴的软化学合成法、沉积法等, 然而这些合成方法还没有系统的概述。因此, 本文综述了该系列化合物的合成方法, 总结了目前面临的挑战并对未来发展方向进行了展望, 期望以此推动该领域更深入、广泛的研究。
2025, 41(9): 1719-1730
doi: 10.11862/CJIC.20250124
摘要:
固体氧化物电池(SOCs)作为高效、清洁的能源转换装置, 能够实现化学能和电能的高效可逆转化, 在分布式发电、工业余热利用及低碳能源系统中展现出战略价值。然而, 传统电极材料中电催化活性与稳定性的相互制约、高温下的元素偏析与界面退化等问题, 严重限制了电池效率与使用寿命。近年来, 高熵工程通过高构型熵诱导的高熵效应、晶格畸变效应、迟滞扩散效应及鸡尾酒效应, 为突破电极材料性能瓶颈提供了新途径。本文综述了近年来报道的高熵SOC电极, 进一步阐述了高熵材料四大效应对SOC电极反应的催化活性、离子/电子传导能力及长期运行的结构稳定性的影响机制。基于此, 本文指出通过多主元设计实现界面反应动力学以及热-机械稳定性的协同提升是高熵SOC电极设计的关键。本文系统总结了高熵电极材料在提升SOC关键性能方面的研究进展, 突出了其在增强电极活性、抗毒化能力及热稳定性方面的潜力, 并就未来研究所面临的核心挑战与发展机遇进行了探讨。
固体氧化物电池(SOCs)作为高效、清洁的能源转换装置, 能够实现化学能和电能的高效可逆转化, 在分布式发电、工业余热利用及低碳能源系统中展现出战略价值。然而, 传统电极材料中电催化活性与稳定性的相互制约、高温下的元素偏析与界面退化等问题, 严重限制了电池效率与使用寿命。近年来, 高熵工程通过高构型熵诱导的高熵效应、晶格畸变效应、迟滞扩散效应及鸡尾酒效应, 为突破电极材料性能瓶颈提供了新途径。本文综述了近年来报道的高熵SOC电极, 进一步阐述了高熵材料四大效应对SOC电极反应的催化活性、离子/电子传导能力及长期运行的结构稳定性的影响机制。基于此, 本文指出通过多主元设计实现界面反应动力学以及热-机械稳定性的协同提升是高熵SOC电极设计的关键。本文系统总结了高熵电极材料在提升SOC关键性能方面的研究进展, 突出了其在增强电极活性、抗毒化能力及热稳定性方面的潜力, 并就未来研究所面临的核心挑战与发展机遇进行了探讨。
2025, 41(9): 1731-1754
doi: 10.11862/CJIC.20240412
摘要:
激光技术是近年来一种应用广泛的合成技术, 具有一定的可控性、低接触性和低污染性, 其操作简单高效, 能够减少材料浪费和能源消耗, 降低对环境的影响。利用激光合成技术制备出的具有多孔结构的电化学功能材料在储能领域, 如光电催化、电池、超级电容器等方面, 有着良好的应用前景。激光合成技术的应用, 能够实现资源的高效利用和环境的可持续发展。本文综述了激光合成技术的原理及其在储能及生物传感方面的应用, 对激光的机遇与挑战进行了讨论。随着激光合成材料研究的持续深入, 其在能量存储领域的应用技术正迎来加速发展。
激光技术是近年来一种应用广泛的合成技术, 具有一定的可控性、低接触性和低污染性, 其操作简单高效, 能够减少材料浪费和能源消耗, 降低对环境的影响。利用激光合成技术制备出的具有多孔结构的电化学功能材料在储能领域, 如光电催化、电池、超级电容器等方面, 有着良好的应用前景。激光合成技术的应用, 能够实现资源的高效利用和环境的可持续发展。本文综述了激光合成技术的原理及其在储能及生物传感方面的应用, 对激光的机遇与挑战进行了讨论。随着激光合成材料研究的持续深入, 其在能量存储领域的应用技术正迎来加速发展。
2025, 41(9): 1702-1718
doi: 10.11862/CJIC.20240387
摘要:
Malignant tumours always threaten human health. For tumour diagnosis, positron emission tomography (PET) is the most sensitive and advanced imaging technique by radiotracers, such as radioactive 18F, 11C, 64Cu, 68Ga, and 89Zr. Among the radiotracers, the radioactive 18F-labelled chemical agent as PET probes plays a predominant role in monitoring, detecting, treating, and predicting tumours due to its perfect half-life. In this paper, the 18F-labelled chemical materials as PET probes are systematically summarized. First, we introduce various radionuclides of PET and elaborate on the mechanism of PET imaging. It highlights the 18F-labelled chemical agents used as PET probes, including [18F]-2-deoxy-2-[18F]fluoro-D-glucose ([18F]-FDG), 18F-labelled amino acids, 18F-labelled nucleic acids, 18F-labelled receptors, 18F-labelled reporter genes, and 18F-labelled hypoxia agents. In addition, some PET probes with metal as a supplementary element are introduced briefly. Meanwhile, the 18F-labelled nanoparticles for the PET probe and the multi-modality imaging probe are summarized in detail. The approach and strategies for the fabrication of 18F-labelled PET probes are also described briefly. The future development of the PET probe is also prospected. The development and application of 18F-labelled PET probes will expand our knowledge and shed light on the diagnosis and theranostics of tumours.
Malignant tumours always threaten human health. For tumour diagnosis, positron emission tomography (PET) is the most sensitive and advanced imaging technique by radiotracers, such as radioactive 18F, 11C, 64Cu, 68Ga, and 89Zr. Among the radiotracers, the radioactive 18F-labelled chemical agent as PET probes plays a predominant role in monitoring, detecting, treating, and predicting tumours due to its perfect half-life. In this paper, the 18F-labelled chemical materials as PET probes are systematically summarized. First, we introduce various radionuclides of PET and elaborate on the mechanism of PET imaging. It highlights the 18F-labelled chemical agents used as PET probes, including [18F]-2-deoxy-2-[18F]fluoro-D-glucose ([18F]-FDG), 18F-labelled amino acids, 18F-labelled nucleic acids, 18F-labelled receptors, 18F-labelled reporter genes, and 18F-labelled hypoxia agents. In addition, some PET probes with metal as a supplementary element are introduced briefly. Meanwhile, the 18F-labelled nanoparticles for the PET probe and the multi-modality imaging probe are summarized in detail. The approach and strategies for the fabrication of 18F-labelled PET probes are also described briefly. The future development of the PET probe is also prospected. The development and application of 18F-labelled PET probes will expand our knowledge and shed light on the diagnosis and theranostics of tumours.
2025, 41(9): 1755-1764
doi: 10.11862/CJIC.20250198
摘要:
用金属盐和硫脲前驱体溶液，通过刮涂工艺制备出Cu(In，Ga)S2半导体材料，并研究了Ga与Ga+In的物质的量浓度之比(GGI)对其对应太阳能电池性能的影响规律。结果表明，Cu(In，Ga)S2带隙随着GGI的增加而逐渐提高；较低的GGI能促进晶粒生长，有效提高器件的开路电压(VOC)和填充因子，但过高的GGI会阻碍晶粒生长，不利于器件性能的提升。在GGI=0.25时，Cu(In，Ga)S2的带隙达到1.69 eV，对应器件的光电转换效率达到9.06%，与未Ga合金化的器件相比提升了37.48%。进一步的研究表明Ga合金化有效降低了体相和界面缺陷浓度，改善了异质结界面质量，抑制了载流子复合。
用金属盐和硫脲前驱体溶液，通过刮涂工艺制备出Cu(In，Ga)S2半导体材料，并研究了Ga与Ga+In的物质的量浓度之比(GGI)对其对应太阳能电池性能的影响规律。结果表明，Cu(In，Ga)S2带隙随着GGI的增加而逐渐提高；较低的GGI能促进晶粒生长，有效提高器件的开路电压(VOC)和填充因子，但过高的GGI会阻碍晶粒生长，不利于器件性能的提升。在GGI=0.25时，Cu(In，Ga)S2的带隙达到1.69 eV，对应器件的光电转换效率达到9.06%，与未Ga合金化的器件相比提升了37.48%。进一步的研究表明Ga合金化有效降低了体相和界面缺陷浓度，改善了异质结界面质量，抑制了载流子复合。
2025, 41(9): 1765-1775
doi: 10.11862/CJIC.20250103
摘要:
