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Title: The role of sub-surface hydrogen on CO2 reduction and dynamics on Ni(110): An ab initio molecular dynamics study

Abstract

The catalytic reduction of carbon dioxide is a crucial step in many chemical industrial reactions, such as methanol synthesis, the reverse water-gas shift reaction (rWGS) and formic acid synthesis. Here, we investigate the role of bulk hydrogen, where hydrogen atoms are found deep inside a metal surface as opposed to subsurface ones, upon CO2 reduction over a Ni(110) surface using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. While it has previously been shown that subsurface hydrogen stabilizes CO2 and can aid in overcoming reaction barriers, the role of bulk hydrogen is less studied and thus unknown with regard to CO2 reduction. Furthermore, we find that the presence of bulk hydrogen can significantly alter the electronic structure of the Ni(110) surface, particularly the work function and d-band center, such that CO2 adsorbs more strongly to the surface and is more easily reduced. Our results show an enhanced CO2 dissociation in the presence of bulk hydrogen, shedding light on a hitherto underappreciated mechanistic pathway for CO2 reduction on metal surfaces.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1820064
Alternate Identifier(s):
OSTI ID: 1809105
Report Number(s):
PNNL-SA-162072
Journal ID: ISSN 0021-9606; TRN: US2214575
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231; 47319
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 155; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Work functions; Catalysts and catalysis; Hydrogen energy; Surface and interface chemistry; Ab-initio molecular dynamics; Hydrogenation process; Density functional theory; Reaction mechanisms

Citation Formats

Allec, Sarah I., Nguyen, Manh-Thuong, Rousseau, Roger, and Glezakou, Vassiliki-Alexandra. The role of sub-surface hydrogen on CO2 reduction and dynamics on Ni(110): An ab initio molecular dynamics study. United States: N. p., 2021. Web. doi:10.1063/5.0048894.
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Allec, Sarah I., Nguyen, Manh-Thuong, Rousseau, Roger, & Glezakou, Vassiliki-Alexandra. The role of sub-surface hydrogen on CO2 reduction and dynamics on Ni(110): An ab initio molecular dynamics study. United States. https://doi.org/10.1063/5.0048894
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Allec, Sarah I., Nguyen, Manh-Thuong, Rousseau, Roger, and Glezakou, Vassiliki-Alexandra. Wed . "The role of sub-surface hydrogen on CO2 reduction and dynamics on Ni(110): An ab initio molecular dynamics study". United States. https://doi.org/10.1063/5.0048894. https://www.osti.gov/servlets/purl/1820064.
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@article{osti_1820064,
title = {The role of sub-surface hydrogen on CO2 reduction and dynamics on Ni(110): An ab initio molecular dynamics study},
author = {Allec, Sarah I. and Nguyen, Manh-Thuong and Rousseau, Roger and Glezakou, Vassiliki-Alexandra},
abstractNote = {The catalytic reduction of carbon dioxide is a crucial step in many chemical industrial reactions, such as methanol synthesis, the reverse water-gas shift reaction (rWGS) and formic acid synthesis. Here, we investigate the role of bulk hydrogen, where hydrogen atoms are found deep inside a metal surface as opposed to subsurface ones, upon CO2 reduction over a Ni(110) surface using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. While it has previously been shown that subsurface hydrogen stabilizes CO2 and can aid in overcoming reaction barriers, the role of bulk hydrogen is less studied and thus unknown with regard to CO2 reduction. Furthermore, we find that the presence of bulk hydrogen can significantly alter the electronic structure of the Ni(110) surface, particularly the work function and d-band center, such that CO2 adsorbs more strongly to the surface and is more easily reduced. Our results show an enhanced CO2 dissociation in the presence of bulk hydrogen, shedding light on a hitherto underappreciated mechanistic pathway for CO2 reduction on metal surfaces.},
doi = {10.1063/5.0048894},
journal = {Journal of Chemical Physics},
number = 4,
volume = 155,
place = {United States},
year = {Wed Jul 28 00:00:00 EDT 2021},
month = {Wed Jul 28 00:00:00 EDT 2021}
}
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