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Title: Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen

Abstract

We present a combined theoretical and experimental study of CO hydrogenation on a Ni(110) surface, including studies of the role of gas-phase atomic hydrogen, surface hydrogen, and subsurface hydrogen reacting with adsorbed CO. Reaction mechanisms leading both to methane and methanol are considered. In the reaction involving surface or subsurface hydrogen, we investigate four possible pathways, using density functional theory to characterize the relative energetics of each intermediate, including the importance of further hydrogenation versus C-O bond breaking, where the latter may lead to methane production. The most energetically favorable outcome is the production of methanol along a pathway involving the sequential hydrogenation of CO to a H 3CO* intermediate, followed by a final hydrogenation to give methanol. In addition, we find that subsurface hydrogen noticeably alters reaction barriers, both passively and through the energy released by diffusion to the surface. Indeed, the effective reaction barriers are even lower than for CO methanolation on Cu(211) and Cu(111) than for Ni(110). In studies of gas-phase H atoms impinging on a CO-adsorbed Ni(110) surface, Born-Oppenheimer molecular dynamics simulations show that direct impact of H is unlikely to result in hydrogenation of CO. This means that Eley-Rideal or hot-atom mechanisms are not important;more » thus, thermal reactions involving subsurface hydrogen are the primary reaction mechanisms leading to methanol. Finally, we demonstrate experimentally for the first time the production of methanol and formaldehyde from CO hydrogenation on Ni(110) and confirm the role of subsurface hydrogen in the mechanism of this reaction.« less

Authors:
 [1]; ORCiD logo [1]; ; ;  [1]; ORCiD logo; ORCiD logo [1]
  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1413067
Alternate Identifier(s):
OSTI ID: 1529566
Grant/Contract Number:  
FG02-03ER15457
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 139 Journal Issue: 48; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ashwell, Adam P., Lin, Wei, Hofman, Michelle S., Yang, Yuxin, Ratner, Mark A., Koel, Bruce E., and Schatz, George C. Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen. United States: N. p., 2017. Web. doi:10.1021/jacs.7b09914.
Ashwell, Adam P., Lin, Wei, Hofman, Michelle S., Yang, Yuxin, Ratner, Mark A., Koel, Bruce E., & Schatz, George C. Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen. United States. doi:10.1021/jacs.7b09914.
Ashwell, Adam P., Lin, Wei, Hofman, Michelle S., Yang, Yuxin, Ratner, Mark A., Koel, Bruce E., and Schatz, George C. Thu . "Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen". United States. doi:10.1021/jacs.7b09914.
@article{osti_1413067,
title = {Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen},
author = {Ashwell, Adam P. and Lin, Wei and Hofman, Michelle S. and Yang, Yuxin and Ratner, Mark A. and Koel, Bruce E. and Schatz, George C.},
abstractNote = {We present a combined theoretical and experimental study of CO hydrogenation on a Ni(110) surface, including studies of the role of gas-phase atomic hydrogen, surface hydrogen, and subsurface hydrogen reacting with adsorbed CO. Reaction mechanisms leading both to methane and methanol are considered. In the reaction involving surface or subsurface hydrogen, we investigate four possible pathways, using density functional theory to characterize the relative energetics of each intermediate, including the importance of further hydrogenation versus C-O bond breaking, where the latter may lead to methane production. The most energetically favorable outcome is the production of methanol along a pathway involving the sequential hydrogenation of CO to a H3CO* intermediate, followed by a final hydrogenation to give methanol. In addition, we find that subsurface hydrogen noticeably alters reaction barriers, both passively and through the energy released by diffusion to the surface. Indeed, the effective reaction barriers are even lower than for CO methanolation on Cu(211) and Cu(111) than for Ni(110). In studies of gas-phase H atoms impinging on a CO-adsorbed Ni(110) surface, Born-Oppenheimer molecular dynamics simulations show that direct impact of H is unlikely to result in hydrogenation of CO. This means that Eley-Rideal or hot-atom mechanisms are not important; thus, thermal reactions involving subsurface hydrogen are the primary reaction mechanisms leading to methanol. Finally, we demonstrate experimentally for the first time the production of methanol and formaldehyde from CO hydrogenation on Ni(110) and confirm the role of subsurface hydrogen in the mechanism of this reaction.},
doi = {10.1021/jacs.7b09914},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 48,
volume = 139,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/jacs.7b09914

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Adsorption Energies for the Intermediates along the Reaction Pathways on Bare Ni(110) (Eads) and for Ni(110) with 1 ML of Hsub (Eads,sub)

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Works referencing / citing this record:

Study on syngas methanation mechanism over Ni 4 /MCM-41 catalyst based on density functional theory
journal, June 2019


Study on syngas methanation mechanism over Ni 4 /MCM-41 catalyst based on density functional theory
journal, June 2019


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.