采用溶剂热法将BiOBr和NH2-MIL-101(Fe)复合制备了BiOBr/NH2-MIL-101(Fe)复合光催化剂，并将其用于光催化还原温室气体CO2。借助傅里叶变换红外光谱、X射线衍射、X射线光电子能谱、扫描电镜-能谱、紫外可见漫反射光谱、光致发光光谱、电化学阻抗谱对光催化剂的结构和性质进行了详细的表征。光催化CO2还原性能研究表明BiOBr/NH2-MIL-101(Fe)的活性明显优于纯BiOBr。当NH2-MIL-101(Fe)与BiOBr的物质的量之比为0.09时制备的复合催化剂活性最高，其在可见光照射下反应6 h后，在纯水体系中的CH3OH产率可达到49.68 μmol·g-1。BiOBr/NH2-MIL-101(Fe)异质结实现了低能载流子的快速消除和高能载流子的有效分离和富集，这使得其光催化还原CO2制备CH3OH的产率是纯BiOBr的2.94倍。该催化剂具有良好的循环使用性，经过5次循环后，产率仍可达到首次的84.9%。
采用溶剂热法将BiOBr和NH2-MIL-101(Fe)复合制备了BiOBr/NH2-MIL-101(Fe)复合光催化剂，并将其用于光催化还原温室气体CO2。借助傅里叶变换红外光谱、X射线衍射、X射线光电子能谱、扫描电镜-能谱、紫外可见漫反射光谱、光致发光光谱、电化学阻抗谱对光催化剂的结构和性质进行了详细的表征。光催化CO2还原性能研究表明BiOBr/NH2-MIL-101(Fe)的活性明显优于纯BiOBr。当NH2-MIL-101(Fe)与BiOBr的物质的量之比为0.09时制备的复合催化剂活性最高，其在可见光照射下反应6 h后，在纯水体系中的CH3OH产率可达到49.68 μmol·g-1。BiOBr/NH2-MIL-101(Fe)异质结实现了低能载流子的快速消除和高能载流子的有效分离和富集，这使得其光催化还原CO2制备CH3OH的产率是纯BiOBr的2.94倍。该催化剂具有良好的循环使用性，经过5次循环后，产率仍可达到首次的84.9%。
2025, 41(9): 1776-1788
doi: 10.11862/CJIC.20250102
摘要:
基于第一性原理方法，通过在石墨烯中掺杂不同类型的氮(吡啶氮、吡咯氮、石墨氮)和负载铁单原子构建了Fe-N-C结构，并通过改变吡啶氮与铁单原子的配位数(x=3~6)，研究了铁单原子、氮原子以及其旁边的碳原子分别作为活性位点时析氧反应(OER)和氧还原反应(ORR)的反应机理。结果表明，氮掺杂和铁单原子负载均有利于提高石墨烯的OER/ORR活性，但在Fe-N-C中石墨氮旁边的碳原子是最佳的OER活性位点，而与吡啶氮形成四配位结构的铁单原子是最佳的ORR活性位点。
基于第一性原理方法，通过在石墨烯中掺杂不同类型的氮(吡啶氮、吡咯氮、石墨氮)和负载铁单原子构建了Fe-N-C结构，并通过改变吡啶氮与铁单原子的配位数(x=3~6)，研究了铁单原子、氮原子以及其旁边的碳原子分别作为活性位点时析氧反应(OER)和氧还原反应(ORR)的反应机理。结果表明，氮掺杂和铁单原子负载均有利于提高石墨烯的OER/ORR活性，但在Fe-N-C中石墨氮旁边的碳原子是最佳的OER活性位点，而与吡啶氮形成四配位结构的铁单原子是最佳的ORR活性位点。
2025, 41(9): 1789-1795
doi: 10.11862/CJIC.20250086
摘要:
通过两步反应制备了一例吡啶鎓-查尔酮探针(1)，并使用1H NMR和质谱表征了探针的结构。在富水溶液中，探针1的自身荧光微弱，而次氯酸根(ClO-)能够显著增强探针1在550 nm处的黄色荧光。探针1对ClO-的响应具有速度快(小于30 s)、灵敏度高(检测限为0.4 μmol·L-1)和斯托克斯位移大(130 nm)等优点。利用质谱和理论计算方法推测了ClO-介导的探针1的氧化-消除反应机理。此外，该探针成功用于活细胞线粒体和斑马鱼中ClO-的荧光成像。
通过两步反应制备了一例吡啶鎓-查尔酮探针(1)，并使用1H NMR和质谱表征了探针的结构。在富水溶液中，探针1的自身荧光微弱，而次氯酸根(ClO-)能够显著增强探针1在550 nm处的黄色荧光。探针1对ClO-的响应具有速度快(小于30 s)、灵敏度高(检测限为0.4 μmol·L-1)和斯托克斯位移大(130 nm)等优点。利用质谱和理论计算方法推测了ClO-介导的探针1的氧化-消除反应机理。此外，该探针成功用于活细胞线粒体和斑马鱼中ClO-的荧光成像。
2025, 41(9): 1796-1804
doi: 10.11862/CJIC.20250033
摘要:
通过溶剂热法合成了具有Z型异质结结构的MOF-74-Mn/g-C3N4光催化剂。在可见光照射下，其对四环素的降解率(60 min)达到95%，分别为MOF-74-Mn和g-C3N4的2.4倍和1.8倍。结果表明，MOF-74-Mn/g-C3N4 Z型异质结可有效地实现光生载流子的空间分离，抑制光生电子-空穴对的复合，加快载流子的传输，从而提升光催化降解性能。
通过溶剂热法合成了具有Z型异质结结构的MOF-74-Mn/g-C3N4光催化剂。在可见光照射下，其对四环素的降解率(60 min)达到95%，分别为MOF-74-Mn和g-C3N4的2.4倍和1.8倍。结果表明，MOF-74-Mn/g-C3N4 Z型异质结可有效地实现光生载流子的空间分离，抑制光生电子-空穴对的复合，加快载流子的传输，从而提升光催化降解性能。
2025, 41(9): 1805-1816
doi: 10.11862/CJIC.20250066
摘要:
通过在TiO2电子传输层上引入甲基氯化胺(MACl)分子，对TiO2/CsPbBr3界面进行修饰，钝化TiO2/CsPbBr3存在的界面缺陷，同时提升CsPbBr3薄膜的结晶度和尺寸，从而提高载流子的传输效率。实验结果表明，采用5.0 mg·mL-1的MACl溶液进行修饰后，器件的最高开路电压(open-circuit voltage，VOC)达到1.58 V，短路电流密度(short circuit current density，JSC)达到7.89 mA·cm-2，同时填充因子(fill factor，FF)达到81.09%，光电转换效率(photoelectric conversion efficiency, PCE)达到10.10%的最优值。
通过在TiO2电子传输层上引入甲基氯化胺(MACl)分子，对TiO2/CsPbBr3界面进行修饰，钝化TiO2/CsPbBr3存在的界面缺陷，同时提升CsPbBr3薄膜的结晶度和尺寸，从而提高载流子的传输效率。实验结果表明，采用5.0 mg·mL-1的MACl溶液进行修饰后，器件的最高开路电压(open-circuit voltage，VOC)达到1.58 V，短路电流密度(short circuit current density，JSC)达到7.89 mA·cm-2，同时填充因子(fill factor，FF)达到81.09%，光电转换效率(photoelectric conversion efficiency, PCE)达到10.10%的最优值。
2025, 41(9): 1817-1826
doi: 10.11862/CJIC.20250058
摘要:
作为乳腺癌细胞的潜在生物标志物，脂肪酶的高灵敏检测有利于提高疾病诊断的准确性。基于脂肪酶的界面催化特性，我们设计合成了一种脂肪酶特异性响应的聚集诱导发光(AIE)荧光探针BTPA，该探针在磷酸盐缓冲溶液中可以发生聚集并与外界溶液形成微小界面，这些界面可快速激活脂肪酶的活性，从而导致BTPA被水解并发出强烈的黄色荧光。在5.0×10-5~4.5×10-4 U·mL-1范围内，BTPA的荧光发射强度与脂肪酶的活性呈线性相关，检出限为4.94×10-6 U·mL-1。此外，探针对脂肪酶的选择性和抗干扰性实验表明探针可用于复杂生物体内的荧光成像。细胞成像实验结果表明，该荧光探针可以精确地原位识别乳腺癌细胞并发出强烈的荧光。
作为乳腺癌细胞的潜在生物标志物，脂肪酶的高灵敏检测有利于提高疾病诊断的准确性。基于脂肪酶的界面催化特性，我们设计合成了一种脂肪酶特异性响应的聚集诱导发光(AIE)荧光探针BTPA，该探针在磷酸盐缓冲溶液中可以发生聚集并与外界溶液形成微小界面，这些界面可快速激活脂肪酶的活性，从而导致BTPA被水解并发出强烈的黄色荧光。在5.0×10-5~4.5×10-4 U·mL-1范围内，BTPA的荧光发射强度与脂肪酶的活性呈线性相关，检出限为4.94×10-6 U·mL-1。此外，探针对脂肪酶的选择性和抗干扰性实验表明探针可用于复杂生物体内的荧光成像。细胞成像实验结果表明，该荧光探针可以精确地原位识别乳腺癌细胞并发出强烈的荧光。
2025, 41(9): 1827-1839
doi: 10.11862/CJIC.20240460
摘要:
采用2种密度泛函方法对C6S6Li6储氢性能进行了理论研究。C6S6Li6动力学稳定，最多可吸附38个H2分子，储氢密度可达20.213%。C6S6Li6(H2)38的平均吸附能接近温和条件下可逆吸附氢气的标准(0.1~0.8 eV)。各种波函数分析表明，C6S6Li6中Li的2s→2p电子跃迁和各带电原子的电场极化共同主导了C6S6Li6对H2的范德瓦耳斯作用。热化学计算表明，在77 K下，压力为0.1、2.5、5.0 MPa时，C6S6Li6分别自发吸附6、32、38个H2分子，并且在298.15 K能够完全释放，可逆储氢密度分别为3.846%、17.582%和20.213%。原子密度矩阵传播动力学模拟表明，C6S6Li6(H2)38中被吸附的H2分子大多可以在室温下脱附，并且母体结构保持稳定，不会坍塌。二聚体(C6S6Li6)2能够吸附53个H2分子，储氢密度为15.014%，也适合在温和条件下可逆储氢。
采用2种密度泛函方法对C6S6Li6储氢性能进行了理论研究。C6S6Li6动力学稳定，最多可吸附38个H2分子，储氢密度可达20.213%。C6S6Li6(H2)38的平均吸附能接近温和条件下可逆吸附氢气的标准(0.1~0.8 eV)。各种波函数分析表明，C6S6Li6中Li的2s→2p电子跃迁和各带电原子的电场极化共同主导了C6S6Li6对H2的范德瓦耳斯作用。热化学计算表明，在77 K下，压力为0.1、2.5、5.0 MPa时，C6S6Li6分别自发吸附6、32、38个H2分子，并且在298.15 K能够完全释放，可逆储氢密度分别为3.846%、17.582%和20.213%。原子密度矩阵传播动力学模拟表明，C6S6Li6(H2)38中被吸附的H2分子大多可以在室温下脱附，并且母体结构保持稳定，不会坍塌。二聚体(C6S6Li6)2能够吸附53个H2分子，储氢密度为15.014%，也适合在温和条件下可逆储氢。
2025, 41(9): 1840-1850
doi: 10.11862/CJIC.20250136
摘要:
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex [Pt(N^C^N′)Cl] with the aryl isocyanide 2,6-dimethylphenyl isocyanide (CNXyl) afforded a mixture of two isomeric species: the ionic complex [Pt(κ3-N^C^N′)(CNXyl)]Cl ([A]Cl) and the molecular complex [Pt(κ2-N^C^N′)(CNXyl)Cl] (B). Isomer B was almost the dominating product. The structures of the isomer B derivatives bearing —CF3 and —Cl substituents on the pyridine ring of the pinene moiety (5B and 7B, respectively) have been confirmed by single-crystal X-ray diffraction, revealing a slightly distorted square planar geometry with trans-NN^C^N′, CNR configuration (The terminal N atom of the κ2-N^C^N′ ligand is trans to the isocyanide ligand CNXyl.). Isomer B is thermodynamically more stable, as confirmed by theoretical calculations.
