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Title: Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper

Abstract

Rational optimization of catalytic performance has been one of the major challenges in catalysis. We report a bottom-up study on the ability of TiO 2 and ZrO 2 to optimize the CO 2 conversion to methanol on Cu, using combined density functional theory (DFT) calculations, kinetic Monte Carlo (KMC) simulations, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements, and steady-state flow reactor tests. Furthermore, the theoretical results from DFT and KMC agree with in situ DRIFTS measurements, showing that both TiO 2 and ZrO 2 help to promote methanol synthesis on Cu via carboxyl intermediates and the reverse water–gas-shift (RWGS) pathway; the formate intermediates, on the other hand, likely act as a spectator eventually. The origin of the superior promoting effect of ZrO 2 is associated with the fine-tuning capability of reduced Zr 3+ at the interface, being able to bind the key reaction intermediates, e.g. *CO 2, *CO, *HCO, and *H 2CO, moderately to facilitate methanol formation. Our study demonstrates the importance of synergy between theory and experiments to elucidate the complex reaction mechanisms of CO 2 hydrogenation for the realization of a better catalyst by design.

Authors:
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1345746
Report Number(s):
BNL-113590-2017-JA
Journal ID: ISSN 0002-7863; R&D Project: CO009; KC0302010
Grant/Contract Number:  
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 38; 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

None, None. Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper. United States: N. p., 2016. Web. doi:10.1021/jacs.6b05791.
None, None. Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper. United States. doi:10.1021/jacs.6b05791.
None, None. Mon . "Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper". United States. doi:10.1021/jacs.6b05791. https://www.osti.gov/servlets/purl/1345746.
@article{osti_1345746,
title = {Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper},
author = {None, None},
abstractNote = {Rational optimization of catalytic performance has been one of the major challenges in catalysis. We report a bottom-up study on the ability of TiO2 and ZrO2 to optimize the CO2 conversion to methanol on Cu, using combined density functional theory (DFT) calculations, kinetic Monte Carlo (KMC) simulations, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements, and steady-state flow reactor tests. Furthermore, the theoretical results from DFT and KMC agree with in situ DRIFTS measurements, showing that both TiO2 and ZrO2 help to promote methanol synthesis on Cu via carboxyl intermediates and the reverse water–gas-shift (RWGS) pathway; the formate intermediates, on the other hand, likely act as a spectator eventually. The origin of the superior promoting effect of ZrO2 is associated with the fine-tuning capability of reduced Zr3+ at the interface, being able to bind the key reaction intermediates, e.g. *CO2, *CO, *HCO, and *H2CO, moderately to facilitate methanol formation. Our study demonstrates the importance of synergy between theory and experiments to elucidate the complex reaction mechanisms of CO2 hydrogenation for the realization of a better catalyst by design.},
doi = {10.1021/jacs.6b05791},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 38,
volume = 138,
place = {United States},
year = {2016},
month = {8}
}

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Works referencing / citing this record:

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