skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction

Abstract

The development of active, durable, and low-cost catalysts to replace noble metal-based materials is highly desirable to promote the sluggish oxygen reduction reaction in fuel cells. Herein, nitrogen and fluorine-codoped three-dimensional carbon nanowire aerogels, composed of interconnected carbon nanowires, were synthesized for the first time by a hydrothermal carbonization process. Owing to their porous nanostructures and heteroatom-doping, the as-prepared carbon nanowire aerogels, with optimized composition, present excellent electrocatalytic activity that is comparable to commercial Pt/C. Remarkably, the aerogels also exhibit superior stability and methanol tolerance. This synthesis procedure paves a new way to design novel heteroatomdoped catalysts.

Authors:
 [1]; ORCiD logo [1];  [1];  [2];  [3];  [1]; ORCiD logo [1]
  1. School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA
  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99352 USA
  3. Energy and Environmental Directory, Pacific Northwest National Laboratory, Richland WA 99352 USA
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1378010
Report Number(s):
PNNL-SA-128735
Journal ID: ISSN 0947-6539; 48877; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry - A European Journal; Journal Volume: 23; Journal Issue: 43
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Environmental Molecular Sciences Laboratory

Citation Formats

Fu, Shaofang, Zhu, Chengzhou, Song, Junhua, Engelhard, Mark H., Xiao, Biwei, Du, Dan, and Lin, Yuehe. Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction. United States: N. p., 2017. Web. doi:10.1002/chem.201701969.
Fu, Shaofang, Zhu, Chengzhou, Song, Junhua, Engelhard, Mark H., Xiao, Biwei, Du, Dan, & Lin, Yuehe. Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction. United States. doi:10.1002/chem.201701969.
Fu, Shaofang, Zhu, Chengzhou, Song, Junhua, Engelhard, Mark H., Xiao, Biwei, Du, Dan, and Lin, Yuehe. 2017. "Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction". United States. doi:10.1002/chem.201701969.
@article{osti_1378010,
title = {Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction},
author = {Fu, Shaofang and Zhu, Chengzhou and Song, Junhua and Engelhard, Mark H. and Xiao, Biwei and Du, Dan and Lin, Yuehe},
abstractNote = {The development of active, durable, and low-cost catalysts to replace noble metal-based materials is highly desirable to promote the sluggish oxygen reduction reaction in fuel cells. Herein, nitrogen and fluorine-codoped three-dimensional carbon nanowire aerogels, composed of interconnected carbon nanowires, were synthesized for the first time by a hydrothermal carbonization process. Owing to their porous nanostructures and heteroatom-doping, the as-prepared carbon nanowire aerogels, with optimized composition, present excellent electrocatalytic activity that is comparable to commercial Pt/C. Remarkably, the aerogels also exhibit superior stability and methanol tolerance. This synthesis procedure paves a new way to design novel heteroatomdoped catalysts.},
doi = {10.1002/chem.201701969},
journal = {Chemistry - A European Journal},
number = 43,
volume = 23,
place = {United States},
year = 2017,
month = 7
}
  • Te nanowires were used as template to synthesize N,S-codoped carbon nanowires. Enhanced electrocatalytic performance on oxygen reduction was demonstrated.
  • Finely controlled synthesis of high active and robust non-precious metal catalysts with excellent electrocatalytic efficiency towards oxygen reduction reaction is extremely vital for successful implementation of fuel cells and metal batteries. Unprecedented oxygen reduction reaction electrocatalytic performances and the diversified synthetic procedure in term of favorable structure/morphology characteristics make transition metals-derived M–N–C (M=Fe, Co) structures the most promising nanocatalysts. Herein, using the nitrogen-containing small molecular and inorganic salt as precursors and ultrathin tellurium nanowires as templates, we successfully synthesized a series of well-defined M-N-doped hollow carbon nanowire aerogels through one step hydrothermal route and subsequent facile annealing treatment. Taking advantagemore » of the porous nanostructures, one-dimensional building block as well as homogeneity of active sites, the resultant Fe-N-doped carbon hollow nanowire aerogels exhibited excellent ORR electrocatalytic performance even better than commercial Pt/C in alkaline solution, holding great potential in fuel cell applications.« less
  • In this study, self-assembled M–N-doped carbon nanotube aerogels with single-atom catalyst feature are for the first time reported through one-step hydrothermal route and subsequent facile annealing treatment. By taking advantage of the porous nanostructures, 1D nanotubes as well as single-atom catalyst feature, the resultant Fe–N-doped carbon nanotube aerogels exhibit excellent oxygen reduction reaction electrocatalytic performance even better than commercial Pt/C in alkaline solution.
  • The role of Cu-ion doping in α-MnO 2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO 2 nanowires (Cu-α-MnO 2) were prepared with varying amounts of Cu 2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO 2 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-MnO 2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn 3+ content for the Cu-α-MnO 2 nanowires. The Mn 3+/Mn 4+ couple is themediator for the rate-limiting redoxmore » driven O 2 -/OH - exchange. It is proposed that O 2 adsorbs viaan axial site (the e g orbital on the Mn 3+ d 4 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 O 2 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 Mn 3+ character of the oxide.« less