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex [Pt(N^C^N′)Cl] with the aryl isocyanide 2,6-dimethylphenyl isocyanide (CNXyl) afforded a mixture of two isomeric species: the ionic complex [Pt(κ3-N^C^N′)(CNXyl)]Cl ([A]Cl) and the molecular complex [Pt(κ2-N^C^N′)(CNXyl)Cl] (B). Isomer B was almost the dominating product. The structures of the isomer B derivatives bearing —CF3 and —Cl substituents on the pyridine ring of the pinene moiety (5B and 7B, respectively) have been confirmed by single-crystal X-ray diffraction, revealing a slightly distorted square planar geometry with trans-NN^C^N′, CNR configuration (The terminal N atom of the κ2-N^C^N′ ligand is trans to the isocyanide ligand CNXyl.). Isomer B is thermodynamically more stable, as confirmed by theoretical calculations.
2025, 41(9): 1851-1858
doi: 10.11862/CJIC.20250131
摘要:
To extend a new family of aminophosphine-coordinated [FeFe]-hydrogenase mimics for catalytic hydrogen (H2) evolution, we carried out the ligand substitutions of diiron hexacarbonyl precursors [Fe2(μ-X2pdt)(CO)6] (X2pdt=(SCH2)2CX2, X=Me, H) with aminodiphosphines (Ph2PCH2)2NY(Y=(CH2)2OH, (CH2)3OH) to obtain two new diiron aminophosphine complexes [Fe2(L1)(μ-Me2pdt)(CO)5] (1) and [Fe2(L2)(μ-H2pdt)(CO)5] (2), where L1=3-[(diphenylphosphaneyl)methyl]oxazolidine, L2=3-[(diphenylphosphaneyl)methyl]-1, 3-oxazinane. Moreover, the structures of 1 and 2 have been fully confirmed by elemental analysis, spectroscopic techniques, and single-crystal X-ray diffraction. Using cyclic voltammetry (CV), we investigated the electrochemical redox performance and proton reduction activities of 1 and 2 in acetic acid (HOAc). The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H2 generation in the presence of HOAc.
To extend a new family of aminophosphine-coordinated [FeFe]-hydrogenase mimics for catalytic hydrogen (H2) evolution, we carried out the ligand substitutions of diiron hexacarbonyl precursors [Fe2(μ-X2pdt)(CO)6] (X2pdt=(SCH2)2CX2, X=Me, H) with aminodiphosphines (Ph2PCH2)2NY(Y=(CH2)2OH, (CH2)3OH) to obtain two new diiron aminophosphine complexes [Fe2(L1)(μ-Me2pdt)(CO)5] (1) and [Fe2(L2)(μ-H2pdt)(CO)5] (2), where L1=3-[(diphenylphosphaneyl)methyl]oxazolidine, L2=3-[(diphenylphosphaneyl)methyl]-1, 3-oxazinane. Moreover, the structures of 1 and 2 have been fully confirmed by elemental analysis, spectroscopic techniques, and single-crystal X-ray diffraction. Using cyclic voltammetry (CV), we investigated the electrochemical redox performance and proton reduction activities of 1 and 2 in acetic acid (HOAc). The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H2 generation in the presence of HOAc.
2025, 41(9): 1859-1866
doi: 10.11862/CJIC.20250128
摘要:
Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation, fast response, high spatial resolution, and so on, for which the luminescent thermometers are the key. Here, a 1D complex [Tb4(HTC4A)(TC4A)(OBBA)2(CH3OH)4(μ4-OH)]n (1) was obtained by solvothermal synthesis, where H4TC4A=p-tert-butylthiacalix[4 ]arene, and H2OBBA=4, 4′-oxybisbenzoic acid. This complex is featured with a chain-like polymer constructed by bridging some sandwich-like Tb4-(TC4A)2 entities through OBBA2- ligands. It exhibited the characteristic emission of the Tb3+ ion. Both fluorescence intensity and lifetime decreased with increasing temperature. The relative sensitivity was up to 8.743%·K-1 at 473 K, indicating it is a good ratiometric luminescent thermometer. This complex had good stability under different pH values and in common solvents.
Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation, fast response, high spatial resolution, and so on, for which the luminescent thermometers are the key. Here, a 1D complex [Tb4(HTC4A)(TC4A)(OBBA)2(CH3OH)4(μ4-OH)]n (1) was obtained by solvothermal synthesis, where H4TC4A=p-tert-butylthiacalix[
2025, 41(9): 1867-1877
doi: 10.11862/CJIC.20250100
摘要:
Two Gd2 complexes, namely [Gd2(dbm)2(HL1)2(CH3OH)2]·4CH3OH (1) and [Gd2(dbm)2(L2)2(CH3OH)2]·2CH3OH (2), where H3L1=(Z)-N′-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide, H2L2=(E)-N′- (5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide, Hdbm=dibenzoylmethane, have been constructed by adopting the solvothermal method. Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd3+ ions, two dbm- ions, two CH3OH molecules, and two polydentate Schiff-base ligands (HL12- or L22-). In addition, complex 1 contains four free methanol molecules, whereas complex 2 harbors two free methanol molecules. By investigating the interactions between complexes 1 and 2 and four types of bacteria (Bacillus subtilis, Escherichia coli, Staphylococcus aureus, Candida albicans), it was found that both complexes 1 and 2 exhibited potent antibacterial activities. The interaction mechanisms between the ligands H3L1, H2L2, complexes 1 and 2, and calf thymus DNA (CT-DNA) were studied using ultraviolet-visible spectroscopy, fluorescence titration, and cyclic voltammetry. The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules, thereby inhibiting bacterial proliferation to achieve the antibacterial effects.
Two Gd2 complexes, namely [Gd2(dbm)2(HL1)2(CH3OH)2]·4CH3OH (1) and [Gd2(dbm)2(L2)2(CH3OH)2]·2CH3OH (2), where H3L1=(Z)-N′-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide, H2L2=(E)-N′- (5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide, Hdbm=dibenzoylmethane, have been constructed by adopting the solvothermal method. Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd3+ ions, two dbm- ions, two CH3OH molecules, and two polydentate Schiff-base ligands (HL12- or L22-). In addition, complex 1 contains four free methanol molecules, whereas complex 2 harbors two free methanol molecules. By investigating the interactions between complexes 1 and 2 and four types of bacteria (Bacillus subtilis, Escherichia coli, Staphylococcus aureus, Candida albicans), it was found that both complexes 1 and 2 exhibited potent antibacterial activities. The interaction mechanisms between the ligands H3L1, H2L2, complexes 1 and 2, and calf thymus DNA (CT-DNA) were studied using ultraviolet-visible spectroscopy, fluorescence titration, and cyclic voltammetry. The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules, thereby inhibiting bacterial proliferation to achieve the antibacterial effects.
2025, 41(9): 1878-1888
doi: 10.11862/CJIC.20250079
摘要:
A Co3O4/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selective photocatalytic CO2 reduction. The optimized Co3O4/BiOBr-0.8 catalyst exhibited CO and CH4 evolution rates of 112.2 and 5.5 μmol·g-1·h-1, respectively, representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr. The heterojunction demonstrated broadened light absorption, enhanced photoelectrochemical activity, reduced charge-transfer resistance, and improved separation efficiency of photogenerated carriers (e-/h+). These synergistic effects were attributed to the formation of a Z-scheme heterostructure, which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.
A Co3O4/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selective photocatalytic CO2 reduction. The optimized Co3O4/BiOBr-0.8 catalyst exhibited CO and CH4 evolution rates of 112.2 and 5.5 μmol·g-1·h-1, respectively, representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr. The heterojunction demonstrated broadened light absorption, enhanced photoelectrochemical activity, reduced charge-transfer resistance, and improved separation efficiency of photogenerated carriers (e-/h+). These synergistic effects were attributed to the formation of a Z-scheme heterostructure, which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.
