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2025, 41(10): 1-2
Abstract:
2025, 41(10): 1929-1952
doi: 10.11862/CJIC.20250122
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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.
