Ling Jie, Zhou Anning, Wang Wenzhen, Jia Xinyu, Ma Mengdan, Li Yizhong
College of Chemistry & Chemical Engineering, Xi'an University of Science and Technology, Xi an 710054, P. R. China.
College of Coal & Chemical Industry, Shaanxi Energy Institute, Hsienyang 712000, P. R. China.
ACS Omega. 2022 Jun 1;7(23):19920-19929. doi: 10.1021/acsomega.2c01717. eCollection 2022 Jun 14.
A magnesium-based metal-organic framework (Mg-MOF-74) exhibits excellent CO adsorption under ambient conditions. However, the photostability of Mg-MOF-74 for CO adsorption is poor. In this study, Mg Cu -MOF-74 was synthesized by using a facile "one-pot" method. Furthermore, the effects of synthesis conditions on the CO adsorption capacity were investigated comprehensively. X-ray diffraction, Fourier transform infrared, scanning electron microscopy, thermo gravimetric analysis, inductively coupled plasma atomic emission spectroscopy, ultraviolet-visible spectroscopy and photoluminescence spectroscopy, and CO static adsorption-desorption techniques were used to characterize the structures, morphology, and physicochemical properties of Mg Cu -MOF-74. CO uptake of Mg Cu -MOF-74 under visible light illumination was measured by the CO static adsorption test combined with the Xe lamp. The results revealed that Mg Cu -MOF-74 exhibited excellent photocatalytic activity. Furthermore, the CO adsorption capacity of Mg Cu -MOF-74 was excellent at a synthesis temperature and time of 398 K and 24 h in dimethylformamide (DMF)-EtOH-MeOH mixing solvents, respectively. Mg Cu -MOF-74 retained a crystal structure similar to that of the corresponding monometallic MOF-74, and its CO uptake under visible light was superior to that of the corresponding monometallic MOF-74. Particularly, the CO uptake of MgCu-MOF-74 under Xe lamp illumination for 24 h was the highest, up to 3.52 mmol·g, which was 1.18 and 2.09 times higher than that of Mg- and Cu-MOF-74, respectively. The yield of the photocatalytic reduction of CO to CO was 49.44 μmol·g over MgCu-MOF-74 under visible light for 8 h. Mg and Cu functioned as open alkali metal that could adsorb and activate CO. The synergistic effect between Mg and Cu metal strengthened Mg Cu -MOF-74 photostability for CO adsorption and broadened the scope of its photocatalytic application. The "bimetallic" strategy exhibits considerable potential for use in MOF-based semiconductor composites and provides a feasible method for catalyst design with remarkable CO adsorption capacity and photocatalytic activity.
一种镁基金属有机框架材料(Mg-MOF-74)在环境条件下表现出优异的CO吸附性能。然而,Mg-MOF-74用于CO吸附的光稳定性较差。在本研究中,采用简便的“一锅法”合成了Mg Cu -MOF-74。此外,还全面研究了合成条件对CO吸附容量的影响。利用X射线衍射、傅里叶变换红外光谱、扫描电子显微镜、热重分析、电感耦合等离子体原子发射光谱、紫外可见光谱和光致发光光谱以及CO静态吸附-脱附技术对Mg Cu -MOF-74的结构、形貌和物理化学性质进行了表征。通过结合Xe灯的CO静态吸附试验测定了Mg Cu -MOF-74在可见光照射下对CO的吸附量。结果表明,Mg Cu -MOF-74表现出优异的光催化活性。此外,在二甲基甲酰胺(DMF)-乙醇-甲醇混合溶剂中,合成温度和时间分别为398 K和24 h时,Mg Cu -MOF-74的CO吸附容量优异。Mg Cu -MOF-74保留了与相应单金属MOF-74相似的晶体结构,其在可见光下对CO的吸附量优于相应的单金属MOF-74。特别地,MgCu-MOF-74在Xe灯照射24 h下对CO的吸附量最高,达到3.52 mmol·g,分别比Mg-MOF-74和Cu-MOF-74高1.18倍和2.09倍。在可见光下8 h内,MgCu-MOF-74上CO光催化还原为CO的产率为49.44 μmol·g 。Mg和Cu起到开放碱金属的作用,能够吸附和活化CO。Mg和Cu金属之间的协同效应增强了Mg Cu -MOF-74对CO吸附的光稳定性,并拓宽了其光催化应用范围。“双金属”策略在基于MOF的半导体复合材料中具有相当大的应用潜力,并为设计具有卓越CO吸附容量和光催化活性的催化剂提供了一种可行的方法。