文献类型：期刊文献

英文题名：Kinetic Study of the Hydrogenation of Unsaturated Aldehydes Promoted by CuPtx/SBA-15 Single-Atom Alloy (SAA) Catalysts

作者：Cao, Yueqiang[1,2,3];Guerrero-Sanchez, Jonathan[4];Lee, Ilkeun[1,2];Zhou, Xinggui[3];Takeuchi, Noboru[1,2,4];Zaera, Francisco[1,2]

机构：[1]Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA;[2]Univ Calif Riverside, UCR Ctr Catalysis, Riverside, CA 92521 USA;[3]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[4]Univ Nacl Autonoma Mexico, Ctr Nanociencias & Nanotecnol, Ensenada, Baja California 22800, Mexico

年份：2020

卷号：10

期号：5

起止页码：3431

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20201208320172);WOS:【SCI-EXPANDED(收录号:WOS:000518876300055)】；

基金：Financial support for this project was provided by a grant from the U.S. National Science Foundation, Division of Chemistry (NSF-CHE 1660433). Y.C. acknowledges the 111 project of China (Grant No. B08021, Ministry of Education of the People's Republic of China and State Administration of Foreign Experts Affairs of People's Republic of China) for traveling support for his visit to Riverside to perform the reported experiments. N.T. and J.G.S. thank DGAPA-UNAM project IN100516, DGAPAUNAM project IN101019, and Conacyt grant A1-S-9070 for partial financial support. N.T. thanks DGAPA-UNAM for a scholarship at the University of California, Riverside. Calculations were performed in the DGCTIC-UNAM Supercomputing Center, project LANCAD-UNAM-DGTIC-051.

语种：英文

外文关键词：selective hydrogenation; unsaturated aldehydes; alloy catalysts; platinum; copper; kinetics

摘要：A comprehensive study of the kinetics of the catalytic hydrogenation of unsaturated aldehydes, in particular of cinnamaldehyde, promoted by CuPtx/SBA-15 single-atom alloy catalysts was carried out in order to identify trends as a function of the composition of the bimetallic nanoparticles, that is, of the value of x. The optimum performance reported by us recently [ACS Catal. 2019, 9, 9150-9157] in terms of selectivity toward the formation of cinnamyl alcohol, the desired product, by the catalyst with x = 0.005 was corroborated. A rapid decrease was seen in catalytic activity in batch reactors with all catalysts, in particular with pure Cu/SBA-15. This was ascribed, based on DFT calculations and microkinetic simulations, to the relative weak adsorption of the reactant compared to that of the products, which leads to the blocking of catalytic sites by the latter early on in the catalytic runs. It was determined that selectivity is controlled by the relative values of the initial rate constants for hydrogenation to the unsaturated alcohol versus the saturated aldehyde. Those were found to vary by up to an order of magnitude as a function of Pt content in the catalyst, in spite of the fact that the hydrogenation steps are presumed to occur on Cu, not Pt, sites. In general, significant changes in equilibrium and kinetic parameters were seen across the series of catalysts tested (versus x), indicating that the addition of even small amounts of Pt to these Cu single-atom alloy (SAA) catalysts affects the intrinsic performance of the hydrogenation catalytic sites.