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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(10): 1929-1952
doi: 10.11862/CJIC.20250122
摘要:
无机纳米X射线闪烁体因其优异的光学性能以及可溶液加工的特性，受到了研究者的广泛关注，在柔性闪烁屏、生物成像、疾病诊疗等领域具有广泛的应用前景。本文综述了无机纳米X射线闪烁体的研究进展，重点介绍了过渡金属离子掺杂纳米晶、量子点、团簇和纳米金属-有机框架闪烁体材料及其闪烁机制。同时，本文还总结了无机纳米X射线闪烁体在探测、信息存储、成像及治疗等领域的最新应用成果。最后，对无机纳米X射线闪烁体未来的发展方向进行了展望，并探讨了其在三维柔性探测器以及近红外Ⅱ区荧光成像领域的巨大应用潜力。
无机纳米X射线闪烁体因其优异的光学性能以及可溶液加工的特性，受到了研究者的广泛关注，在柔性闪烁屏、生物成像、疾病诊疗等领域具有广泛的应用前景。本文综述了无机纳米X射线闪烁体的研究进展，重点介绍了过渡金属离子掺杂纳米晶、量子点、团簇和纳米金属-有机框架闪烁体材料及其闪烁机制。同时，本文还总结了无机纳米X射线闪烁体在探测、信息存储、成像及治疗等领域的最新应用成果。最后，对无机纳米X射线闪烁体未来的发展方向进行了展望，并探讨了其在三维柔性探测器以及近红外Ⅱ区荧光成像领域的巨大应用潜力。
2025, 41(10): 1953-1972
doi: 10.11862/CJIC.20250160
摘要:
电化学传感器因其具有灵敏度高、选择性好、成本低廉、操作简便等特点，在疾病诊断、环境监测和食品安全等领域得到了广泛应用。电子导电金属有机框架(electrically conductive metal-organic frameworks，EC-MOFs)凭借其高比表面积、丰富的孔结构、灵活可调的设计特性以及优异的催化性能、高效的电子传输能力和显著的信号放大效应，为电化学传感领域提供了全新的研究机遇和发展方向。本文系统总结了EC-MOFs材料在电化学传感领域的最新研究进展，重点探讨了基于EC-MOFs电化学传感器工作电极的设计合成策略，详细评述了其在生物分子识别、环境污染物监测等方面的突破性应用，同时深入分析了EC-MOFs在电化学传感领域面临的关键挑战，并对其未来发展方向进行了展望。
电化学传感器因其具有灵敏度高、选择性好、成本低廉、操作简便等特点，在疾病诊断、环境监测和食品安全等领域得到了广泛应用。电子导电金属有机框架(electrically conductive metal-organic frameworks，EC-MOFs)凭借其高比表面积、丰富的孔结构、灵活可调的设计特性以及优异的催化性能、高效的电子传输能力和显著的信号放大效应，为电化学传感领域提供了全新的研究机遇和发展方向。本文系统总结了EC-MOFs材料在电化学传感领域的最新研究进展，重点探讨了基于EC-MOFs电化学传感器工作电极的设计合成策略，详细评述了其在生物分子识别、环境污染物监测等方面的突破性应用，同时深入分析了EC-MOFs在电化学传感领域面临的关键挑战，并对其未来发展方向进行了展望。
2025, 41(10): 2011-2028
doi: 10.11862/CJIC.20250185
摘要:
电催化析氧反应(OER)作为水裂解和金属-空气电池等清洁能源技术的关键半反应，对缓解能源危机与解决环境污染问题具有重要意义。然而，OER复杂的电子/质子转移机理和缓慢的反应动力学过程导致了较高的过电位，限制了能源转换的效率。因此急需开发高效、稳定的OER催化剂来提高反应效率。金属有机框架(MOFs)因其充足的金属中心、较大的比表面积和灵活可调节的结构，被认为是极具潜力的电催化剂。本文系统地介绍了高效MOFs基电催化剂的设计策略，并探讨了该领域目前面临的挑战与未来的发展方向。
电催化析氧反应(OER)作为水裂解和金属-空气电池等清洁能源技术的关键半反应，对缓解能源危机与解决环境污染问题具有重要意义。然而，OER复杂的电子/质子转移机理和缓慢的反应动力学过程导致了较高的过电位，限制了能源转换的效率。因此急需开发高效、稳定的OER催化剂来提高反应效率。金属有机框架(MOFs)因其充足的金属中心、较大的比表面积和灵活可调节的结构，被认为是极具潜力的电催化剂。本文系统地介绍了高效MOFs基电催化剂的设计策略，并探讨了该领域目前面临的挑战与未来的发展方向。
2025, 41(10): 2029-2038
doi: 10.11862/CJIC.20250186
摘要:
超级电容器是一种高效的电化学储能器件，电极材料是影响其性能的关键因素。近年来，金属有机骨架(MOF)材料由于其独特的结构和性质，成为提升超级电容器性能的理想选择。特别是镍基金属有机骨架(Ni-MOF)材料，因其良好的稳定性和适宜的反应电位，表现出优异的电化学储能性能。然而，该材料在实际应用中仍面临一些问题，并通过材料复合或衍生化处理，有望进一步提升其电化学性能。本文综述了Ni-MOF及其复合物、衍生物在超级电容器中的应用，为高性能储能设备的开发提供了新的思路。
超级电容器是一种高效的电化学储能器件，电极材料是影响其性能的关键因素。近年来，金属有机骨架(MOF)材料由于其独特的结构和性质，成为提升超级电容器性能的理想选择。特别是镍基金属有机骨架(Ni-MOF)材料，因其良好的稳定性和适宜的反应电位，表现出优异的电化学储能性能。然而，该材料在实际应用中仍面临一些问题，并通过材料复合或衍生化处理，有望进一步提升其电化学性能。本文综述了Ni-MOF及其复合物、衍生物在超级电容器中的应用，为高性能储能设备的开发提供了新的思路。
2025, 41(10): 1973-2010
doi: 10.11862/CJIC.20250175
摘要:
The selective hydrogenation of α, β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule. This approach serves as a critical strategy for the directional synthesis of high-value molecules. However, achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds in α, β-unsaturated systems. Consequently, constructing precisely targeted catalytic systems is essential to overcome these limitations, offering both fundamental scientific significance and industrial application potential. Metal-organic frameworks (MOFs) and their derivatives have emerged as innovative platforms for designing such systems, owing to their programmable topology, tunable pore microenvironments, spatially controllable active sites, and modifiable electronic structures. This review systematically summarizes the research progress of MOF-based catalysts for selective hydrogenation of α, β-unsaturated aldehydes/ketones in the last decade, with emphasis on the design strategy, conformational relationship, and catalytic mechanism, aiming to provide new ideas for the design of targeted catalytic systems for the selective hydrogenation of α, β-unsaturated aldehydes/ketones.
