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Title: In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction

Abstract

To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, themore » fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.« less

Authors:
 [1];  [2];  [3];  [3];  [2];  [1];  [4];  [5];  [5];  [2];  [2];  [6]
  1. Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400, United States
  2. Chemistry Department, Brookhaven National Laboratory, Building 555, Upton, New York 11973, United States
  3. Department of Physics, Yeshiva University, New York, New York 10016, United States
  4. Center for Functional Nanomaterials, Brookhaven National Laboratory, Building 735, Upton, New York 11973, United States
  5. Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712-1224, United States
  6. Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400, United States, Condensed Matter Physics and Materials Science Department, Brookhaven National Laboratory, Building 480, Upton, New York 11973, United States
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1414809
Alternate Identifier(s):
OSTI ID: 1226057
Report Number(s):
BNL-108458-2015-JA
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
AC02-98CH10886; FG02-13ER16428; SC-00112704; FG02-03ER15476; SC00112704
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 39; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; density functional theory; X-ray absorption spectroscopy; ultrathin nanowires; oxygen reduction reaction; surface segregation

Citation Formats

Liu, Haiqing, An, Wei, Li, Yuanyuan, Frenkel, Anatoly I., Sasaki, Kotaro, Koenigsmann, Christopher, Su, Dong, Anderson, Rachel M., Crooks, Richard M., Adzic, Radoslav R., Liu, Ping, and Wong, Stanislaus S. In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction. United States: N. p., 2015. Web. doi:10.1021/jacs.5b07093.
Liu, Haiqing, An, Wei, Li, Yuanyuan, Frenkel, Anatoly I., Sasaki, Kotaro, Koenigsmann, Christopher, Su, Dong, Anderson, Rachel M., Crooks, Richard M., Adzic, Radoslav R., Liu, Ping, & Wong, Stanislaus S. In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction. United States. https://doi.org/10.1021/jacs.5b07093
Liu, Haiqing, An, Wei, Li, Yuanyuan, Frenkel, Anatoly I., Sasaki, Kotaro, Koenigsmann, Christopher, Su, Dong, Anderson, Rachel M., Crooks, Richard M., Adzic, Radoslav R., Liu, Ping, and Wong, Stanislaus S. Thu . "In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction". United States. https://doi.org/10.1021/jacs.5b07093.
@article{osti_1414809,
title = {In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction},
author = {Liu, Haiqing and An, Wei and Li, Yuanyuan and Frenkel, Anatoly I. and Sasaki, Kotaro and Koenigsmann, Christopher and Su, Dong and Anderson, Rachel M. and Crooks, Richard M. and Adzic, Radoslav R. and Liu, Ping and Wong, Stanislaus S.},
abstractNote = {To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.},
doi = {10.1021/jacs.5b07093},
journal = {Journal of the American Chemical Society},
number = 39,
volume = 137,
place = {United States},
year = {Thu Sep 24 00:00:00 EDT 2015},
month = {Thu Sep 24 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.5b07093

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