Testing the predictive power of theory for PdxIr(100-x) alloy nanoparticles for the oxygen reduction reaction
Abstract
Here, density functional theory (DFT) calculations of O and OH binding energies on triatomic surface ensembles of PdxIr(100-x) nanoalloys successfully predicted the overall trend in experimental oxygen reduction reaction (ORR) activity as a function of nanoparticle (NP) composition. Specifically, triatomic Pd3 ensembles were found to possess optimal O and OH binding energies and were predicted to be highly active sites for the ORR, rivaling that of Pt(111). However, DFT calculations suggest that the O binding energy increases at active sites containing Ir, thereby decreasing ORR activity. PdxIr(100-x) nanoalloys were synthesized using a microwave-assisted method and their activity towards the ORR was tested using rotating disk voltammetry (RDV). As predicted, the bimetallic electrocatalysts exhibited worse catalytic activity than the Pd-only NPs. The strong qualitative correlation between the theoretical and experimental results demonstrates that the activity of individual active sites on the surface of NPs can serve as a proxy for overall activity. This is a particularly useful strategy for applying DFT calculations to electrocatalysts that are too large for true first-principle analysis.
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); Robert A; Welch Foundation
- OSTI Identifier:
- 1617193
- Alternate Identifier(s):
- OSTI ID: 1615133
- Grant/Contract Number:
- SC0010576; CHE-1807847; F-0032; F-1841; F-1738
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 17; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Guo, Hongyu, Trindell, Jamie A., Li, Hao, Fernandez, Desiree, Humphrey, Simon M., Henkelman, Graeme, and Crooks, Richard M. Testing the predictive power of theory for PdxIr(100-x) alloy nanoparticles for the oxygen reduction reaction. United States: N. p., 2020.
Web. doi:10.1039/C9TA13711D.
Guo, Hongyu, Trindell, Jamie A., Li, Hao, Fernandez, Desiree, Humphrey, Simon M., Henkelman, Graeme, & Crooks, Richard M. Testing the predictive power of theory for PdxIr(100-x) alloy nanoparticles for the oxygen reduction reaction. United States. https://doi.org/10.1039/C9TA13711D
Guo, Hongyu, Trindell, Jamie A., Li, Hao, Fernandez, Desiree, Humphrey, Simon M., Henkelman, Graeme, and Crooks, Richard M. Fri .
"Testing the predictive power of theory for PdxIr(100-x) alloy nanoparticles for the oxygen reduction reaction". United States. https://doi.org/10.1039/C9TA13711D. https://www.osti.gov/servlets/purl/1617193.
@article{osti_1617193,
title = {Testing the predictive power of theory for PdxIr(100-x) alloy nanoparticles for the oxygen reduction reaction},
author = {Guo, Hongyu and Trindell, Jamie A. and Li, Hao and Fernandez, Desiree and Humphrey, Simon M. and Henkelman, Graeme and Crooks, Richard M.},
abstractNote = {Here, density functional theory (DFT) calculations of O and OH binding energies on triatomic surface ensembles of PdxIr(100-x) nanoalloys successfully predicted the overall trend in experimental oxygen reduction reaction (ORR) activity as a function of nanoparticle (NP) composition. Specifically, triatomic Pd3 ensembles were found to possess optimal O and OH binding energies and were predicted to be highly active sites for the ORR, rivaling that of Pt(111). However, DFT calculations suggest that the O binding energy increases at active sites containing Ir, thereby decreasing ORR activity. PdxIr(100-x) nanoalloys were synthesized using a microwave-assisted method and their activity towards the ORR was tested using rotating disk voltammetry (RDV). As predicted, the bimetallic electrocatalysts exhibited worse catalytic activity than the Pd-only NPs. The strong qualitative correlation between the theoretical and experimental results demonstrates that the activity of individual active sites on the surface of NPs can serve as a proxy for overall activity. This is a particularly useful strategy for applying DFT calculations to electrocatalysts that are too large for true first-principle analysis.},
doi = {10.1039/C9TA13711D},
journal = {Journal of Materials Chemistry. A},
number = 17,
volume = 8,
place = {United States},
year = {Fri Apr 17 00:00:00 EDT 2020},
month = {Fri Apr 17 00:00:00 EDT 2020}
}
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