The selective hydrogenation of α, β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule. This approach serves as a critical strategy for the directional synthesis of high-value molecules. However, achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds in α, β-unsaturated systems. Consequently, constructing precisely targeted catalytic systems is essential to overcome these limitations, offering both fundamental scientific significance and industrial application potential. Metal-organic frameworks (MOFs) and their derivatives have emerged as innovative platforms for designing such systems, owing to their programmable topology, tunable pore microenvironments, spatially controllable active sites, and modifiable electronic structures. This review systematically summarizes the research progress of MOF-based catalysts for selective hydrogenation of α, β-unsaturated aldehydes/ketones in the last decade, with emphasis on the design strategy, conformational relationship, and catalytic mechanism, aiming to provide new ideas for the design of targeted catalytic systems for the selective hydrogenation of α, β-unsaturated aldehydes/ketones.
2025, 41(10): 2039-2053
doi: 10.11862/CJIC.20250036
摘要:
Hollow multi-shelled structure (HoMS) is the novel multifunctional structural system, which are constructed with nanoparticles as structural units, featuring two or more shells, multiple interfaces, and numerous channels and demonstrating outstanding properties in energy conversion and mass transfer. In recent years, owing to the breakthroughs in synthetic methods, the diversity of composition and structure of HoMS has been greatly enriched, showing broad application prospects in energy, catalysis, environment and other fields. This review focuses on the research status of HoMS for catalytic applications. Firstly, the new synthesis method for HoMS, namely the sequential templating approach, is introduced from both practical and theoretical perspectives. Then, it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance. The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed. Finally, it looks forward to the opportunities and challenges in the development of HoMS.
Hollow multi-shelled structure (HoMS) is the novel multifunctional structural system, which are constructed with nanoparticles as structural units, featuring two or more shells, multiple interfaces, and numerous channels and demonstrating outstanding properties in energy conversion and mass transfer. In recent years, owing to the breakthroughs in synthetic methods, the diversity of composition and structure of HoMS has been greatly enriched, showing broad application prospects in energy, catalysis, environment and other fields. This review focuses on the research status of HoMS for catalytic applications. Firstly, the new synthesis method for HoMS, namely the sequential templating approach, is introduced from both practical and theoretical perspectives. Then, it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance. The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed. Finally, it looks forward to the opportunities and challenges in the development of HoMS.
