Microkinetics of steam methane reforming on platinum and rhodium metal surfaces

被引：47

作者：

Zhu, Tianwei ^{[1
,2
]}

van Grootel, Pieter W. ^{[1
]}

Filot, Ivo A. W. ^{[1
]}

Sun, Shi-Gang ^{[2
]}

van Santen, Rutger A. ^{[1
]}

Hensen, Emiel J. M. ^{[1
]}

机构：

[1] Eindhoven Univ Technol, Lab Inorgan Mat Chem, Schuit Inst Catalysis, NL-5612 AZ Eindhoven, Netherlands

[2] Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China

来源：

JOURNAL OF CATALYSIS | 2013年 / 297卷

关键词：

Platinum; Steam reforming; CO formation; H2O dissociation; Surface topology; Density functional calculations; Microkinetic simulations; TOTAL-ENERGY CALCULATIONS; CHEMICAL CONVERSION; REACTION PATHWAYS; STRUCTURAL REQUIREMENTS; SITE REQUIREMENTS; CO DISSOCIATION; ACTIVATION; RH; RU; SYNGAS;

D O I：

10.1016/j.jcat.2012.10.010

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

` We have investigated the most important elementary reaction steps in the steam methane reforming (SMR) process for planar and stepped Pt surfaces (dissociative CH4 adsorption, CHads-O-ads recombination, H2O activation) and compared activation barriers for Rh surfaces. Compared to Rh, the lower reactivity of Pt results in (i) higher barriers for dissociative CH4 adsorption and (ii) endothermic formation of OHads and O-ads. Microkinetic simulations show that Rh nanoparticle catalysts will be more active than Pt ones. The rate-controlling step is dissociative CH4 adsorption occurring on low-coordinated surface atoms (edges, corners, step-edges). The stepped surfaces are much more reactive than planar surfaces of the corresponding metals. For stepped Pt surfaces, CO formation via recombination of C-ads + OHads is favored because of the low O-ads coverage. At higher temperatures, deactivation may occur due to poisoning by carbonaceous species because the rate of OHads/O-ads formation becomes too low compared to the rate of CHads formation. This occurs at lower temperature for Pt than for Rh because of the lower Pt-O bond energy. (c) 2012 Elsevier Inc. All rights reserved.

引用

页码：227 / 235

页数：9

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