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Title: Enhancement in Oxygen Reduction Reaction Activity of Nitrogen-Doped Carbon Nanostructures in Acidic Media through Chloride-Ion Exposure

Abstract

Nitrogen-doped carbon nanostructures (CNx) are promising cathode materials as catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane (PEM) fuel cells. Incorporation of chlorine into CN x catalysts using a facile methodology can lead to a significant improvement in the ORR activity in acidic media, as confirmed by electrochemical half-cell measurements. The chlorine-containing CN x catalyst (CN x-Cl) is synthesized by soaking CN x powder in 0.3 M HCl. The analysis of near-edge X-ray absorption fine structure spectra collected in the C K-edge region and Fourier-transform infrared spectra confirm the formation of C-Cl bonds in CN x-Cl. X-ray photoelectron spectroscopy (XPS) results reveal the presence of three distinct chlorine species in the CN x-Cl sample: (i) organic chlorine (C-Cl), (ii) anionic chloride in the positively charged environment of a pyridinium ring (N +Cl -), and (iii) physisorbed ionic chloride. Results from temperature-programmed desorption studies under inert atmosphere corroborate the conclusions from XPS depth profiling analysis. The improvement in ORR activity after exposure of the CN x catalyst to chloride anions can be attributed to the creation of C-Cl functionalities as additional active sites. The difference in the electronegativity of C and Cl atoms results in a net positivemore » charge on adjacent carbon sites, leading to the side-on adsorption of oxygen molecules and breakage of the O-O bond during ORR.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [2];  [3]; ORCiD logo [1]
  1. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  3. The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1480962
Report Number(s):
BNL-209368-2018-JAAM
Journal ID: ISSN 2196-0216
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Volume: 5; Journal Issue: 14; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Jain, Deeksha, Mamtani, Kuldeep, Gustin, Vance, Gunduz, Seval, Celik, Gokhan, Waluyo, Iradwikanari, Hunt, Adrian, Co, Anne C., and Ozkan, Umit S.. Enhancement in Oxygen Reduction Reaction Activity of Nitrogen-Doped Carbon Nanostructures in Acidic Media through Chloride-Ion Exposure. United States: N. p., 2018. Web. doi:10.1002/celc.201800134.
Jain, Deeksha, Mamtani, Kuldeep, Gustin, Vance, Gunduz, Seval, Celik, Gokhan, Waluyo, Iradwikanari, Hunt, Adrian, Co, Anne C., & Ozkan, Umit S.. Enhancement in Oxygen Reduction Reaction Activity of Nitrogen-Doped Carbon Nanostructures in Acidic Media through Chloride-Ion Exposure. United States. doi:10.1002/celc.201800134.
Jain, Deeksha, Mamtani, Kuldeep, Gustin, Vance, Gunduz, Seval, Celik, Gokhan, Waluyo, Iradwikanari, Hunt, Adrian, Co, Anne C., and Ozkan, Umit S.. Tue . "Enhancement in Oxygen Reduction Reaction Activity of Nitrogen-Doped Carbon Nanostructures in Acidic Media through Chloride-Ion Exposure". United States. doi:10.1002/celc.201800134.
@article{osti_1480962,
title = {Enhancement in Oxygen Reduction Reaction Activity of Nitrogen-Doped Carbon Nanostructures in Acidic Media through Chloride-Ion Exposure},
author = {Jain, Deeksha and Mamtani, Kuldeep and Gustin, Vance and Gunduz, Seval and Celik, Gokhan and Waluyo, Iradwikanari and Hunt, Adrian and Co, Anne C. and Ozkan, Umit S.},
abstractNote = {Nitrogen-doped carbon nanostructures (CNx) are promising cathode materials as catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane (PEM) fuel cells. Incorporation of chlorine into CNx catalysts using a facile methodology can lead to a significant improvement in the ORR activity in acidic media, as confirmed by electrochemical half-cell measurements. The chlorine-containing CNx catalyst (CNx-Cl) is synthesized by soaking CNx powder in 0.3 M HCl. The analysis of near-edge X-ray absorption fine structure spectra collected in the C K-edge region and Fourier-transform infrared spectra confirm the formation of C-Cl bonds in CNx-Cl. X-ray photoelectron spectroscopy (XPS) results reveal the presence of three distinct chlorine species in the CNx-Cl sample: (i) organic chlorine (C-Cl), (ii) anionic chloride in the positively charged environment of a pyridinium ring (N+Cl-), and (iii) physisorbed ionic chloride. Results from temperature-programmed desorption studies under inert atmosphere corroborate the conclusions from XPS depth profiling analysis. The improvement in ORR activity after exposure of the CNx catalyst to chloride anions can be attributed to the creation of C-Cl functionalities as additional active sites. The difference in the electronegativity of C and Cl atoms results in a net positive charge on adjacent carbon sites, leading to the side-on adsorption of oxygen molecules and breakage of the O-O bond during ORR.},
doi = {10.1002/celc.201800134},
journal = {ChemElectroChem},
number = 14,
volume = 5,
place = {United States},
year = {Tue May 08 00:00:00 EDT 2018},
month = {Tue May 08 00:00:00 EDT 2018}
}

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