2025, 41(10): 2054-2062
doi: 10.11862/CJIC.20250096
摘要:
本研究采用溶剂热法制备了一种具有狭缝孔结构的铝基-卟啉金属有机骨架(Al-TCPP)材料，并研究了其对电子特种气体C3F8的吸附分离和回收性能。所合成的Al-TCPP具有狭长平板孔结构，其孔尺寸为0.6 nm×1.1 nm，略微大于C3F8的分子尺寸(0.57 nm×0.52 nm)。同时，Al-TCPP孔道内密布的C—H键与μ-OH基团可与C3F8的F原子形成多重氢键作用位点，进一步增强了对C3F8的亲和力。吸附实验结果表明，在298 K、100 kPa下Al-TCPP对C3F8的吸附量高达96.1 cm3·g-1，而N2吸附量仅为6.1 cm3·g-1，其理想选择性高达244.8，超过了目前已报道的吸附剂材料。同时，C3F8在低压区的吸附热为50.6 kJ·mol-1，远高于N2的16.5 kJ·mol-1。密度泛函理论(DFT)计算表明，Al-TCPP结构中相邻的卟啉单元上的多个H原子可以同时与C3F8的多个F原子形成氢键。穿透实验证实Al-TCPP可以实现C3F8/N2混合物的有效分离，并且通过脱附可以回收获得高纯度的C3F8。
本研究采用溶剂热法制备了一种具有狭缝孔结构的铝基-卟啉金属有机骨架(Al-TCPP)材料，并研究了其对电子特种气体C3F8的吸附分离和回收性能。所合成的Al-TCPP具有狭长平板孔结构，其孔尺寸为0.6 nm×1.1 nm，略微大于C3F8的分子尺寸(0.57 nm×0.52 nm)。同时，Al-TCPP孔道内密布的C—H键与μ-OH基团可与C3F8的F原子形成多重氢键作用位点，进一步增强了对C3F8的亲和力。吸附实验结果表明，在298 K、100 kPa下Al-TCPP对C3F8的吸附量高达96.1 cm3·g-1，而N2吸附量仅为6.1 cm3·g-1，其理想选择性高达244.8，超过了目前已报道的吸附剂材料。同时，C3F8在低压区的吸附热为50.6 kJ·mol-1，远高于N2的16.5 kJ·mol-1。密度泛函理论(DFT)计算表明，Al-TCPP结构中相邻的卟啉单元上的多个H原子可以同时与C3F8的多个F原子形成氢键。穿透实验证实Al-TCPP可以实现C3F8/N2混合物的有效分离，并且通过脱附可以回收获得高纯度的C3F8。
2025, 41(10): 2063-2068
doi: 10.11862/CJIC.20250020
摘要:
氨气是一种有毒气体，排放到空气中会对人类和环境造成不可估量的危害，制备廉价、绿色的氨气吸附材料对于氨气处理具有重要意义。本研究采用低成本的8-羟基喹啉-5-磺酸(H2QS)作为配体，通过简单的低温水热法合成了La3+基金属有机框架{[La4(QS)6(H2O)6]·18H2O}n (MOF-LaQS)。实验结果显示，MOF-LaQS在273 K、101 kPa条件下对氨气的最大吸附量可达228 cm3·g-1(10.2 mmol·g-1)，且在极低压力(0.101 kPa)下仍能吸附48 cm3·g-1(2.14 mmol·g-1)的氨气。通过原位红外光谱和密度泛函理论计算证实了MOF-LaQS中开放的La3+金属位点是吸附氨气的关键位点，揭示了其高效吸附氨气的机理。
氨气是一种有毒气体，排放到空气中会对人类和环境造成不可估量的危害，制备廉价、绿色的氨气吸附材料对于氨气处理具有重要意义。本研究采用低成本的8-羟基喹啉-5-磺酸(H2QS)作为配体，通过简单的低温水热法合成了La3+基金属有机框架{[La4(QS)6(H2O)6]·18H2O}n (MOF-LaQS)。实验结果显示，MOF-LaQS在273 K、101 kPa条件下对氨气的最大吸附量可达228 cm3·g-1(10.2 mmol·g-1)，且在极低压力(0.101 kPa)下仍能吸附48 cm3·g-1(2.14 mmol·g-1)的氨气。通过原位红外光谱和密度泛函理论计算证实了MOF-LaQS中开放的La3+金属位点是吸附氨气的关键位点，揭示了其高效吸附氨气的机理。
2025, 41(10): 2069-2077
doi: 10.11862/CJIC.20250129
摘要:
以(Et4N)[Tp*WS3(CuCl)3] (A)(Tp*=三(3，5-二甲基吡唑)氢合硼酸根)为前驱簇，经Ag(OTf)脱氯后，分别与2种含炔基双齿吡啶配体1，3-双[4-(吡啶-4-基乙炔基)苯基]丙烷(L1)和1，3-双[4-(吡啶-4-基乙炔基)苯基]丙-2-酮(L2)进行自组装，构筑了2个W/Cu/S簇基超分子矩形大环化合物[(Tp*WS3Cu2Cl)4(L1)2]·6CH2Cl2 (1·6CH2Cl2)和[(Tp*WS3Cu2Cl)4(L2)2]·6CH2Cl2 (2·6CH2Cl2)。在构筑这2个簇合物的过程中，L1或L2中的1个炔基与前驱簇A中2个S发生了不多见的环加成反应，从而形成了1和2簇基超分子矩形大环。在1·6CH2Cl2和2·6CH2Cl2的反应体系中引入吡啶(Py)作为第二配体，获得了新型簇合物[Tp*WS3Cu3(μ3-Cl)(Py)3](OTf) (3)。通过单晶X射线衍射、电喷雾电离质谱、红外光谱、紫外可见光谱和元素分析对3个簇合物进行了系统表征。单晶X射线衍射结果表明，1·6CH2Cl2和2·6CH2Cl2均是由2个双齿配体(L1或L2)桥联4个[Tp*WS3Cu2Cl]簇单元形成的簇基超分子矩形大环。簇合物3含有3个吡啶分子配位的阳离子[Tp*WS3Cu3(μ3-Cl)]+类立方烷型结构。采用Z扫描法对簇合物1·6CH2Cl2、2·6CH2Cl2和3的溶液的三阶非线性光学(NLO)性质进行测试，结果表明它们具有良好的三阶NLO响应。
以(Et4N)[Tp*WS3(CuCl)3] (A)(Tp*=三(3，5-二甲基吡唑)氢合硼酸根)为前驱簇，经Ag(OTf)脱氯后，分别与2种含炔基双齿吡啶配体1，3-双[4-(吡啶-4-基乙炔基)苯基]丙烷(L1)和1，3-双[4-(吡啶-4-基乙炔基)苯基]丙-2-酮(L2)进行自组装，构筑了2个W/Cu/S簇基超分子矩形大环化合物[(Tp*WS3Cu2Cl)4(L1)2]·6CH2Cl2 (1·6CH2Cl2)和[(Tp*WS3Cu2Cl)4(L2)2]·6CH2Cl2 (2·6CH2Cl2)。在构筑这2个簇合物的过程中，L1或L2中的1个炔基与前驱簇A中2个S发生了不多见的环加成反应，从而形成了1和2簇基超分子矩形大环。在1·6CH2Cl2和2·6CH2Cl2的反应体系中引入吡啶(Py)作为第二配体，获得了新型簇合物[Tp*WS3Cu3(μ3-Cl)(Py)3](OTf) (3)。通过单晶X射线衍射、电喷雾电离质谱、红外光谱、紫外可见光谱和元素分析对3个簇合物进行了系统表征。单晶X射线衍射结果表明，1·6CH2Cl2和2·6CH2Cl2均是由2个双齿配体(L1或L2)桥联4个[Tp*WS3Cu2Cl]簇单元形成的簇基超分子矩形大环。簇合物3含有3个吡啶分子配位的阳离子[Tp*WS3Cu3(μ3-Cl)]+类立方烷型结构。采用Z扫描法对簇合物1·6CH2Cl2、2·6CH2Cl2和3的溶液的三阶非线性光学(NLO)性质进行测试，结果表明它们具有良好的三阶NLO响应。
2025, 41(10): 2078-2086
doi: 10.11862/CJIC.20250167
摘要:
在溶剂热条件下以4，4′，4″-三甲酸三苯胺(H3NTB)为电子给体、4，4′-联吡啶(bipy)为电子受体，与金属盐Zn(NO3)2·6H2O反应，制备了一例具有电荷转移特性和三维多轮烷结构的金属有机框架荧光粉[Zn3(NTB)2(bipy)]·4H2O (1)。利用X射线单晶衍射、X射线粉末衍射、热重分析等技术确定了化合物1的晶体结构、相纯度和稳定性。晶体结构分析表明化合物1结晶于三斜晶系，P1空间群，晶胞参数a=1.374 87(15) nm，b=1.376 65(15) nm，c=1.795 50(18) nm，α=86.994(9)°，β=82.384(9)°，γ=64.835(11)°。室温下，该化合物具有亮黄色的荧光(发射峰为575 nm)，发光寿命为16.01 ns。温度依赖光致发光测试表明，该化合物在150 ℃时仍能保持92.05%的发光强度(相对于室温)，高于部分硼酸、硅酸盐基无机荧光粉。
在溶剂热条件下以4，4′，4″-三甲酸三苯胺(H3NTB)为电子给体、4，4′-联吡啶(bipy)为电子受体，与金属盐Zn(NO3)2·6H2O反应，制备了一例具有电荷转移特性和三维多轮烷结构的金属有机框架荧光粉[Zn3(NTB)2(bipy)]·4H2O (1)。利用X射线单晶衍射、X射线粉末衍射、热重分析等技术确定了化合物1的晶体结构、相纯度和稳定性。晶体结构分析表明化合物1结晶于三斜晶系，P1空间群，晶胞参数a=1.374 87(15) nm，b=1.376 65(15) nm，c=1.795 50(18) nm，α=86.994(9)°，β=82.384(9)°，γ=64.835(11)°。室温下，该化合物具有亮黄色的荧光(发射峰为575 nm)，发光寿命为16.01 ns。温度依赖光致发光测试表明，该化合物在150 ℃时仍能保持92.05%的发光强度(相对于室温)，高于部分硼酸、硅酸盐基无机荧光粉。
2025, 41(10): 2087-2094
doi: 10.11862/CJIC.20250182
摘要:
在溶剂热条件下，合成了双金属镧系金属有机框架Eu0.52Tb0.48-TCPP(H4TCPP=4，4′，4″，4‴-(吡嗪-2，3，5，6-四)四苯甲酸)，并通过粉末X射线衍射、热重、红外光谱以及元素分析对其结构与组成进行了表征。Eu0.52Tb0.48-TCPP表现出良好的化学稳定性、热稳定性及荧光传感性能，实现了对2，4，6-三硝基苯酚(TNP)的高效、灵敏检测，检测限为0.49 μmol·L-1。此外，探究了Eu0.52Tb0.48-TCPP检测TNP的荧光传感机理，并成功制备了一种便携试纸及聚合物器件，用于污染物的原位实时检测。