2025, 41(9): 1889-1902
doi: 10.11862/CJIC.20250097
摘要:
A cobalt-based metal-organic framework [Co3(L)2(1, 4-bib)4]·4H2O (Co-MOF) was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid (H3L) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib) as ligands. Then, an electrochemical sensor modified with Co-MOF on a glassy carbon electrode (Co-MOF@GCE) was constructed for detecting Cd2+ and Pb2+ in aqueous solutions. The sensor exhibited a linear range of 1.0-16.0 μmol·L-1 with a detection limit (LOD) of 4.609 nmol·L-1 for Cd2+, and 0.5-10.0 μmol·L-1 with an LOD of 1.307 nmol·L-1 for Pb2+. Simultaneous detection of both ions within 0.5-7.0 μmol·L-1 achieved LOD values of 0.47 nmol·L-1 (Cd2+) and 0.008 nmol·L-1 (Pb2+), respectively. Analysis of real water samples (tap water, mineral water, and river water) yielded recoveries of 95%-105%, validating practical applicability. Density functional theory (DFT) calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency. CCDC: 2160744.
A cobalt-based metal-organic framework [Co3(L)2(1, 4-bib)4]·4H2O (Co-MOF) was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid (H3L) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib) as ligands. Then, an electrochemical sensor modified with Co-MOF on a glassy carbon electrode (Co-MOF@GCE) was constructed for detecting Cd2+ and Pb2+ in aqueous solutions. The sensor exhibited a linear range of 1.0-16.0 μmol·L-1 with a detection limit (LOD) of 4.609 nmol·L-1 for Cd2+, and 0.5-10.0 μmol·L-1 with an LOD of 1.307 nmol·L-1 for Pb2+. Simultaneous detection of both ions within 0.5-7.0 μmol·L-1 achieved LOD values of 0.47 nmol·L-1 (Cd2+) and 0.008 nmol·L-1 (Pb2+), respectively. Analysis of real water samples (tap water, mineral water, and river water) yielded recoveries of 95%-105%, validating practical applicability. Density functional theory (DFT) calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency. CCDC: 2160744.
2025, 41(9): 1903-1915
doi: 10.11862/CJIC.20250026
摘要:
Herein, copper nanoclusters (Cu NCs) were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand, with Cu(NO3)2 as copper source. Subsequently, composite fluorescent nanoparticles, chitosan-functionalized silica nanoparticles (CSNPs)-coated Cu NCs (Cu NCs/CSNPs), were synthesized via a reverse microemulsion method. Compared with Cu NCs, the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance. Based on the composite Cu NCs/CSNPs, a fluorescence method for the detection of cefixime fluorescence quenching was established. The technique was simple, sensitive, and selective for detecting cefixime. The fluorescence quenching efficiency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5 μmol·L-1 (1.81-17.46 mg·L-1), with a limit of detection of 0.045 5 μmol·L-1 (20.6 μg·L-1).
Herein, copper nanoclusters (Cu NCs) were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand, with Cu(NO3)2 as copper source. Subsequently, composite fluorescent nanoparticles, chitosan-functionalized silica nanoparticles (CSNPs)-coated Cu NCs (Cu NCs/CSNPs), were synthesized via a reverse microemulsion method. Compared with Cu NCs, the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance. Based on the composite Cu NCs/CSNPs, a fluorescence method for the detection of cefixime fluorescence quenching was established. The technique was simple, sensitive, and selective for detecting cefixime. The fluorescence quenching efficiency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5 μmol·L-1 (1.81-17.46 mg·L-1), with a limit of detection of 0.045 5 μmol·L-1 (20.6 μg·L-1).
2025, 41(9): 1916-1926
doi: 10.11862/CJIC.20240442
摘要:
Herein, an FMS/CC composite was successfully fabricated by depositing FeMoS4 onto a pristine carbon fiber cloth (CC) substrate via a facile two-step hydrothermal method. The amorphous nature of the FMS/CC composite endows it with abundant catalytically active sites, thereby accelerating the reduction of I3-. More importantly, the dye-sensitized solar cells (DSSCs) prepared by scraping it on flexible titanium mesh with low resistance had low series resistance (Rs). Electrochemical characterizations revealed that the DSSCs employing the FMS/CC counter electrode achieved a power conversion efficiency (PCE) of ca. 9.51% (surpassing the ca. 8.15% efficiency of the Pt counter electrode), open-circuit voltage (Voc) of ca. 0.79 V, short-circuit current density (Jsc) of ca. 18.31 mA·cm-2, and fill factor (FF) of ca. 0.65. Moreover, after 100 times of cyclic voltammetry (CV) test, the CV curve remainedunchanged, indicating the excellent stability of FMS/CC in the electrolyte containing I3-/I-.
