文献类型：期刊文献

英文题名：Computational Investigation of the Thermochemistry and Kinetics of Steam Methane Reforming Over a Multi-Faceted Nickel Catalyst

作者：Blaylock, D. Wayne[1];Zhu, Yi-An[2];Green, William H.[1]

机构：[1]MIT, Dept Chem Engn, Cambridge, MA 02139 USA;[2]E China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2011

卷号：54

期号：13-15

起止页码：828

外文期刊名：TOPICS IN CATALYSIS

收录：;EI(收录号：20114414475769);WOS:【SCI-EXPANDED(收录号:WOS:000300179100009)】；

基金：The authors acknowledge the catalysis researchers at the Norwegian University of Science and Technology (NTNU), in particular Professors Anders Holmen and De Chen, for many helpful conversations. This work is funded, in part, through a collaboration with NTNU supported by StatoilHydro and the Norwegian Research Council. The National Science Foundation is also acknowledged for supporting D. W. B. through the Graduate Research Fellowship Program. In addition, the Norwegian Research Council and the National Science Foundation are acknowledged for support of D. W. B. through the Nordic Research Opportunity. This publication is also based on work supported, in part by King Abdullah University of Science and Technology (KAUST). The computations in this work have been supported in part by the National Science Foundation through TeraGrid resources provided by the NCSA, grant number TG-CHE080047. Finally, Yi-An Zhu acknowledges support by the Doctoral Fund of Ministry of Education of China (No. 200802511007).

语种：英文

外文关键词：Computational thermal chemistry; Steam reforming of methane; Nickel catalysts; Computational heterogeneous catalysis

摘要：A microkinetic model of steam methane reforming over a multi-faceted nickel surface using plane-wave, periodic boundary condition density functional theory is presented. The multi-faceted model consists of a Ni(111) surface, a Ni(100) surface, and nickel step edge sites that are modeled as a Ni(211) surface. Flux and sensitivity analysis are combined to gain an increased understanding of the important reactions, intermediates, and surface facets in SMR. Statistical thermodynamics are applied to allow for the investigation of SMR under industrially-relevant conditions (e. g., temperatures in excess of 500 degrees C and pressures in excess of 1 bar). The most important surface reactions are found to occur at the under-coordinated step edge sites modeled using the Ni(211) surface as well as on the Ni(100) surface. The primary reforming pathway is predicted to be through C* + O* -> CO* at high temperatures; however, hydrogen-mediated reactions such as C* + OH* -> COH* and CH* + O* -> CHO* are predicted to become more important at low temperatures. The rate-limiting reactions are predicted to be dissociative chemisorption of methane in addition to the aforementioned C-O addition reactions.