在溶剂热条件下，合成了双金属镧系金属有机框架Eu0.52Tb0.48-TCPP(H4TCPP=4，4′，4″，4‴-(吡嗪-2，3，5，6-四)四苯甲酸)，并通过粉末X射线衍射、热重、红外光谱以及元素分析对其结构与组成进行了表征。Eu0.52Tb0.48-TCPP表现出良好的化学稳定性、热稳定性及荧光传感性能，实现了对2，4，6-三硝基苯酚(TNP)的高效、灵敏检测，检测限为0.49 μmol·L-1。此外，探究了Eu0.52Tb0.48-TCPP检测TNP的荧光传感机理，并成功制备了一种便携试纸及聚合物器件，用于污染物的原位实时检测。
2025, 41(10): 2095-2102
doi: 10.11862/CJIC.20250025
摘要:
Ultrafine, highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74. Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms, the obtained Pt-on-Co/C400 catalysts exhibited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency (TOF) value of 3 022 min-1 at 303 K. Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability, and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
Ultrafine, highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74. Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms, the obtained Pt-on-Co/C400 catalysts exhibited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency (TOF) value of 3 022 min-1 at 303 K. Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability, and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
2025, 41(10): 2103-2114
doi: 10.11862/CJIC.20250110
摘要:
Perfluoroalkyl acids of different chain lengths, including trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid, were used as second ligands to replace the formic acid on the Zr6 clusters in MOF-808. This led to the formation of a series of MOF-808-R materials (R=F3, F7, F9, corresponding to trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid) with multiple ligands, and we investigated the impact of the second ligand modification on pore size and pore environment. The loading amount of the second ligand was determined using NMR and other methods. We conducted adsorption tests for acetylene and carbon dioxide at different temperatures on both MOF-808 and MOF-808-R to explore the effects of the ligand diversification on acetylene separation performance. It was found that MOF-808-F7 exhibited the best performance in acetylene-carbon dioxide separation.
