Zheng Xiao-Xiao, Fang Zhong-Pu, Dai Zhao-Jin, Cai Jia-Ming, Shen Li-Juan, Zhang Yong-Fan, Au Chak-Tong, Jiang Li-Long
National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou 350002, Fujian PR China.
College of Chemistry, Fuzhou University, Fuzhou, Fujian 350116, PR China.
Inorg Chem. 2020 Apr 6;59(7):4483-4492. doi: 10.1021/acs.inorgchem.9b03648. Epub 2020 Mar 16.
Three classical Fe-MOFs, viz., MIL-100(Fe), MIL-101(Fe), and MIL-53(Fe), were synthesized to serve as platforms for the investigation of structure-activity relationship and catalytic mechanism in the selective conversion of HS to sulfur. The physicochemical properties of the Fe-MOFs were characterized by various techniques. It was disclosed that the desulfurization performances of Fe-MOFs with well-defined microstructures are obviously different. Among these, MIL-100(Fe) exhibits the highest catalytic performance (ca. 100% HS conversion and 100% S selectivity at 100-180 °C) that is superior to that of commercial FeO. Furthermore, the results of systematic characterization and DFT calculation reveal that the difference in catalytic performance is mainly because of discrepancy in the amount of Lewis acid sites. A plausible catalytic mechanism has been proposed for HS selective conversion over Fe-MOFs. This work provides critical insights that are helpful for rational design of desulfurization catalysts.
合成了三种经典的铁基金属有机框架材料，即MIL-100(Fe)、MIL-101(Fe)和MIL-53(Fe)，作为研究HS选择性转化为硫的构效关系和催化机理的平台。采用多种技术对铁基金属有机框架材料的物理化学性质进行了表征。结果表明，具有明确微观结构的铁基金属有机框架材料的脱硫性能明显不同。其中，MIL-100(Fe)表现出最高的催化性能（在100-180°C下，HS转化率约为100%，硫选择性为100%），优于商业FeO。此外，系统表征和密度泛函理论计算结果表明，催化性能的差异主要是由于路易斯酸位点数量的差异。提出了一种合理的铁基金属有机框架材料上HS选择性转化的催化机理。这项工作提供了重要的见解，有助于合理设计脱硫催化剂。
