Journal
JOURNAL OF CATALYSIS
Volume 359, Issue -, Pages 272-286Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2018.01.006
Keywords
Hydrogenation; Tautomerization; Hydrodeoxygenation; Cresol; Microkinetics; Ni; NiFe; DFT
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Funding
- National Natural Science Foundation of China [21673137]
- Natural Science Foundation of Shanghai City [16ZR1413900]
- Shanghai University of Engineering Science [nhrc-2015-01]
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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.
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