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用于水煤气变换反应的二氧化铈负载铂催化剂活性位点的动态结构

Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction.

作者信息

Li Yuanyuan, Kottwitz Matthew, Vincent Joshua L, Enright Michael J, Liu Zongyuan, Zhang Lihua, Huang Jiahao, Senanayake Sanjaya D, Yang Wei-Chang D, Crozier Peter A, Nuzzo Ralph G, Frenkel Anatoly I

机构信息

Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, 11794, USA.

Department of Chemistry, University of Illinois, Urbana, IL, 61801, USA.

出版信息

Nat Commun. 2021 Feb 10;12(1):914. doi: 10.1038/s41467-021-21132-4.

Abstract

Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding-perhaps most importantly the temporal dynamic changes occurring therein-serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt - O vacancy-Ce sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction.

摘要

几十年来,负载型贵金属氧化物催化剂一直被广泛研究用于水煤气变换(WGS)反应,这是许多大量使用或生产氢气的工艺中的核心催化转化反应。关于活性金属-载体界面键合的具体特征——也许最重要的是其中发生的时间动态变化——如何导致高活性和选择性,仍然存在相当大的不确定性。在此,我们报告了用于WGS反应的Pt/CeO体系在原子水平上的动态特性,并特别揭示了周边区域金属-载体键合的协同效应。我们发现,活性结构中形成了周边Pt-O空位-Ce位点,在工作温度下发生转变,其出现调节了吸附质行为。我们发现,该位点的动态性质是WGS反应的关键机理步骤。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d272/7876036/50c44058a95f/41467_2021_21132_Fig1_HTML.jpg

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