Role of Cu-Ion Doping in Cu-α-MnO2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction
Abstract
The role of Cu-ion doping in α-MnO2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO2 nanowires (Cu-α-MnO2) were prepared with varying amounts of Cu2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn3+ content for the Cu-α-MnO2 nanowires. The Mn3+/Mn4+ couple is themediator for the rate-limiting redox driven O2-/OH- exchange. It is proposed that O2 adsorbs viaan axial site (the eg orbital on the Mn3+ d4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn3+ character of the oxide.
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Materials, Devices & Energy Technologies
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Materials Characterization & Performance
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Advanced Materials Laboratory
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Physics based Microsystems
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1140890
- Report Number(s):
- SAND2014-1394J
Journal ID: ISSN 1932-7447; 503570
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 118; Journal Issue: 31; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Davis, Danae J., Lambert, Timothy N., Vigil, Julian A., Rodriguez, Mark A., Brumbach, Michael T., Coker, Eric N., and Limmer, Steven J. Role of Cu-Ion Doping in Cu-α-MnO2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction. United States: N. p., 2014.
Web. doi:10.1021/jp5039865.
Davis, Danae J., Lambert, Timothy N., Vigil, Julian A., Rodriguez, Mark A., Brumbach, Michael T., Coker, Eric N., & Limmer, Steven J. Role of Cu-Ion Doping in Cu-α-MnO2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction. United States. https://doi.org/10.1021/jp5039865
Davis, Danae J., Lambert, Timothy N., Vigil, Julian A., Rodriguez, Mark A., Brumbach, Michael T., Coker, Eric N., and Limmer, Steven J. Wed .
"Role of Cu-Ion Doping in Cu-α-MnO2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction". United States. https://doi.org/10.1021/jp5039865. https://www.osti.gov/servlets/purl/1140890.
@article{osti_1140890,
title = {Role of Cu-Ion Doping in Cu-α-MnO2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction},
author = {Davis, Danae J. and Lambert, Timothy N. and Vigil, Julian A. and Rodriguez, Mark A. and Brumbach, Michael T. and Coker, Eric N. and Limmer, Steven J.},
abstractNote = {The role of Cu-ion doping in α-MnO2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO2 nanowires (Cu-α-MnO2) were prepared with varying amounts of Cu2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn3+ content for the Cu-α-MnO2 nanowires. The Mn3+/Mn4+ couple is themediator for the rate-limiting redox driven O2-/OH- exchange. It is proposed that O2 adsorbs viaan axial site (the eg orbital on the Mn3+ d4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn3+ character of the oxide.},
doi = {10.1021/jp5039865},
journal = {Journal of Physical Chemistry. C},
number = 31,
volume = 118,
place = {United States},
year = {Wed Jul 09 00:00:00 EDT 2014},
month = {Wed Jul 09 00:00:00 EDT 2014}
}
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