Perfluoroalkyl acids of different chain lengths, including trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid, were used as second ligands to replace the formic acid on the Zr6 clusters in MOF-808. This led to the formation of a series of MOF-808-R materials (R=F3, F7, F9, corresponding to trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid) with multiple ligands, and we investigated the impact of the second ligand modification on pore size and pore environment. The loading amount of the second ligand was determined using NMR and other methods. We conducted adsorption tests for acetylene and carbon dioxide at different temperatures on both MOF-808 and MOF-808-R to explore the effects of the ligand diversification on acetylene separation performance. It was found that MOF-808-F7 exhibited the best performance in acetylene-carbon dioxide separation.
2025, 41(10): 2115-2126
doi: 10.11862/CJIC.20250139
摘要:
In the paper, we report a highly robust and porous bimetallic Ti-MOF (designated Mg2Ti-ABTC) by utilizing a trinuclear [Mg2TiO(COO)6] cluster and a tetradentate H4ABTC (3, 3′, 5, 5′-azobenzene tetracarboxylic acid) ligand. Mg2Ti-ABTC exhibited permanent porosity for N2, CO2, CH4, C2H2, C2H4, and C2H6 gas adsorption. Furthermore, Mg2Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corresponding sulfoxides under ambient air conditions. Mechanism studies reveal that photoinduced holes (h+), the superoxide radical (•O2-), and singlet oxygen (1O2) are pivotal species involved in the photocatalytic oxidation reaction.
In the paper, we report a highly robust and porous bimetallic Ti-MOF (designated Mg2Ti-ABTC) by utilizing a trinuclear [Mg2TiO(COO)6] cluster and a tetradentate H4ABTC (3, 3′, 5, 5′-azobenzene tetracarboxylic acid) ligand. Mg2Ti-ABTC exhibited permanent porosity for N2, CO2, CH4, C2H2, C2H4, and C2H6 gas adsorption. Furthermore, Mg2Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corresponding sulfoxides under ambient air conditions. Mechanism studies reveal that photoinduced holes (h+), the superoxide radical (•O2-), and singlet oxygen (1O2) are pivotal species involved in the photocatalytic oxidation reaction.
2025, 41(10): 2127-2137
doi: 10.11862/CJIC.20250149
摘要:
To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis, two new lanthanum phosphite-oxalates with 3D frameworks, designated as [La(HPO3)(C2O4)0.5(H2O)2] (La-1) and (C6H16N2)(H3O)[La2(H2PO3)3(C2O4)3(H2O)] (La-2) (C6H14N2=cis-, 6-dimethylpiperazine), were prepared by hydrothermal and solvothermal conduction, respectively. La-1 was constructed with lanthanum phosphite 2D layers and C2O42- groups, whereas La-2 was constructed with lanthanum oxalate 2D layers and H2PO3- groups. Alternating current (AC) impedance spectra indicate that the proton conductivities of both compounds could reach 10-4 S•cm-1 and remain highly durable at 75 ℃ and 98% of relative humidity (RH). Due to the abundance of H-bonds in La-2, the σ of La-2 was higher than that of La-1. La-1 exhibited excellent water and pH stability.
To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis, two new lanthanum phosphite-oxalates with 3D frameworks, designated as [La(HPO3)(C2O4)0.5(H2O)2] (La-1) and (C6H16N2)(H3O)[La2(H2PO3)3(C2O4)3(H2O)] (La-2) (C6H14N2=cis-, 6-dimethylpiperazine), were prepared by hydrothermal and solvothermal conduction, respectively. La-1 was constructed with lanthanum phosphite 2D layers and C2O42- groups, whereas La-2 was constructed with lanthanum oxalate 2D layers and H2PO3- groups. Alternating current (AC) impedance spectra indicate that the proton conductivities of both compounds could reach 10-4 S•cm-1 and remain highly durable at 75 ℃ and 98% of relative humidity (RH). Due to the abundance of H-bonds in La-2, the σ of La-2 was higher than that of La-1. La-1 exhibited excellent water and pH stability.