Herein, an FMS/CC composite was successfully fabricated by depositing FeMoS4 onto a pristine carbon fiber cloth (CC) substrate via a facile two-step hydrothermal method. The amorphous nature of the FMS/CC composite endows it with abundant catalytically active sites, thereby accelerating the reduction of I3-. More importantly, the dye-sensitized solar cells (DSSCs) prepared by scraping it on flexible titanium mesh with low resistance had low series resistance (Rs). Electrochemical characterizations revealed that the DSSCs employing the FMS/CC counter electrode achieved a power conversion efficiency (PCE) of ca. 9.51% (surpassing the ca. 8.15% efficiency of the Pt counter electrode), open-circuit voltage (Voc) of ca. 0.79 V, short-circuit current density (Jsc) of ca. 18.31 mA·cm-2, and fill factor (FF) of ca. 0.65. Moreover, after 100 times of cyclic voltammetry (CV) test, the CV curve remainedunchanged, indicating the excellent stability of FMS/CC in the electrolyte containing I3-/I-.
2025, 41(8): 1465-1482
doi: 10.11862/CJIC.20240430
摘要:
2D过渡金属碳/氮化物或碳氮化物(MXenes)因其独特的物理和化学性质，在电学、光学、催化和环境等多个领域展现出了广泛的应用潜力。这些独特的性质为MXenes材料在各个领域的创新应用奠定了坚实的基础。近年来，2D MXenes纳米材料的界面调控策略受到了广泛关注。研究者通过不同的方法，如表面基团控制、表面吸附、表面复合和交联等，对MXenes进行了深入的改性研究。本文综述了MXenes的界面调控策略及其功能化材料在能量存储、催化、光电探测、电磁屏蔽、污染物吸附和生物医药领域的研究进展。
2D过渡金属碳/氮化物或碳氮化物(MXenes)因其独特的物理和化学性质，在电学、光学、催化和环境等多个领域展现出了广泛的应用潜力。这些独特的性质为MXenes材料在各个领域的创新应用奠定了坚实的基础。近年来，2D MXenes纳米材料的界面调控策略受到了广泛关注。研究者通过不同的方法，如表面基团控制、表面吸附、表面复合和交联等，对MXenes进行了深入的改性研究。本文综述了MXenes的界面调控策略及其功能化材料在能量存储、催化、光电探测、电磁屏蔽、污染物吸附和生物医药领域的研究进展。
2025, 41(8): 1483-1494
doi: 10.11862/CJIC.20250031
摘要:
将天然产物脱氢松香酸(DHA)引入环金属铱中，成功合成了一种新型环金属铱配合物CycIr-DHA，并通过 1H NMR对配体及配合物进行表征。该配合物在多种肿瘤细胞株中表现出显著的抗肿瘤活性，尤其是对人乳腺癌细胞(MCF-7)的抑制效果最为明显，其半数抑制浓度(IC50)仅为2.5 μmol·L-1，优于传统化疗药物顺铂。实验结果显示，CycIr-DHA主要在MCF-7的线粒体中富集，能够显著提高细胞内活性氧水平，导致线粒体功能障碍。此外，该配合物还能调节凋亡相关蛋白(Bax和Bcl-2)的表达，促进细胞凋亡，并上调LC3-Ⅱ蛋白，诱导细胞自噬。在3D细胞球模型中，CycIr-DHA显著抑制了细胞球的生长。
将天然产物脱氢松香酸(DHA)引入环金属铱中，成功合成了一种新型环金属铱配合物CycIr-DHA，并通过 1H NMR对配体及配合物进行表征。该配合物在多种肿瘤细胞株中表现出显著的抗肿瘤活性，尤其是对人乳腺癌细胞(MCF-7)的抑制效果最为明显，其半数抑制浓度(IC50)仅为2.5 μmol·L-1，优于传统化疗药物顺铂。实验结果显示，CycIr-DHA主要在MCF-7的线粒体中富集，能够显著提高细胞内活性氧水平，导致线粒体功能障碍。此外，该配合物还能调节凋亡相关蛋白(Bax和Bcl-2)的表达，促进细胞凋亡，并上调LC3-Ⅱ蛋白，诱导细胞自噬。在3D细胞球模型中，CycIr-DHA显著抑制了细胞球的生长。
2025, 41(8): 1495-1504
doi: 10.11862/CJIC.20250144
摘要:
本文报道了一种基于二茂铁与苯并硒二唑(SeNBD)偶联物的前药FcNH-SeNBD，用于肿瘤细胞化学动力学治疗(CDT)与荧光成像。FcNH-SeNBD利用肿瘤细胞中过表达的过氧化氢(H2O2)氧化二茂铁发生芬顿反应，高效生成羟基自由基(·OH)，诱导肿瘤细胞凋亡。与此同时，二茂铁的氧化阻断了其与苯并硒二唑之间的光致电子转移(PET)效应，使得原本被猝灭的SeNBD荧光得以恢复，实现了荧光信号“Off-On”的转变，用于实时监测前药在肿瘤细胞中的活化与富集，便于治疗效果的预测与评估。体外实验表明 FcNH-SeNBD对肝癌细胞HepG2[IC50=(7.95±0.98) μg·mL-1]和结直肠癌细胞HCT116[IC50=(15.74±1.5) μg· mL-1]具有显著的选择性杀伤作用，而对正常结肠上皮细胞NCM-460无显著毒性(IC50>100 μg·mL-1)。机制研究证实，FcNH-SeNBD通过激活caspase-3依赖性凋亡通路发挥对肿瘤细胞的杀伤作用。细胞成像实验表明 FcNH-SeNBD可在肿瘤细胞中富集并产生强烈的红色荧光。
本文报道了一种基于二茂铁与苯并硒二唑(SeNBD)偶联物的前药FcNH-SeNBD，用于肿瘤细胞化学动力学治疗(CDT)与荧光成像。FcNH-SeNBD利用肿瘤细胞中过表达的过氧化氢(H2O2)氧化二茂铁发生芬顿反应，高效生成羟基自由基(·OH)，诱导肿瘤细胞凋亡。与此同时，二茂铁的氧化阻断了其与苯并硒二唑之间的光致电子转移(PET)效应，使得原本被猝灭的SeNBD荧光得以恢复，实现了荧光信号“Off-On”的转变，用于实时监测前药在肿瘤细胞中的活化与富集，便于治疗效果的预测与评估。体外实验表明 FcNH-SeNBD对肝癌细胞HepG2[IC50=(7.95±0.98) μg·mL-1]和结直肠癌细胞HCT116[IC50=(15.74±1.5) μg· mL-1]具有显著的选择性杀伤作用，而对正常结肠上皮细胞NCM-460无显著毒性(IC50>100 μg·mL-1)。机制研究证实，FcNH-SeNBD通过激活caspase-3依赖性凋亡通路发挥对肿瘤细胞的杀伤作用。细胞成像实验表明 FcNH-SeNBD可在肿瘤细胞中富集并产生强烈的红色荧光。
2025, 41(8): 1505-1512
doi: 10.11862/CJIC.20250125
摘要:
将[Ag9(Tab)8(MeCN)8]2(PF6)18·4MeCN(Tab=4-(三甲基铵)苯硫酚盐，MeCN=乙腈)与三苯基膦(L1)和二苯基-2-吡啶膦(L2)分别进行固相研磨反应，得到的固体粉末经溶剂溶解、离心分离后，通过溶剂扩散法结晶得到了2个膦配体保护的银硫醇团簇[Ag7(Tab)6(L1)6Cl](PF6)6·8DMF (1)和[Ag17(Tab)20(L2)2](PF6)17·32DMF (2)。对2个簇合物分别进行了单晶X射线衍射、粉末X射线衍射、红外、紫外可见、热重和元素分析表征。单晶X射线衍射分析表明，2个簇合物均由有机磷配体和Tab配体共同保护，且簇合物2结构表面的二苯基-2-吡啶膦配体的P和N原子同时参与了配位。Z扫描技术测试结果表明2个簇合物在溶液中具有一定的三阶非线性光学响应。
将[Ag9(Tab)8(MeCN)8]2(PF6)18·4MeCN(Tab=4-(三甲基铵)苯硫酚盐，MeCN=乙腈)与三苯基膦(L1)和二苯基-2-吡啶膦(L2)分别进行固相研磨反应，得到的固体粉末经溶剂溶解、离心分离后，通过溶剂扩散法结晶得到了2个膦配体保护的银硫醇团簇[Ag7(Tab)6(L1)6Cl](PF6)6·8DMF (1)和[Ag17(Tab)20(L2)2](PF6)17·32DMF (2)。对2个簇合物分别进行了单晶X射线衍射、粉末X射线衍射、红外、紫外可见、热重和元素分析表征。单晶X射线衍射分析表明，2个簇合物均由有机磷配体和Tab配体共同保护，且簇合物2结构表面的二苯基-2-吡啶膦配体的P和N原子同时参与了配位。Z扫描技术测试结果表明2个簇合物在溶液中具有一定的三阶非线性光学响应。
2025, 41(8): 1513-1522
doi: 10.11862/CJIC.20250113
摘要:
合成了膦蒽配体1, 8-双(二苯基磷)蒽(Hbdpa)及其配合物[Au(Hbdpa)2]PF6 (1)和[Ir(tpy)(bdpa)](PF6)2 (2)，其中tpy=2，2′∶6′，2″-三联吡啶。在光照作用下，这些化合物发生光化学反应，生成Hbdpa-2O、[Au(Hbdpa-O)2]PF6 (1-O)和[Ir(tpy)(bdpa-OH)](PF6)2 (2-OH)。通过核磁、质谱和单晶X射线衍射表征了这些化合物的结构。讨论了化合物Hbdpa及其配合物1和2的光化学反应特性以及相关的发光行为调控。研究结果表明，Au(Ⅰ)和Ir(Ⅲ)的配位显著提高了配体Hbdpa的光反应活性。化合物2是首例能发生蒽基去芳构化反应的铱配合物。
合成了膦蒽配体1, 8-双(二苯基磷)蒽(Hbdpa)及其配合物[Au(Hbdpa)2]PF6 (1)和[Ir(tpy)(bdpa)](PF6)2 (2)，其中tpy=2，2′∶6′，2″-三联吡啶。在光照作用下，这些化合物发生光化学反应，生成Hbdpa-2O、[Au(Hbdpa-O)2]PF6 (1-O)和[Ir(tpy)(bdpa-OH)](PF6)2 (2-OH)。通过核磁、质谱和单晶X射线衍射表征了这些化合物的结构。讨论了化合物Hbdpa及其配合物1和2的光化学反应特性以及相关的发光行为调控。研究结果表明，Au(Ⅰ)和Ir(Ⅲ)的配位显著提高了配体Hbdpa的光反应活性。化合物2是首例能发生蒽基去芳构化反应的铱配合物。
2025, 41(8): 1523-1532
doi: 10.11862/CJIC.20250073
摘要:
用N′-[(1E)-吡啶-2-亚甲基]吡啶-4-碳酰肼(HL)配体与铟离子/镝离子合成了2种金属配合物[In(HL)(NO3)3] (1)和[Dy(L)(CH3OH)0.89(H2O)1.11(NO3)2]·0.11H2O (2)。单晶X射线衍射表明，配合物1和2均具有由1个配体连接1个金属离子形成的零维单核结构。体外抗增殖活性研究表明，配合物1对人肝癌细胞SMMC-7721、人乳腺癌细胞MDA-MB-231及人非小细胞肺癌细胞A549的抗肿瘤活性均优于顺铂；配合物2对SMMC-7721及A549的抗肿瘤活性也优于顺铂。伤口愈合实验显示配合物1和2可以抑制A549细胞迁移能力，且呈浓度依赖性。此外，配合物2对大肠杆菌具有显著的抑菌效果，抑菌圈直径达到22 mm。
