Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals
Abstract
Replacement of platinum-based electrocatalysts to facilitate the oxygen reduction reaction (ORR) in proton exchange fuel cells remains an outstanding challenge. Significant progress in the development of platinum group metal-free (PGM-free) electrocatalysts has been reported but a fundamental understanding of how these materials catalyze the ORR remains elusive. In this work, we report our efforts to synthesize and characterize PGM-free electrocatalysts with different transition metals (M = Fe, Co, and Mn) in order to better understand the most plausible active site structures and ORR reaction pathways. Our findings indicate that PGM-free electrocatalysts synthesized via a dual nitrogen precursor, polyaniline and cyanamide, synthesis process but with varied transition metal precursors resulted in the following ORR activity trend: Fe > Co > Mn. Furthermore, similar densities of active sites across the three synthesized materials were calculated using an established molecular probe technique. The relative experimental activities are consistent with trends determined via density functional theory (DFT) modeling that suggests spontaneous OH ligand modification of active sites.
- Authors:
-
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Univ. of New Mexico, Albuquerque, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Guangdong Univ. of Technology, Guangdong (China)
- Univ. of Idaho, Moscow, ID (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
- OSTI Identifier:
- 1525854
- Report Number(s):
- LA-UR-19-20441
Journal ID: ISSN 0013-4651
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Volume: 166; Journal Issue: 7; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Energy Sciences; Electrocatalysis; Fuel Cells; fuel cells; oxygen reduction reaction; PGM-free catalysts
Citation Formats
Martinez, Ulises, Holby, Edward F., Babu, Siddharth Komini, Artyushkova, Kateryna, Lin, Ling, Choudhury, Samrat, Purdy, Geraldine M., and Zelenay, Piotr. Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals. United States: N. p., 2019.
Web. doi:10.1149/2.0201907jes.
Martinez, Ulises, Holby, Edward F., Babu, Siddharth Komini, Artyushkova, Kateryna, Lin, Ling, Choudhury, Samrat, Purdy, Geraldine M., & Zelenay, Piotr. Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals. United States. https://doi.org/10.1149/2.0201907jes
Martinez, Ulises, Holby, Edward F., Babu, Siddharth Komini, Artyushkova, Kateryna, Lin, Ling, Choudhury, Samrat, Purdy, Geraldine M., and Zelenay, Piotr. Mon .
"Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals". United States. https://doi.org/10.1149/2.0201907jes. https://www.osti.gov/servlets/purl/1525854.
@article{osti_1525854,
title = {Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals},
author = {Martinez, Ulises and Holby, Edward F. and Babu, Siddharth Komini and Artyushkova, Kateryna and Lin, Ling and Choudhury, Samrat and Purdy, Geraldine M. and Zelenay, Piotr},
abstractNote = {Replacement of platinum-based electrocatalysts to facilitate the oxygen reduction reaction (ORR) in proton exchange fuel cells remains an outstanding challenge. Significant progress in the development of platinum group metal-free (PGM-free) electrocatalysts has been reported but a fundamental understanding of how these materials catalyze the ORR remains elusive. In this work, we report our efforts to synthesize and characterize PGM-free electrocatalysts with different transition metals (M = Fe, Co, and Mn) in order to better understand the most plausible active site structures and ORR reaction pathways. Our findings indicate that PGM-free electrocatalysts synthesized via a dual nitrogen precursor, polyaniline and cyanamide, synthesis process but with varied transition metal precursors resulted in the following ORR activity trend: Fe > Co > Mn. Furthermore, similar densities of active sites across the three synthesized materials were calculated using an established molecular probe technique. The relative experimental activities are consistent with trends determined via density functional theory (DFT) modeling that suggests spontaneous OH ligand modification of active sites.},
doi = {10.1149/2.0201907jes},
journal = {Journal of the Electrochemical Society},
number = 7,
volume = 166,
place = {United States},
year = {Mon Apr 15 00:00:00 EDT 2019},
month = {Mon Apr 15 00:00:00 EDT 2019}
}
Web of Science
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