2025, 41(10): 2138-2148
doi: 10.11862/CJIC.20250154
摘要:
We report a robust pillar-layered metal-organic framework, Zn-tfbdc-dabco (tfbdc: tetrafluoroterephthalate, dabco: 1, 4-diazabicyclo[2.2.2]octane), featuring the fluorinated pore environment, for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture. The inverse propane-selective performance of Zn-tfbdc-dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms, isosteric enthalpy of adsorption calculations, ideal adsorbed solution theory calculations, along with the breakthrough experiment. The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane, as unveiled by the simulation studies at the molecular level. With the advantage of inverse propane-selective adsorption behavior, high adsorption capacity, good cycling stability, and low isosteric enthalpy of adsorption, Zn-tfbdc-dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.
We report a robust pillar-layered metal-organic framework, Zn-tfbdc-dabco (tfbdc: tetrafluoroterephthalate, dabco: 1, 4-diazabicyclo[2.2.2]octane), featuring the fluorinated pore environment, for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture. The inverse propane-selective performance of Zn-tfbdc-dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms, isosteric enthalpy of adsorption calculations, ideal adsorbed solution theory calculations, along with the breakthrough experiment. The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane, as unveiled by the simulation studies at the molecular level. With the advantage of inverse propane-selective adsorption behavior, high adsorption capacity, good cycling stability, and low isosteric enthalpy of adsorption, Zn-tfbdc-dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.
2025, 41(10): 2149-2156
doi: 10.11862/CJIC.20250177
摘要:
Herein, we report the synthesis and third-order nonlinear optical (NLO) properties of a novel cage-based 2D metal-organic framework constructed from Ti4L6 (L4-=embonate) cage combined with Mg2+ and tris[4-(1H-imidazol-1-yl)phenyl]amine (tipa) ligand, whose molecular formula is (Me2CH2)2[Mg3(Ti4L6)(tipa)(H2O)12] (PTC-378). The Ti4L6 tetrahedral cages serve as robust building units, while the Mg2+ ions and tipa ligands provide structural stability and tunable optical properties. The resulting PTC-378 film exhibited intriguing third-order NLO property, which was systematically investigated using Z-scan techniques. Our results demonstrate that the synergistic interaction between Ti4L6 cages and π-conjugated ligands significantly enhances the NLO performance of the materials.
Herein, we report the synthesis and third-order nonlinear optical (NLO) properties of a novel cage-based 2D metal-organic framework constructed from Ti4L6 (L4-=embonate) cage combined with Mg2+ and tris[4-(1H-imidazol-1-yl)phenyl]amine (tipa) ligand, whose molecular formula is (Me2CH2)2[Mg3(Ti4L6)(tipa)(H2O)12] (PTC-378). The Ti4L6 tetrahedral cages serve as robust building units, while the Mg2+ ions and tipa ligands provide structural stability and tunable optical properties. The resulting PTC-378 film exhibited intriguing third-order NLO property, which was systematically investigated using Z-scan techniques. Our results demonstrate that the synergistic interaction between Ti4L6 cages and π-conjugated ligands significantly enhances the NLO performance of the materials.
2025, 41(10): 2157-2164
doi: 10.11862/CJIC.20250179
摘要:
To obtain materials capable of efficiently separating acetylene (C2H2) from carbon dioxide (CO2) and ethylene (C2H4), In this work, based on the pore space partition strategy, a pacs-metal-organic framework (MOF): (NH2Me2)2[Fe3(μ3-O)(bdc)3][In(FA)3Cl3] (Fe-FAIn-bdc) was synthesized successfully by using the metal-formate complex [In(FA)3Cl3]3- as the pore partition units, where bdc2-=terephthalate, FA-=formate. Owing to the pore partition effect of this metal-organic building block, fruitful confined spaces are formed in the network of Fe-FAIn-bdc, endowing this MOF with superior separation performance of acetylene and carbon dioxide. According to the adsorption test, this MOF exhibited a high adsorption capacity for C2H2 (50.79 cm3·g-1) at 298 K and 100 kPa, which was much higher than that for CO2 (29.99 cm3·g-1) and C2H4 (30.94 cm3·g-1) under the same conditions. Ideal adsorbed solution theory (IAST) calculations demonstrate that the adsorption selectivity of Fe-FAIn-bdc for the mixture of C2H2/CO2 and C2H2/C2H4 in a volume ratio of 50∶50 was 3.08 and 3.65, respectively, which was higher than some reported MOFs such as NUM-11 and SNNU-18.
