文献类型：期刊文献

英文题名：Reaction mechanism and kinetics for Pt/CNTs catalyzed base-free oxidation of glycerol

作者：Ma, Yuanyuan[1];Gan, Jie[1];Pan, Minjian[1];Zhang, Yanfang[1];Fu, Wenzhao[1];Duan, Xuezhi[1];Chen, Wenyao[1];Chen, De[2];Qian, Gang[1];Zhou, Xinggui[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2019

卷号：203

起止页码：228

外文期刊名：CHEMICAL ENGINEERING SCIENCE

收录：;EI(收录号：20191406725434);WOS:【SCI-EXPANDED(收录号:WOS:000465363600019)】；

基金：This work was financially supported by the Natural Science Foundation of China (21776077), the Shanghai Natural Science Foundation (17ZR1407300 and 17ZR1407500), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning, the Shanghai Rising-Star Program (17QA1401200), the Open Project of State Key Laboratory of Chemical Engineering (SKLChe-15C03), the State Key Laboratory of Organic-Inorganic Composites (oic-201801007), the Fundamental Research Funds for the Central Universities (222201718003), and the 111 Project of the Ministry of Education of China (B08021).

语种：英文

外文关键词：Base-free oxidation of glycerol; Solvent effects; DFT calculations; Kinetic isotope effects; Kinetics analysis

摘要：Fundamental understanding of heterogeneously catalyzed aerobic, base-free oxidation of glycerol is highly desirable for sustainable and highly efficient chemical synthesis. In this work, Pt/CNTs catalyzed base-free oxidation of glycerol is investigated by combining experiments, DFT calculations and kinetics analysis. The solvent effects and kinetic isotope effects measurements as well as DFT calculations reveal that water-assisted O-2 activation to form active OH* intermediates is not in rate-determining step (RDS) but in equilibrium. Then, Langmuir-Hinshelwood kinetic models are developed and fitted with the experimental data. The OH*-assisted C-H bond cleavage of glycerol is discriminated as the RDS for the two parallel oxidation pathways of glycerol via primary or secondary hydroxyl groups, where the former case exhibits lower activation energy. The insights revealed here could guide the design and optimization of this catalytic process to generate the targeted products. (C) 2019 Elsevier Ltd. All rights reserved.