Trends in Formic Acid Electro-Oxidation on Transition Metals Alloyed with Platinum and Palladium
Abstract
Direct formic acid fuel cells (DFAFCs) have emerged as a promising power source to meet increased demands for alternative energy sources in the transportation and portable energy storage sectors. Furthermore, these fuel cells utilize formic acid (FA), a nontoxic and carbon-neutral fuel when produced from biomass or via CO2 reduction. Despite the promise of DFAFCs, the best monometallic catalysts, platinum and palladium, are poisoned by CO through the indirect oxidation pathway and require large overpotentials. By alloying Pt and Pd with other metals, we aim to improve both the activity and selectivity of these catalysts. Here, we present a systematic density functional theory (GGA-PW91) study of FA electro-oxidation (FAO) on the (111) facet of bimetallic Pt (Pt3M) or Pd (Pd3M) catalysts (M = Au, Ag, Cu, Pt, Pd, Ir, Rh, Ru, or Re) to evaluate the catalytic performance of these surfaces. For each surface, we calculate free energy diagrams and onset potentials of three key reaction mechanisms: direct oxidation of FA via carboxyl (COOH), direct oxidation of FA via formate (HCOO), and the indirect oxidation of FA that first forms CO en route to full oxidation to CO2. We then display the trends in the form of phase diagrams thatmore »
- Authors:
-
[1];
[2]
- Univ. of Wisconsin, Madison, WI (United States); Cairo Univ., Giza (Egypt)
- Univ. of Wisconsin, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1876057
- Grant/Contract Number:
- FG02-05ER15731; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 126; Journal Issue: 9; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; formic acid; fuel cells; electrocatalysis; alloys; DFT; carboxyls; oxidation; palladium; platinum
Citation Formats
Elnabawy, Ahmed O., Murray, Ellen A., and Mavrikakis, Manos. Trends in Formic Acid Electro-Oxidation on Transition Metals Alloyed with Platinum and Palladium. United States: N. p., 2022.
Web. doi:10.1021/acs.jpcc.1c10488.
Elnabawy, Ahmed O., Murray, Ellen A., & Mavrikakis, Manos. Trends in Formic Acid Electro-Oxidation on Transition Metals Alloyed with Platinum and Palladium. United States. https://doi.org/10.1021/acs.jpcc.1c10488
Elnabawy, Ahmed O., Murray, Ellen A., and Mavrikakis, Manos. Mon .
"Trends in Formic Acid Electro-Oxidation on Transition Metals Alloyed with Platinum and Palladium". United States. https://doi.org/10.1021/acs.jpcc.1c10488. https://www.osti.gov/servlets/purl/1876057.
@article{osti_1876057,
title = {Trends in Formic Acid Electro-Oxidation on Transition Metals Alloyed with Platinum and Palladium},
author = {Elnabawy, Ahmed O. and Murray, Ellen A. and Mavrikakis, Manos},
abstractNote = {Direct formic acid fuel cells (DFAFCs) have emerged as a promising power source to meet increased demands for alternative energy sources in the transportation and portable energy storage sectors. Furthermore, these fuel cells utilize formic acid (FA), a nontoxic and carbon-neutral fuel when produced from biomass or via CO2 reduction. Despite the promise of DFAFCs, the best monometallic catalysts, platinum and palladium, are poisoned by CO through the indirect oxidation pathway and require large overpotentials. By alloying Pt and Pd with other metals, we aim to improve both the activity and selectivity of these catalysts. Here, we present a systematic density functional theory (GGA-PW91) study of FA electro-oxidation (FAO) on the (111) facet of bimetallic Pt (Pt3M) or Pd (Pd3M) catalysts (M = Au, Ag, Cu, Pt, Pd, Ir, Rh, Ru, or Re) to evaluate the catalytic performance of these surfaces. For each surface, we calculate free energy diagrams and onset potentials of three key reaction mechanisms: direct oxidation of FA via carboxyl (COOH), direct oxidation of FA via formate (HCOO), and the indirect oxidation of FA that first forms CO en route to full oxidation to CO2. We then display the trends in the form of phase diagrams that compare the activity of the calculated surfaces against regions of high activity using the free energies of adsorbed CO and OH as descriptors, enabling high-throughput screening and design of improved catalysts, particularly those alloying Pt or Pd with Ir, Ru, or Re.},
doi = {10.1021/acs.jpcc.1c10488},
journal = {Journal of Physical Chemistry. C},
number = 9,
volume = 126,
place = {United States},
year = {Mon Feb 28 00:00:00 EST 2022},
month = {Mon Feb 28 00:00:00 EST 2022}
}
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