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

Journal Article · Mon Nov 10 04:00:00 EST 2014 · ACS Catalysis

DOI:https://doi.org/10.1021/cs500737p· OSTI ID:1385878

Herron, Jeffrey A. ^[1]; Scaranto, Jessica ^[1]; Ferrin, Peter ^[1]; Li, Sha ^[1]; Mavrikakis, Manos ^[1]

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1. Department of Chemical and Biological Engineering, University of Wisconsin − Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States

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.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1385878
• Journal Information: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 4; ISSN 2155-5435
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

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