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Title: 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:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [3];  [4];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of New Mexico, Albuquerque, NM (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Guangdong Univ. of Technology, Guangdong (China)
  4. 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), Transportation Office. 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:
Journal Article: 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. doi: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. doi: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},
issn = {0013-4651},
number = 7,
volume = 166,
place = {United States},
year = {2019},
month = {4}
}

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

Citation Metrics:
Cited by: 7 works
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Figures / Tables:

Figure 1 Figure 1: Zig-zag nanoribbon edge hosted M-N4 active site structure with OH ligand used in this study. Gray spheres represent C. White spheres represent H. Blue spheres represent N. Red sphere represents O. Brown sphere represents M. In the case of the OH ligand, ORR intermediates are free to bindmore » underneath the M in the orientation depicted.« less

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    Works referencing / citing this record:

    Systematic exploration of N,C coordination effects on the ORR performance of Mn–N x doped graphene catalysts based on DFT calculations
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.