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Title: A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces

Abstract

Density functional theory (DFT) calculations and Kinetic Monte Carlo (KMC) simulations were employed to investigate the methanol synthesis reaction from CO{sub 2} hydrogenation (CO{sub 2} + 3H{sub 2} {yields} CH{sub 3}OH + H{sub 2}O) on metal-doped Cu(111) surfaces. Both the formate pathway and the reverse water-gas shift (RWGS) reaction followed by a CO hydrogenation pathway (RWGS + CO-Hydro) were considered in the study. Our calculations showed that the overall methanol yield increased in the sequence: Au/Cu(111) < Cu(111) < Pd/Cu(111) < Rh/Cu(111) < Pt/Cu(111) < Ni/Cu(111). On Au/Cu(111) and Cu(111), the formate pathway dominates the methanol production. Doping Au does not help the methanol synthesis on Cu(111). Pd, Rh, Pt, and Ni are able to promote the methanol production on Cu(111), where the conversion via the RWGS + CO-Hydro pathway is much faster than that via the formate pathway. Further kinetic analysis revealed that the methanol yield on Cu(111) was controlled by three factors: the dioxomethylene hydrogenation barrier, the CO binding energy, and the CO hydrogenation barrier. Accordingly, two possible descriptors are identified which can be used to describe the catalytic activity of Cu-based catalysts toward methanol synthesis. One is the activation barrier of dioxomethylene hydrogenation, and the other ismore » the CO binding energy. An ideal Cu-based catalyst for the methanol synthesis via CO{sub 2} hydrogenation should be able to hydrogenate dioxomethylene easily and bond CO moderately, being strong enough to favor the desired CO hydrogenation rather than CO desorption but weak enough to prevent CO poisoning. In this way, the methanol production via both the formate and the RWGS + CO-Hydro pathways can be facilitated.« less

Authors:
; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) Center for Functional Nanomaterials
Sponsoring Org.:
USDOE SC OFFICE OF SCIENCE (SC)
OSTI Identifier:
1043405
Report Number(s):
BNL-96294-2012-JA
Journal ID: ISSN 1932-7447; R&D Project: CO-019; KC0302010; TRN: US201213%%353
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry C
Additional Journal Information:
Journal Volume: 116; Journal Issue: 1; Journal ID: ISSN 1932-7447
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 30 DIRECT ENERGY CONVERSION; BINDING ENERGY; CATALYSTS; DESORPTION; FORMATES; FUNCTIONALS; HYDROGENATION; KINETICS; METHANOL; POISONING; PRODUCTION; SYNTHESIS; WATER GAS; density functional theory; catalysis; methanol synthesis; functional nanomaterials

Citation Formats

Liu, P, Yang, Y, and White, M G. A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces. United States: N. p., 2012. Web.
Liu, P, Yang, Y, & White, M G. A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces. United States.
Liu, P, Yang, Y, and White, M G. Thu . "A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces". United States.
@article{osti_1043405,
title = {A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces},
author = {Liu, P and Yang, Y and White, M G},
abstractNote = {Density functional theory (DFT) calculations and Kinetic Monte Carlo (KMC) simulations were employed to investigate the methanol synthesis reaction from CO{sub 2} hydrogenation (CO{sub 2} + 3H{sub 2} {yields} CH{sub 3}OH + H{sub 2}O) on metal-doped Cu(111) surfaces. Both the formate pathway and the reverse water-gas shift (RWGS) reaction followed by a CO hydrogenation pathway (RWGS + CO-Hydro) were considered in the study. Our calculations showed that the overall methanol yield increased in the sequence: Au/Cu(111) < Cu(111) < Pd/Cu(111) < Rh/Cu(111) < Pt/Cu(111) < Ni/Cu(111). On Au/Cu(111) and Cu(111), the formate pathway dominates the methanol production. Doping Au does not help the methanol synthesis on Cu(111). Pd, Rh, Pt, and Ni are able to promote the methanol production on Cu(111), where the conversion via the RWGS + CO-Hydro pathway is much faster than that via the formate pathway. Further kinetic analysis revealed that the methanol yield on Cu(111) was controlled by three factors: the dioxomethylene hydrogenation barrier, the CO binding energy, and the CO hydrogenation barrier. Accordingly, two possible descriptors are identified which can be used to describe the catalytic activity of Cu-based catalysts toward methanol synthesis. One is the activation barrier of dioxomethylene hydrogenation, and the other is the CO binding energy. An ideal Cu-based catalyst for the methanol synthesis via CO{sub 2} hydrogenation should be able to hydrogenate dioxomethylene easily and bond CO moderately, being strong enough to favor the desired CO hydrogenation rather than CO desorption but weak enough to prevent CO poisoning. In this way, the methanol production via both the formate and the RWGS + CO-Hydro pathways can be facilitated.},
doi = {},
url = {https://www.osti.gov/biblio/1043405}, journal = {Journal of Physical Chemistry C},
issn = {1932-7447},
number = 1,
volume = 116,
place = {United States},
year = {2012},
month = {1}
}