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Title: Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study

Abstract

We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Department of Chemical and Biological Engineering, University of Wisconsin − Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1385878
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 4; Journal Issue: 12; Related Information: IACT partners with Argonne National Laboratory (lead); Brookhaven National Laboratory; Northwestern University; Purdue University; University of Wisconsin at Madison; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous), catalysis (heterogeneous), biofuels (including algae and biomass), bio-inspired, materials and chemistry by design, synthesis (novel materials), synthesis (scalable processing)

Citation Formats

Herron, Jeffrey A., Scaranto, Jessica, Ferrin, Peter, Li, Sha, and Mavrikakis, Manos. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study. United States: N. p., 2014. Web. doi:10.1021/cs500737p.
Herron, Jeffrey A., Scaranto, Jessica, Ferrin, Peter, Li, Sha, & Mavrikakis, Manos. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study. United States. https://doi.org/10.1021/cs500737p
Herron, Jeffrey A., Scaranto, Jessica, Ferrin, Peter, Li, Sha, and Mavrikakis, Manos. 2014. "Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study". United States. https://doi.org/10.1021/cs500737p.
@article{osti_1385878,
title = {Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study},
author = {Herron, Jeffrey A. and Scaranto, Jessica and Ferrin, Peter and Li, Sha and Mavrikakis, Manos},
abstractNote = {We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.},
doi = {10.1021/cs500737p},
url = {https://www.osti.gov/biblio/1385878}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 12,
volume = 4,
place = {United States},
year = {2014},
month = {11}
}