skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study

Abstract

Formic acid presents several advantages for use as a fuel in fuel cells. We present a first-principles based analysis of electrooxidation trends for formic acid on the close-packed facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh, and four hcp metals: Co, Os, Ru, and Re. To explore the structure sensitivity of this reaction on the fcc metals, we also studied the open (100) facet of these eight metals. We find that the open facets of Au, Ag, Cu, Pt, and Pd are more energy-efficient (i.e. require less overpotential) for formic acid electrooxidation when compared to their close-packed facets. The opposite is true for the stronger-binding metals: Ni, Ir, and Rh. Using the free energy of adsorbed CO* and OH* as reactivity descriptors, we cast the thermochemistry of the reaction network into phase diagrams showing regions of rate-determining steps, together with their calculated free energies. This allows the identification of bimetallic alloys, potentially possessing improved electrocatalysis for formic acid electrooxidation, compared to Pt or Pd. We discuss the need for anode catalysts for direct formic acid fuel cells (DFAFCs) to diminish CO* poisoning, by promoting the formation of formate instead of carboxyl intermediate.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1494744
Grant/Contract Number:  
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 15; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alloys; electroxidation; formic acid

Citation Formats

Elnabawy, Ahmed O., Herron, Jeffrey A., Scaranto, Jessica, and Mavrikakis, Manos. Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study. United States: N. p., 2018. Web. doi:10.1149/2.0161815jes.
Elnabawy, Ahmed O., Herron, Jeffrey A., Scaranto, Jessica, & Mavrikakis, Manos. Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study. United States. doi:10.1149/2.0161815jes.
Elnabawy, Ahmed O., Herron, Jeffrey A., Scaranto, Jessica, and Mavrikakis, Manos. Sat . "Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study". United States. doi:10.1149/2.0161815jes. https://www.osti.gov/servlets/purl/1494744.
@article{osti_1494744,
title = {Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study},
author = {Elnabawy, Ahmed O. and Herron, Jeffrey A. and Scaranto, Jessica and Mavrikakis, Manos},
abstractNote = {Formic acid presents several advantages for use as a fuel in fuel cells. We present a first-principles based analysis of electrooxidation trends for formic acid on the close-packed facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh, and four hcp metals: Co, Os, Ru, and Re. To explore the structure sensitivity of this reaction on the fcc metals, we also studied the open (100) facet of these eight metals. We find that the open facets of Au, Ag, Cu, Pt, and Pd are more energy-efficient (i.e. require less overpotential) for formic acid electrooxidation when compared to their close-packed facets. The opposite is true for the stronger-binding metals: Ni, Ir, and Rh. Using the free energy of adsorbed CO* and OH* as reactivity descriptors, we cast the thermochemistry of the reaction network into phase diagrams showing regions of rate-determining steps, together with their calculated free energies. This allows the identification of bimetallic alloys, potentially possessing improved electrocatalysis for formic acid electrooxidation, compared to Pt or Pd. We discuss the need for anode catalysts for direct formic acid fuel cells (DFAFCs) to diminish CO* poisoning, by promoting the formation of formate instead of carboxyl intermediate.},
doi = {10.1149/2.0161815jes},
journal = {Journal of the Electrochemical Society},
number = 15,
volume = 165,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Recent advances in direct formic acid fuel cells (DFAFC)
journal, July 2008


Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes
journal, October 2010

  • Sasaki, Kotaro; Naohara, Hideo; Cai, Yun
  • Angewandte Chemie International Edition, Vol. 49, Issue 46, p. 8602-8607
  • DOI: 10.1002/anie.201004287

Near-surface alloys for hydrogen fuel cell applications
journal, January 2006


Metal monolayer deposition by replacement of metal adlayers on electrode surfaces
journal, March 2001