用N′-[(1E)-吡啶-2-亚甲基]吡啶-4-碳酰肼(HL)配体与铟离子/镝离子合成了2种金属配合物[In(HL)(NO3)3] (1)和[Dy(L)(CH3OH)0.89(H2O)1.11(NO3)2]·0.11H2O (2)。单晶X射线衍射表明，配合物1和2均具有由1个配体连接1个金属离子形成的零维单核结构。体外抗增殖活性研究表明，配合物1对人肝癌细胞SMMC-7721、人乳腺癌细胞MDA-MB-231及人非小细胞肺癌细胞A549的抗肿瘤活性均优于顺铂；配合物2对SMMC-7721及A549的抗肿瘤活性也优于顺铂。伤口愈合实验显示配合物1和2可以抑制A549细胞迁移能力，且呈浓度依赖性。此外，配合物2对大肠杆菌具有显著的抑菌效果，抑菌圈直径达到22 mm。
2025, 41(8): 1533-1544
doi: 10.11862/CJIC.20250063
摘要:
采用固相烧结法制备了Li4GeO4、Li6Ge2O7、Li2GeO3和Li2Ge2O5四种Li2O-GeO2二元系晶体，并通过原位高温拉曼光谱技术结合理论计算的方法对晶态到熔态的结构演变过程以及熔体微结构进行定性和定量分析。研究表明：Li4GeO4、Li6Ge2O7和Li2GeO3熔体分别由[GeO4]4-、[Ge2O7]6-、[GeO3]2-和Li+构成，而Li2Ge2O5晶体在升温至熔融状态过程中由[GeO4]4-四面体形成的三维网络结构逐渐向更小的[Ge3O9]6-三元环递变。另外，通过量子化学从头计算法对团簇结构单元进行了设计、优化和计算，并将理论计算模拟与实验相结合，提出了一种校正熔体实验拉曼光谱的新方法。我们通过引入精细结构概念并利用高斯函数对拉曼光谱中[GeO4]4-四面体非桥氧的伸缩振动包络峰进行了分峰解谱，得到了这4种晶体在熔融状态下的不同结构(Qi，i表示每个[GeO4]4-四面体中桥氧的个数，i=0~4)单元含量的定量分布。
采用固相烧结法制备了Li4GeO4、Li6Ge2O7、Li2GeO3和Li2Ge2O5四种Li2O-GeO2二元系晶体，并通过原位高温拉曼光谱技术结合理论计算的方法对晶态到熔态的结构演变过程以及熔体微结构进行定性和定量分析。研究表明：Li4GeO4、Li6Ge2O7和Li2GeO3熔体分别由[GeO4]4-、[Ge2O7]6-、[GeO3]2-和Li+构成，而Li2Ge2O5晶体在升温至熔融状态过程中由[GeO4]4-四面体形成的三维网络结构逐渐向更小的[Ge3O9]6-三元环递变。另外，通过量子化学从头计算法对团簇结构单元进行了设计、优化和计算，并将理论计算模拟与实验相结合，提出了一种校正熔体实验拉曼光谱的新方法。我们通过引入精细结构概念并利用高斯函数对拉曼光谱中[GeO4]4-四面体非桥氧的伸缩振动包络峰进行了分峰解谱，得到了这4种晶体在熔融状态下的不同结构(Qi，i表示每个[GeO4]4-四面体中桥氧的个数，i=0~4)单元含量的定量分布。
2025, 41(8): 1545-1554
doi: 10.11862/CJIC.20250046
摘要:
为开发在温和条件下高效、高选择性氧化5-羟甲基糠醛(HMF)的多功能催化材料和反应体系，构筑了双金属有机框架(BMOF)材料及其衍生材料，用于低电压下的HMF电催化氧化。采用溶剂热法合成了双金属CoNi-MOF-74，并采用2种方式制备相应的催化材料。其一，对CoNi-MOF-74进行热解处理，制得石墨碳层包覆、碳基体稳定的CoNi合金(CoNi@C)纳米颗粒；其二，在电催化过程中，CoNi-MOF-74发生原位水解反应，生成相应的氢氧化物(CoNi(OH)2)，进而将其作为电极材料使用。研究发现，当Co、Ni的物质的量之比设定为1∶3时，所制备的Co1Ni3-MOF-74材料在800 ℃进行热解处理后，生成的Co1Ni3@C在低电位下对HMF电催化氧化表现出优异的催化活性和高的2, 5-呋喃二甲酸(FDCA)选择性(87.26%)。而Co1Ni1-MOF-74(Co、Ni物质的量之比为1∶1)电解时原位生成的Co0.5Ni0.5(OH)2对中间产物5-(羟甲基)呋喃-2-羧酸(HMFCA)具有很高的选择性(88.59%)和高转化率。这主要得益于衍生材料较好的孔隙结构、Co和Ni双金属之间的协同作用和石墨碳的良好导电性。
为开发在温和条件下高效、高选择性氧化5-羟甲基糠醛(HMF)的多功能催化材料和反应体系，构筑了双金属有机框架(BMOF)材料及其衍生材料，用于低电压下的HMF电催化氧化。采用溶剂热法合成了双金属CoNi-MOF-74，并采用2种方式制备相应的催化材料。其一，对CoNi-MOF-74进行热解处理，制得石墨碳层包覆、碳基体稳定的CoNi合金(CoNi@C)纳米颗粒；其二，在电催化过程中，CoNi-MOF-74发生原位水解反应，生成相应的氢氧化物(CoNi(OH)2)，进而将其作为电极材料使用。研究发现，当Co、Ni的物质的量之比设定为1∶3时，所制备的Co1Ni3-MOF-74材料在800 ℃进行热解处理后，生成的Co1Ni3@C在低电位下对HMF电催化氧化表现出优异的催化活性和高的2, 5-呋喃二甲酸(FDCA)选择性(87.26%)。而Co1Ni1-MOF-74(Co、Ni物质的量之比为1∶1)电解时原位生成的Co0.5Ni0.5(OH)2对中间产物5-(羟甲基)呋喃-2-羧酸(HMFCA)具有很高的选择性(88.59%)和高转化率。这主要得益于衍生材料较好的孔隙结构、Co和Ni双金属之间的协同作用和石墨碳的良好导电性。
2025, 41(8): 1555-1564
doi: 10.11862/CJIC.20250040
摘要:
以废旧棉织物为原料，氯化锌为活化剂，采用一步活化-炭化法制备具有丰富孔隙结构的废旧棉织物基炭吸波材料(CCF)，并探讨了不同氯化锌质量分数对CCF吸波性能的影响。结果表明：氯化锌能够有效丰富CCF的孔隙结构，提高其吸波效果。在炭化温度为700 ℃(N2气氛下)、氯化锌质量分数为10%时制备的CCF-10的比表面积高达1 310 m2·g-1，其在厚度为2.0mm时的最小反射损耗达-35.02 dB，有效吸收带宽为5.6 GHz。
以废旧棉织物为原料，氯化锌为活化剂，采用一步活化-炭化法制备具有丰富孔隙结构的废旧棉织物基炭吸波材料(CCF)，并探讨了不同氯化锌质量分数对CCF吸波性能的影响。结果表明：氯化锌能够有效丰富CCF的孔隙结构，提高其吸波效果。在炭化温度为700 ℃(N2气氛下)、氯化锌质量分数为10%时制备的CCF-10的比表面积高达1 310 m2·g-1，其在厚度为2.0mm时的最小反射损耗达-35.02 dB，有效吸收带宽为5.6 GHz。
2025, 41(8): 1565-1573
doi: 10.11862/CJIC.20250054
摘要:
将MoO3纳米片与2，2，6，6-四甲基哌啶氧化物(TEMPO)氧化的纤维素纳米纤维(TEMPO-CNF)复合，并经过高温碳化工艺制备了MoO3/T-CNF碳化复合气凝胶材料，其中T-CNF指TEMPO-CNT碳化后得到的多孔碳。MoO3/T-CNF具有高导电性、发达的孔隙结构和大的比表面积等特性，将其作为锂硫电池阴极时，能够有效吸附多硫化物，抑制穿梭效应，并缓解充放电过程中的体积膨胀。其中，最佳样品MoO3/T-CNF-3在0.1C倍率下的最高放电比容量达到1 721.8 mAh·g-1，且在200次循环后仍能保持84.8%的容量保持率和99.6%的库仑效率。
将MoO3纳米片与2，2，6，6-四甲基哌啶氧化物(TEMPO)氧化的纤维素纳米纤维(TEMPO-CNF)复合，并经过高温碳化工艺制备了MoO3/T-CNF碳化复合气凝胶材料，其中T-CNF指TEMPO-CNT碳化后得到的多孔碳。MoO3/T-CNF具有高导电性、发达的孔隙结构和大的比表面积等特性，将其作为锂硫电池阴极时，能够有效吸附多硫化物，抑制穿梭效应，并缓解充放电过程中的体积膨胀。其中，最佳样品MoO3/T-CNF-3在0.1C倍率下的最高放电比容量达到1 721.8 mAh·g-1，且在200次循环后仍能保持84.8%的容量保持率和99.6%的库仑效率。
2025, 41(8): 1574-1588
doi: 10.11862/CJIC.20250032
摘要:
在研究沼渣生物炭吸附氨氮(NH4+)的特性及机理的基础上，我们重点探讨了饱和沼渣生物炭的热再生性能，并研究了热再生参数(再生温度、再生时间、升温速率、保护气以及气体流速)对生物炭吸附性能的影响机制。沼渣生物炭对NH4+的吸附量可达19.12 mg·g-1，符合Langmuir模型，吸附机理主要是表面配位和离子交换反应。最佳热再生参数如下：温度为200 ℃，保护气为N2，流速为0.5 L·min-1，以5 ℃·min-1的升温速率再生1 h。饱和生物炭首次吸附再生率为99.59%，经10次吸附-再生循环后，吸附再生率仍达89.55%，失重率小于5%。通过热重-红外联用仪(TG?IR)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、比表面及孔隙度分析和扫描电子显微镜(SEM)等多种手段进行表征，结果表明，多次循环热再生可破坏饱和生物炭表面的C=O、—OH和—COOH等含氧官能团，同时部分吸附位点被永久占用，导致吸附再生率逐渐下降。热再生可实现饱和生物炭中绝大部分氨氮的热解脱附，有效恢复生物炭孔隙结构和表面含氧官能团的吸附位点。
在研究沼渣生物炭吸附氨氮(NH4+)的特性及机理的基础上，我们重点探讨了饱和沼渣生物炭的热再生性能，并研究了热再生参数(再生温度、再生时间、升温速率、保护气以及气体流速)对生物炭吸附性能的影响机制。沼渣生物炭对NH4+的吸附量可达19.12 mg·g-1，符合Langmuir模型，吸附机理主要是表面配位和离子交换反应。最佳热再生参数如下：温度为200 ℃，保护气为N2，流速为0.5 L·min-1，以5 ℃·min-1的升温速率再生1 h。饱和生物炭首次吸附再生率为99.59%，经10次吸附-再生循环后，吸附再生率仍达89.55%，失重率小于5%。通过热重-红外联用仪(TG?IR)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、比表面及孔隙度分析和扫描电子显微镜(SEM)等多种手段进行表征，结果表明，多次循环热再生可破坏饱和生物炭表面的C=O、—OH和—COOH等含氧官能团，同时部分吸附位点被永久占用，导致吸附再生率逐渐下降。热再生可实现饱和生物炭中绝大部分氨氮的热解脱附，有效恢复生物炭孔隙结构和表面含氧官能团的吸附位点。
2025, 41(8): 1589-1600
doi: 10.11862/CJIC.20250011
摘要:
