文献类型：期刊文献

英文题名：Ruthenium/TiO2-Catalyzed Hydrogenolysis of Polyethylene Terephthalate: Reaction Pathways Dominated by Coordination Environment

作者：Ye, Mingxing[1];Li, Yurou[1];Yang, Zhirong[1];Yao, Chang[1];Sun, Weixiao[1];Zhang, Xiangxue[1];Chen, Wenyao[1];Qian, Gang[1];Duan, Xuezhi[1];Cao, Yueqiang[1];Li, Lina[2];Zhou, Xinggui[1];Zhang, Jing[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Chinese Acad Sci, Shanghai Adv Res Inst, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China

年份：2023

卷号：62

期号：19

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20231413840931);WOS:【SCI-EXPANDED(收录号:WOS:000961323500001)】；

基金：Acknowledgments This work was financially supported by the National Key R&D Program of China (2022YFA1503502 and 2022YFA1503503), the National Natural Science Foundation of China (22008074, 21991103, 22008072, 21991104); Natural Science Foundation of Shanghai (20ZR1415700), China Postdoctoral Science Foundation (2020M671025, 2019TQ0093). We thank the staff of the 11B beamline at the Shanghai Synchrotron Radiation Facility (SSRF) for data collection. The authors are also thankful to Dr. Yanqin Wang, Dr. Yaxuan Jing, Dr. Xiaohui Liu from East China University of Science and Technology for helpful discussion.

语种：英文

外文关键词：Arenes; Heterogeneous Catalysis; Hydrogenolysis; Plastic; Ruthenium

摘要：Polyethylene terephthalate (PET) hydrogenolysis can produce benzene, toluene, and xylene (BTX), where the selectivity control is challenging. We report a reaction pathway dictated by the Ru coordination environment by examining the binding geometries of adsorbates on differently coordinated Ru centers and their evolution during PET hydrogenolysis. A BTX yield of 77 % was obtained using a Ru/TiO2 with a Ru coordination number of ca. 5.0 where edge/corner sites are dominant, while more gas and saturated products were formed for Ru/TiO2 containing primarily terrace sites. Density functional theory and isotopic labelling revealed that under-coordinated Ru edge sites favor "upright" adsorption of aromatic adsorbates while well-coordinated Ru sites favor "flat-lying" adsorption, where the former mitigates ring hydrogenation and opening. This study demonstrates that reaction pathways can be directed through controlled reactant/intermediate binding via tuning of the Ru coordination environment for efficient conversion of PET to BTX.