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Title: Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

Abstract

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substrate with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion andmore » promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Authors:
 [1];  [2];  [1];  [3]; ORCiD logo [4];  [1];  [1]; ORCiD logo [3];  [2]; ORCiD logo [1]
  1. Univ. at Buffalo, NY (United States). Dept. of Chemical and Biological Engineering
  2. Giner Inc., Newton, MA (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  4. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Giner Inc., Newton, MA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. at Buffalo, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1425082
Report Number(s):
BNL-203254-2018-JAAM
Journal ID: ISSN 2155-5435
Grant/Contract Number:
SC0012704; EE0006960; CBET-1604392
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nanocarbon; metal oxides; oxygen reduction; oxygen evolution; bifunctional catalysis

Citation Formats

Gupta, Shiva, Zhao, Shuai, Wang, Xiao Xia, Hwang, Sooyeon, Karakalos, Stavros, Devaguptapu, Surya V., Mukherjee, Shreya, Su, Dong, Xu, Hui, and Wu, Gang. Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b02949.
Gupta, Shiva, Zhao, Shuai, Wang, Xiao Xia, Hwang, Sooyeon, Karakalos, Stavros, Devaguptapu, Surya V., Mukherjee, Shreya, Su, Dong, Xu, Hui, & Wu, Gang. Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon. United States. doi:10.1021/acscatal.7b02949.
Gupta, Shiva, Zhao, Shuai, Wang, Xiao Xia, Hwang, Sooyeon, Karakalos, Stavros, Devaguptapu, Surya V., Mukherjee, Shreya, Su, Dong, Xu, Hui, and Wu, Gang. Tue . "Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon". United States. doi:10.1021/acscatal.7b02949.
@article{osti_1425082,
title = {Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon},
author = {Gupta, Shiva and Zhao, Shuai and Wang, Xiao Xia and Hwang, Sooyeon and Karakalos, Stavros and Devaguptapu, Surya V. and Mukherjee, Shreya and Su, Dong and Xu, Hui and Wu, Gang},
abstractNote = {The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substrate with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.},
doi = {10.1021/acscatal.7b02949},
journal = {ACS Catalysis},
number = 12,
volume = 7,
place = {United States},
year = {Tue Oct 31 00:00:00 EDT 2017},
month = {Tue Oct 31 00:00:00 EDT 2017}
}

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