首先通过水热法合成了Fe掺杂ZnO(ZnFeO)花状微球，然后采用物理沉积法将Mn掺杂碳量子点(Mn?CQDs)均匀负载于ZnFeO表面，成功构筑了Mn?CQDs/ZnFeO异质结复合材料。结合粉末X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、紫外可见漫反射光谱和N2脱附-吸附分析，探究了该材料结构与光催化性能的关系。结果表明，Mn掺杂显著提升了CQDs的光吸收范围和荧光稳定性；Mn和Fe双掺杂协同拓展了Mn?CQDs/ZnFeO的可见光吸收边，提高了吸收强度，促进了界面光生电子-空穴对的分离，改善了光催化性能。氙灯光照80 min时，复合材料对甲基橙(MO)的降解率达到91.4%，经过4次循环实验后，降解率仍保持在80.7%。自由基捕获实验证实，光生空穴(h+)和超氧自由基(·O2-)是MO光降解过程中的主要活性物种。
首先通过水热法合成了Fe掺杂ZnO(ZnFeO)花状微球，然后采用物理沉积法将Mn掺杂碳量子点(Mn?CQDs)均匀负载于ZnFeO表面，成功构筑了Mn?CQDs/ZnFeO异质结复合材料。结合粉末X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、紫外可见漫反射光谱和N2脱附-吸附分析，探究了该材料结构与光催化性能的关系。结果表明，Mn掺杂显著提升了CQDs的光吸收范围和荧光稳定性；Mn和Fe双掺杂协同拓展了Mn?CQDs/ZnFeO的可见光吸收边，提高了吸收强度，促进了界面光生电子-空穴对的分离，改善了光催化性能。氙灯光照80 min时，复合材料对甲基橙(MO)的降解率达到91.4%，经过4次循环实验后，降解率仍保持在80.7%。自由基捕获实验证实，光生空穴(h+)和超氧自由基(·O2-)是MO光降解过程中的主要活性物种。
2025, 41(8): 1601-1609
doi: 10.11862/CJIC.20250012
摘要:
合成了二(邻氟苄基)锡-2，2′-联吡啶-6，6′-二甲酸(H2bpdc)配合物[Sn(o-F-C6H4CH2)2(bpdc)(H2O)]2·H2O (1)和二正丁基锡-2，2′-联吡啶-6，6′-二甲酸配合物[Sn(n-C4H9)2(bpdc)(H2O)]·H2O (2)。通过元素分析、红外光谱、核磁共振谱(1H、13C和119Sn)、差热分析进行了表征；用单晶X射线衍射方法测定了配合物的晶体结构，对其结构进行量子化学计算，测定了配合物对人胃腺癌细胞(AGS)、人急性淋巴母细胞白血病细胞(MOLT4)和人乳腺癌细胞(MDA-MB-231)的体外抑制活性。结果显示: 配合物均为单核分子，中心锡原子均为七配位的畸变五角双锥构型；除配合物2对MDA-MB-231的抑制活性相对较弱外，配合物对其它细胞均显示了较强的抑制活性。
合成了二(邻氟苄基)锡-2，2′-联吡啶-6，6′-二甲酸(H2bpdc)配合物[Sn(o-F-C6H4CH2)2(bpdc)(H2O)]2·H2O (1)和二正丁基锡-2，2′-联吡啶-6，6′-二甲酸配合物[Sn(n-C4H9)2(bpdc)(H2O)]·H2O (2)。通过元素分析、红外光谱、核磁共振谱(1H、13C和119Sn)、差热分析进行了表征；用单晶X射线衍射方法测定了配合物的晶体结构，对其结构进行量子化学计算，测定了配合物对人胃腺癌细胞(AGS)、人急性淋巴母细胞白血病细胞(MOLT4)和人乳腺癌细胞(MDA-MB-231)的体外抑制活性。结果显示: 配合物均为单核分子，中心锡原子均为七配位的畸变五角双锥构型；除配合物2对MDA-MB-231的抑制活性相对较弱外，配合物对其它细胞均显示了较强的抑制活性。
2025, 41(8): 1610-1616
doi: 10.11862/CJIC.20240444
摘要:
首先采用水热法在碳布(CC)上生长了Ni掺杂WO3纳米线(Ni-WO3 NWs/CC)，然后利用高真空固相磷化法将其磷化，得到CC表面生长Ni掺杂WP2纳米线复合材料(Ni-WP2 NWs/CC)。研究其电催化析氢性能发现，Ni掺杂能够有效降低电催化析氢反应中的过电位。其中，当Ni、W物质的量之比为10%时制备得到的10%Ni-WP2 NWs/CC表现出最佳的催化性能。在碱性条件下，当电流密度为10和100 mA·cm-2时，10%Ni-WP2 NWs/CC所需的过电位分别为115和190 mV。经过Ni掺杂后，10%Ni-WP2 NWs/CC的电化学活性表面积明显增加。此外，在长时间的电催化条件下，该催化剂依然能保持良好的工作稳定性。
首先采用水热法在碳布(CC)上生长了Ni掺杂WO3纳米线(Ni-WO3 NWs/CC)，然后利用高真空固相磷化法将其磷化，得到CC表面生长Ni掺杂WP2纳米线复合材料(Ni-WP2 NWs/CC)。研究其电催化析氢性能发现，Ni掺杂能够有效降低电催化析氢反应中的过电位。其中，当Ni、W物质的量之比为10%时制备得到的10%Ni-WP2 NWs/CC表现出最佳的催化性能。在碱性条件下，当电流密度为10和100 mA·cm-2时，10%Ni-WP2 NWs/CC所需的过电位分别为115和190 mV。经过Ni掺杂后，10%Ni-WP2 NWs/CC的电化学活性表面积明显增加。此外，在长时间的电催化条件下，该催化剂依然能保持良好的工作稳定性。
2025, 41(8): 1617-1631
doi: 10.11862/CJIC.20240420
摘要:
以六水合硝酸铈(Ce(NO3)3·6H2O)和可溶性淀粉(ST)为原料，通过生物模板法制备了CeO2非均相光芬顿催化剂(ST-CeO2)。采用X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)、拉曼光谱、固体紫外可见漫反射光谱(UV-Vis DRS)和X射线光电子能谱(XPS)对催化剂进行表征。FTIR和Raman光谱证实了Ce—O键及氧空位的存在。UV-Vis DRS显示其在紫外和可见光区域有强吸收，XPS光谱分析表明催化剂表面存在Ce3+和Ce4+的混合价态，这可有效促进光生电荷的分离和H2O2的活化。甲基橙(MO)降解结果表明，ST-CeO2在紫外光下照射60 min时对MO染料的降解率可达82.8%;加入H2O2后，其在60 min时对MO染料的降解率可达99.7%，而且重复回收利用5次后仍然保持优良的催化性能。自由基捕获实验证明空穴(h+)和羟基自由基(·OH)是在MO染料降解反应中起主导作用的活性物质，而超氧自由基(·O2-)起次要作用。此外还详细探讨了ST-CeO2光芬顿降解MO染料的机理。
以六水合硝酸铈(Ce(NO3)3·6H2O)和可溶性淀粉(ST)为原料，通过生物模板法制备了CeO2非均相光芬顿催化剂(ST-CeO2)。采用X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)、拉曼光谱、固体紫外可见漫反射光谱(UV-Vis DRS)和X射线光电子能谱(XPS)对催化剂进行表征。FTIR和Raman光谱证实了Ce—O键及氧空位的存在。UV-Vis DRS显示其在紫外和可见光区域有强吸收，XPS光谱分析表明催化剂表面存在Ce3+和Ce4+的混合价态，这可有效促进光生电荷的分离和H2O2的活化。甲基橙(MO)降解结果表明，ST-CeO2在紫外光下照射60 min时对MO染料的降解率可达82.8%;加入H2O2后，其在60 min时对MO染料的降解率可达99.7%，而且重复回收利用5次后仍然保持优良的催化性能。自由基捕获实验证明空穴(h+)和羟基自由基(·OH)是在MO染料降解反应中起主导作用的活性物质，而超氧自由基(·O2-)起次要作用。此外还详细探讨了ST-CeO2光芬顿降解MO染料的机理。
2025, 41(8): 1632-1640
doi: 10.11862/CJIC.20240398
摘要:
以ZIF-8作为牺牲模板剂，利用其固有的多面体空间结构特征来抑制纳米颗粒催化剂的聚积行为，同时通过进一步引入过渡金属镍(Ni)元素对二氧化钌(RuO2)进行掺杂，以达到优化材料电子结构，提高活性位点的本征活性的目的，从而制备出粒径为8~10 nm的高性能析氧电催化剂(Ni-RuO2)。结果表明，Ni-RuO2具有优异的析氧反应(OER)催化性能，超越了商业RuO2。在碱性条件下，Ni-RuO2在电流密度为10 mA·cm-2时所需的过电位仅为257 mV，且具有较高的电化学活性面积、较快的电荷转移能力和良好的循环稳定性，优于商业RuO2和未进行Ni掺杂的RuO2。将Ni-RuO2作为阳极进行全解水测试时，其获得10 mA·cm-2的电流密度时仅需要1.476 V的分解电压。
以ZIF-8作为牺牲模板剂，利用其固有的多面体空间结构特征来抑制纳米颗粒催化剂的聚积行为，同时通过进一步引入过渡金属镍(Ni)元素对二氧化钌(RuO2)进行掺杂，以达到优化材料电子结构，提高活性位点的本征活性的目的，从而制备出粒径为8~10 nm的高性能析氧电催化剂(Ni-RuO2)。结果表明，Ni-RuO2具有优异的析氧反应(OER)催化性能，超越了商业RuO2。在碱性条件下，Ni-RuO2在电流密度为10 mA·cm-2时所需的过电位仅为257 mV，且具有较高的电化学活性面积、较快的电荷转移能力和良好的循环稳定性，优于商业RuO2和未进行Ni掺杂的RuO2。将Ni-RuO2作为阳极进行全解水测试时，其获得10 mA·cm-2的电流密度时仅需要1.476 V的分解电压。
2025, 41(8): 1641-1649
doi: 10.11862/CJIC.20250152
摘要:
A novel 3D metal-organic framework (MOF) [Pr2(L)3(H2O)5·H2O]n (Pr-1), (H2L=4, 4′-oxybis(benzoic acid)) with a rare structure of broken layer net, was constructed under the condition of solvothermal synthesis. The structure and crystal net were analyzed and characterized. This rod net of Pr-1 is new to both RCSR and ToposPro databases, and is named as rn-12 as suggested. Due to the luminescent properties of H2L and Pr(Ⅲ), the solid-state fluorescence property and sensing performance (solvents and metal ions) of Pr-1 were investigated. The sensing experiments indicated that Pr-1 could act as a fluorescence sensor to detect Cd2+ ions with good sensitivity. In addition, antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Bacillus subtilis (B. subtilis) compared to synthetic materials.
