Co-aromatization of methane and hexane over Pt encapsulated in ZSM-5 zeolite and the electronic effect of K promoters

作     者：Bei Liu Fan Wang Xiaomeng Dou Pengfei Li Hongwei Xiang Yong Yang Peng He 

作者机构：State Key Laboratory of Coal ConversionInstitute of Coal ChemistryChinese Academy of SciencesTaiyuan 030001China Department of ChemistryTsinghua UniversityBeijing 100084China National Energy R&D Center for Coal to Liquid FuelsSynfuels China Technology Co.Ltd.Beijing 101407China University of Chinese Academy of SciencesBeijing 101408China Leibniz-Institut für Katalyse e.V.an der Universitat RostockRostock 18059Germany 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2024年第67卷第3期

页      面：1017-1027页

核心收录：

学科分类：081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(22002179) the Shanxi Provincial Science and Technology Department(YDZJSX2022A074) 

主　　题：Pt encapsulation MFI zeolite methane activation co-aromatization ^(13)C solid-state NMR 

摘      要：The co-aromatization of methane with higher hydrocarbons represents a promising route to valorize methane, an abundant but underexploited carbon resource. In this study, we elucidate a novel approach to enhance the catalytic co-aromatization of hexane and methane by confining Pt within zeolite catalysts and modulating its electron density. Our findings show that encapsulating Pt within MFI structure is pivotal for activating the feedstock and fostering the formation of aromatic products. Interaction between K atoms and the silanol nest forms siloxy groups which are critical for the stabilization of Pt species. Tuning the K content in PtSn@MFI catalysts adeptly alters the electronic configuration of Pt clusters. This modification is corroborated by infrared and X-ray photoelectron spectroscopy analysis, and density functional theory calculations. Remarkably, the catalyst with 0.8 wt% K exhibits an optimal Pt electron density, driving its superior efficacy in the co-aromatization reaction, converting 0.78 mol of methane for each mole of hexane processed. By employing ~(13)C isotopic labeling and solid-state NMR studies, we demonstrate the participation of methane in the adsorbed species inside the zeolite channel and its incorporation to the benzyl site of the substitute group and phenyl rings in aromatic compounds, underscoring the importance of Pt encapsulation.