論文

査読有り 国際誌
2018年11月

Effects of Sulfate on the Oxygen Reduction Reaction Activity on Stabilized Pt Skin/PtCo Alloy Catalysts from 30 to 80 degrees C

LANGMUIR
  • Honami Nishikawa
  • ,
  • Hiroshi Yano
  • ,
  • Junji Inukai
  • ,
  • Donald A. Tryk
  • ,
  • Akihiro Iiyama
  • ,
  • Hiroyuki Uchida

34
45
開始ページ
13558
終了ページ
13564
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.langmuir.8b02945
出版者・発行元
AMER CHEMICAL SOC

The effects of the concentration of H2SO4 ([H2SO4]), which is the major decomposition product of polymer electrolyte membranes during the operation of fuel cells, on the performance of stabilized Pt skin/PtCo alloy nanocatalysts supported on high-surface-area carbon (Pt-xAL-PtCo/C) were investigated. Kinetically controlled activities for the oxygen reduction reaction (ORR) and the H2O2 yields (P(H2O2)) on the Pt-xAL-L-PtCo/C were examined based on hydrodynamic voltammograms in O-2-saturated 0.1 M HClO4 + X M H2SO4 (X = 0 to 5 X 10(-2)) by use of the channel flow double electrode method at temperatures between 30 and 80 degrees C. At X 10(-6) (1 mu M) and all temperatures examined, the apparent ORR rate constants k(app@0.85) (v) (per unit electrochemically active surface area) on Pt-xAL-PtCo/C at 0.85 V vs the reversible hydrogen electrode (RHE) were nearly identical with those in sulfate-free 0.1 M HClO4 and were at least twice as high as those on a commercial Pt/C catalyst (c-Pt/C). The values of k(app@0.85 v) on both Pt-xAL-PtCo/C and c-Pt/C decreased linearly with log[H2SO4] in the concentration range 10(-6) < X <= 5 X 10(-2). The detrimental effect by H2SO4 was less pronounced on Pt-xAL-PtCo/C than on c-Pt/C at high temperatures; the k(app@0.8.5 v) value at X = 5 X 10(-2) on the former at 80 C was maintained as high as 87%, whereas that of the latter was 66% (34% loss). The values of peroxide production percentage P(H2O2) on Pt-xAL-PtCo/C at 80 degrees C were nearly constant (ca. 0.22% at 0.76 V vs RHE) up to X = 5 X 10(-2). These superior characteristics are ascribed to weakened adsorption of sulfate on the Pt skin surface, supported by DFT calculations, which provides the great advantage of robustness in the presence of impurities, maintaining active sites for the ORR during the PEFC operation.

リンク情報
DOI
https://doi.org/10.1021/acs.langmuir.8b02945
PubMed
https://www.ncbi.nlm.nih.gov/pubmed/30378419
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000450695000012&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/acs.langmuir.8b02945
  • ISSN : 0743-7463
  • PubMed ID : 30378419
  • Web of Science ID : WOS:000450695000012

エクスポート
BibTeX RIS