Bioinspired microenvironment modulation of metal-organic framework-based catalysts for selective methane oxidation

Jianfei Sui; Ming-Liang Gao; Bing Qian; Chengyuan Liu; Yang Pan; Zheng Meng; Daqiang Yuan; Hai-Long Jiang

doi:10.1016/j.scib.2023.07.031

Bioinspired microenvironment modulation of metal-organic framework-based catalysts for selective methane oxidation

Sci Bull (Beijing). 2023 Sep 15;68(17):1886-1893. doi: 10.1016/j.scib.2023.07.031. Epub 2023 Jul 24.

Authors

Jianfei Sui¹, Ming-Liang Gao¹, Bing Qian², Chengyuan Liu², Yang Pan², Zheng Meng³, Daqiang Yuan⁴, Hai-Long Jiang⁵

Affiliations

¹ Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
² National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei 230029, China.
³ Department of Chemistry, University of Science and Technology of China, Hefei 230026, China. Electronic address: zhengmeng@ustc.edu.cn.
⁴ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
⁵ Department of Chemistry, University of Science and Technology of China, Hefei 230026, China. Electronic address: jianglab@ustc.edu.cn.

PMID: 37544879
DOI: 10.1016/j.scib.2023.07.031

Abstract

Inspiration from natural enzymes enabling creationary catalyst design is appealing yet remains extremely challenging for selective methane (CH₄) oxidation. This study presents the construction of a biomimetic catalyst platform for CH₄ oxidation, which is constructed by incorporating Fe-porphyrin into a robust metal-organic framework, UiO-66, furnished with saturated monocarboxylic fatty acid bearing different long alkyl chains. The catalysts demonstrate the high efficiency in the CH₄ to methanol (CH₃OH) conversion at 50 °C. Moreover, the selectivity to CH₃OH can be effectively regulated and promoted through a fine-tuned microenvironment by hydrophobic modification around the Fe-porphyrin. The long-chain fatty acids anchored on the Zr-oxo cluster of UiO-66 can not only tune the electronic state of the Fe sites to improve CH₄ adsorption, but also restrict the amount of H₂O₂ around the Fe sites to reduce the overoxidation. This behavior resembles the microenvironment regulation in methane monooxygenase, resulting in high CH₃OH selectivity.

Keywords: Bioinspired; Catalysis; Metal–organic frameworks; Methane oxidation; Microenvironment modulation.