A novel 3D metal-organic framework (MOF) [Pr2(L)3(H2O)5·H2O]n (Pr-1), (H2L=4, 4′-oxybis(benzoic acid)) with a rare structure of broken layer net, was constructed under the condition of solvothermal synthesis. The structure and crystal net were analyzed and characterized. This rod net of Pr-1 is new to both RCSR and ToposPro databases, and is named as rn-12 as suggested. Due to the luminescent properties of H2L and Pr(Ⅲ), the solid-state fluorescence property and sensing performance (solvents and metal ions) of Pr-1 were investigated. The sensing experiments indicated that Pr-1 could act as a fluorescence sensor to detect Cd2+ ions with good sensitivity. In addition, antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Bacillus subtilis (B. subtilis) compared to synthetic materials.
2025, 41(8): 1650-1660
doi: 10.11862/CJIC.20250143
摘要:
Two metal-organic frameworks (MOFs), trans-[Co(L)(μ2-H2O)(H2O)2]·2H2O (1) and cis-[Mn(L)(Bipy)] (2) (H2L=2, 2′-dimethyl-4, 4′-biphenyldicarboxylic acid, Bipy=4, 4′-bipyridine), have been synthesized and characterized by FTIR, thermogravimetric analysis (TGA), powder and single crystal X-ray diffraction. MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Co(Ⅱ) ions. Each trans-[CoO6] octahedron is connected by μ2-H2O and L2- ligand with a bis(unidentate) coordination mode to produce a 2D sql topological network. MOF 2 crystallizes in the monoclinic system with a C2/c space group. The Mn(Ⅱ) cation adopts a cis-[MnO4N2] octahedron as a 6-connected node and is linked by L2- ligand as a 4-connected node to generate a binodal (4, 6)-connected 3D fsc framework. The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1, and H…H and C…H/H…C contacts in 2. The TGA indicated that 1 and 2 were stable below 390 and 370 ℃, respectively.
Two metal-organic frameworks (MOFs), trans-[Co(L)(μ2-H2O)(H2O)2]·2H2O (1) and cis-[Mn(L)(Bipy)] (2) (H2L=2, 2′-dimethyl-4, 4′-biphenyldicarboxylic acid, Bipy=4, 4′-bipyridine), have been synthesized and characterized by FTIR, thermogravimetric analysis (TGA), powder and single crystal X-ray diffraction. MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Co(Ⅱ) ions. Each trans-[CoO6] octahedron is connected by μ2-H2O and L2- ligand with a bis(unidentate) coordination mode to produce a 2D sql topological network. MOF 2 crystallizes in the monoclinic system with a C2/c space group. The Mn(Ⅱ) cation adopts a cis-[MnO4N2] octahedron as a 6-connected node and is linked by L2- ligand as a 4-connected node to generate a binodal (4, 6)-connected 3D fsc framework. The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1, and H…H and C…H/H…C contacts in 2. The TGA indicated that 1 and 2 were stable below 390 and 370 ℃, respectively.
2025, 41(8): 1661-1671
doi: 10.11862/CJIC.20250075
摘要:
A functional interlayer based on two-dimensional (2D) porous modified vermiculite nanosheets (PVS) was obtained by acid-etching vermiculite nanosheets. The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m2•g-1 and rich surface active sites, which help restrain polysulfides (LiPSs) through good physical and chemical adsorption, while simultaneously accelerating the nucleation and dissolution kinetics of Li2S, effectively suppressing the shuttle effect. The assembled lithium-sulfur batteries (LSBs) employing the PVS-based interlayer delivered a high initial discharge capacity of 1 386 mAh•g-1 at 0.1C (167.5 mAh•g-1), long-term cycling stability, and good rate property.
A functional interlayer based on two-dimensional (2D) porous modified vermiculite nanosheets (PVS) was obtained by acid-etching vermiculite nanosheets. The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m2•g-1 and rich surface active sites, which help restrain polysulfides (LiPSs) through good physical and chemical adsorption, while simultaneously accelerating the nucleation and dissolution kinetics of Li2S, effectively suppressing the shuttle effect. The assembled lithium-sulfur batteries (LSBs) employing the PVS-based interlayer delivered a high initial discharge capacity of 1 386 mAh•g-1 at 0.1C (167.5 mAh•g-1), long-term cycling stability, and good rate property.
2025, 41(8): 1672-1680
doi: 10.11862/CJIC.20250013
摘要:
One Yb(Ⅲ)-based coordination polymer, {[Yb(H2dhtp)1.5(H2O)4]·3H2O}n (1) (H4dhtp=2, 5-dihydroxyterephthalic acid), was fabricated and structurally characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction, X-ray diffraction, and elemental analysis. Complex 1 displays a 1D chain structure, and belongs to P1 group. The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm (λex=408 nm). It exhibited the emission characteristic of the H4dhtp ligand. The fluorescence of 1 in water displayed the strongest intensity. In detecting various metal ions, adding Zr4+ led to a blue shift in fluorescence, accompanied by an increase in intensity, whereas the presence of Fe3+ resulted in a decrease in luminescence. The changes observed in the IR spectrum indicate an interaction between Fe3+/Zr4+ and complex 1, resulting in the variation of luminescence properties.
One Yb(Ⅲ)-based coordination polymer, {[Yb(H2dhtp)1.5(H2O)4]·3H2O}n (1) (H4dhtp=2, 5-dihydroxyterephthalic acid), was fabricated and structurally characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction, X-ray diffraction, and elemental analysis. Complex 1 displays a 1D chain structure, and belongs to P1 group. The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm (λex=408 nm). It exhibited the emission characteristic of the H4dhtp ligand. The fluorescence of 1 in water displayed the strongest intensity. In detecting various metal ions, adding Zr4+ led to a blue shift in fluorescence, accompanied by an increase in intensity, whereas the presence of Fe3+ resulted in a decrease in luminescence. The changes observed in the IR spectrum indicate an interaction between Fe3+/Zr4+ and complex 1, resulting in the variation of luminescence properties.
2025, 41(8): 1681-1688
doi: 10.11862/CJIC.20250004
摘要:
Six coordination polymers based on 9, 10-di(pyridine-4-yl)-anthracene (DPA) and 1, 6-di(1H-imidazol-1-yl)pyrene (DIP) were obtained by solvothermal reactions. {[Zn(DPA)Cl2]·DMF·2H2O}n (1) and {[Zn1.5(DPA)1.5Cl3]·5H2O}n (2) are framework isomers, which both contain zigzag chains formed by DPA, Zn2+, and Cl-. The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers, and these layers exhibit two different orientations, displaying a rare 2D to 3D interpenetration mode. The zigzag chains in 2 are parallelly arranged. {[Zn3(DPA)3Br6]·2DMF·1.5H2O}n (3) is isostructural to 2. 3 was obtained using ZnBr2 instead of ZnCl2.[M(DPA) (formate)2(H2O)2]n[M=Co (4), Cu (5)] are isostructural, contain chain structures formed by DPA, Cu2+/Co2+, and formate ions, which were formed in situ in the solvothermal reaction. {[Zn(DIP)2Cl]ClO4}n (6) contains a layer structure formed by DIP and Zn2+. Free DPA and DIP ligands exhibited high fluorescence at room temperature, and coordination polymers 3 and 6 displayed enhanced fluorescent emissions.
Six coordination polymers based on 9, 10-di(pyridine-4-yl)-anthracene (DPA) and 1, 6-di(1H-imidazol-1-yl)pyrene (DIP) were obtained by solvothermal reactions. {[Zn(DPA)Cl2]·DMF·2H2O}n (1) and {[Zn1.5(DPA)1.5Cl3]·5H2O}n (2) are framework isomers, which both contain zigzag chains formed by DPA, Zn2+, and Cl-. The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers, and these layers exhibit two different orientations, displaying a rare 2D to 3D interpenetration mode. The zigzag chains in 2 are parallelly arranged. {[Zn3(DPA)3Br6]·2DMF·1.5H2O}n (3) is isostructural to 2. 3 was obtained using ZnBr2 instead of ZnCl2.[M(DPA) (formate)2(H2O)2]n[M=Co (4), Cu (5)] are isostructural, contain chain structures formed by DPA, Cu2+/Co2+, and formate ions, which were formed in situ in the solvothermal reaction. {[Zn(DIP)2Cl]ClO4}n (6) contains a layer structure formed by DIP and Zn2+. Free DPA and DIP ligands exhibited high fluorescence at room temperature, and coordination polymers 3 and 6 displayed enhanced fluorescent emissions.