To obtain materials capable of efficiently separating acetylene (C2H2) from carbon dioxide (CO2) and ethylene (C2H4), In this work, based on the pore space partition strategy, a pacs-metal-organic framework (MOF): (NH2Me2)2[Fe3(μ3-O)(bdc)3][In(FA)3Cl3] (Fe-FAIn-bdc) was synthesized successfully by using the metal-formate complex [In(FA)3Cl3]3- as the pore partition units, where bdc2-=terephthalate, FA-=formate. Owing to the pore partition effect of this metal-organic building block, fruitful confined spaces are formed in the network of Fe-FAIn-bdc, endowing this MOF with superior separation performance of acetylene and carbon dioxide. According to the adsorption test, this MOF exhibited a high adsorption capacity for C2H2 (50.79 cm3·g-1) at 298 K and 100 kPa, which was much higher than that for CO2 (29.99 cm3·g-1) and C2H4 (30.94 cm3·g-1) under the same conditions. Ideal adsorbed solution theory (IAST) calculations demonstrate that the adsorption selectivity of Fe-FAIn-bdc for the mixture of C2H2/CO2 and C2H2/C2H4 in a volume ratio of 50∶50 was 3.08 and 3.65, respectively, which was higher than some reported MOFs such as NUM-11 and SNNU-18.
2025, 41(10): 2165-2174
doi: 10.11862/CJIC.20250190
摘要:
Herein, a luminescent europium-based metal-organic framework (Eu-MOF, [Eu3(L)(HL)(NO3)2(DMF)2]·4DMF·5H2O, H4L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid, DMF=N,N-dimethylformamide) was developed for the dual-functional detection of environmental pollutants. This fluorescence-quenching-based sensor exhibited exceptional sensitivity for both 2,4,6-trinitrophenol (TNP) and tetracycline (TC), achieving remarkably low detection limits of 1.96×10-6 and 1.71×10-7 mol·L-1, respectively. Notably, the system exhibited 99% fluorescence quenching efficiency for TC, indicating ultra-efficient analyte recognition. The detection performance surpasses most reported luminescent MOF sensors, attributed to synergistic mechanisms of fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET).
Herein, a luminescent europium-based metal-organic framework (Eu-MOF, [Eu3(L)(HL)(NO3)2(DMF)2]·4DMF·5H2O, H4L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid, DMF=N,N-dimethylformamide) was developed for the dual-functional detection of environmental pollutants. This fluorescence-quenching-based sensor exhibited exceptional sensitivity for both 2,4,6-trinitrophenol (TNP) and tetracycline (TC), achieving remarkably low detection limits of 1.96×10-6 and 1.71×10-7 mol·L-1, respectively. Notably, the system exhibited 99% fluorescence quenching efficiency for TC, indicating ultra-efficient analyte recognition. The detection performance surpasses most reported luminescent MOF sensors, attributed to synergistic mechanisms of fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET).
2025, 41(10): 2175-2185
doi: 10.11862/CJIC.20250218
摘要:
Through employing zeolitic imidazolate framework-67 (ZIF-67) templates, the straightforward hydrothermal and electrodeposition methods were applied to synthesize FeOOH@CoMoO4 heterostructure attached to the surface of nickel foam (NF). The specific structure of the as-prepared FeOOH@CoMoO4/NF-400s provided pronounced porosity and extensive surface area, enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions. Furthermore, the introduction of FeOOH, which induces electron transfer from FeOOH to CoMoO4, confirms their strong electronic interaction, thereby leading to an accelerated surface catalytic reaction. Consequently, the constructed FeOOH@CoMoO4/NF-400s heterostructure demonstrated exceptional oxygen evolution reaction (OER) activity, requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm-2, coupled with the superior Tafel slope value of 49.56 mV·dec-1 and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm-2.
Through employing zeolitic imidazolate framework-67 (ZIF-67) templates, the straightforward hydrothermal and electrodeposition methods were applied to synthesize FeOOH@CoMoO4 heterostructure attached to the surface of nickel foam (NF). The specific structure of the as-prepared FeOOH@CoMoO4/NF-400s provided pronounced porosity and extensive surface area, enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions. Furthermore, the introduction of FeOOH, which induces electron transfer from FeOOH to CoMoO4, confirms their strong electronic interaction, thereby leading to an accelerated surface catalytic reaction. Consequently, the constructed FeOOH@CoMoO4/NF-400s heterostructure demonstrated exceptional oxygen evolution reaction (OER) activity, requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm-2, coupled with the superior Tafel slope value of 49.56 mV·dec-1 and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm-2.
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.
