期刊
JOURNAL OF CATALYSIS
卷 359, 期 -, 页码 272-286出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2018.01.006
关键词
Hydrogenation; Tautomerization; Hydrodeoxygenation; Cresol; Microkinetics; Ni; NiFe; DFT
资金
- National Natural Science Foundation of China [21673137]
- Natural Science Foundation of Shanghai City [16ZR1413900]
- Shanghai University of Engineering Science [nhrc-2015-01]
Developing mechanistic insights into the reaction network of hydrodeoxygenation (HDO) of lignin derived compounds is key to rational design of high-performance catalysts for bio-oils upgrading. Herein, we present a comprehensive theoretical study on HDO of m-cresol, a model compound of phenolics, on Ni(111) and NiFe(111) surfaces using periodic density functional theory calculations and microkinetic modeling techniques, with a focus on the several competing reaction pathways including enol-keto tautomerization, hydrogenation, and dehydroxylation. Our results show that the activation of the C-OH bond of m-cresol and phenolic intermediates can be greatly promoted on oxophilic NiFe (111), evidenced by the elongated C-OH bond length and the enhanced dehydroxylation activity with respect to Ni(111). It is found that m-cresol HDO on NiFe(111) shares certain common features with that on Ni(111), but exhibits important differences that result in dramatic changes in selectivity. We show that the C-OH bond length of adsorbed phenolic intermediates can be used as a good descriptor for prediction on the C OH bond scission reaction in HDO. Finally, microkinetic modeling augmented by degree of rate control analysis is applied to rationalize the experimentally-observed differences in product distributions over Ni and NiFe catalysts when kinetic factors still dominate. (C) 2018 Elsevier Inc. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据