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Title: Trends in electrocatalysis : from extended to nanoscale surfaces.

Abstract

One of the key objectives in fuel-cell technology is to improve and reduce Pt loading as the oxygen-reduction catalyst. Here, we show a fundamental relationship in electrocatalytic trends on Pt{sub 3}M (M=Ni, Co, Fe, Ti, V) surfaces between the experimentally determined surface electronic structure (the d-band centre) and activity for the oxygen-reduction reaction. This relationship exhibits 'volcano-type' behavior, where the maximum catalytic activity is governed by a balance between adsorption energies of reactive intermediates and surface coverage by spectator (blocking) species. The electrocatalytic trends established for extended surfaces are used to explain the activity pattern of Pt{sub 3}M nanocatalysts as well as to provide a fundamental basis for the catalytic enhancement of cathode catalysts. By combining simulations with experiments in the quest for surfaces with desired activity, an advanced concept in nanoscale catalyst engineering has been developed.

Authors:
; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
962549
Report Number(s):
ANL/MSD/JA-58383
TRN: US200916%%23
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nature Mater.; Journal Volume: 6; Journal Issue: 3 ; 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
30 DIRECT ENERGY CONVERSION; 36 MATERIALS SCIENCE; ELECTROCATALYSTS; FUEL CELLS; PLATINUM ALLOYS; CATALYTIC EFFECTS; ELECTRONIC STRUCTURE; NICKEL ALLOYS; COBALT ALLOYS; IRON ALLOYS; TITANIUM ALLOYS; VANADIUM ALLOYS; REDOX REACTIONS; NANOSTRUCTURES

Citation Formats

Stamenkovic, V. R., Mun, B. S., Arenz, M., Mayrhofer, K. J. J., Lucas, C. A., Wang, G., Ross, P. N., Markovic, N. M., Materials Science Division, Lawrence Berkeley Nat. Lab., Technical Univ. Munich, Univ. of Liverpool, and Univ. of South Carolina. Trends in electrocatalysis : from extended to nanoscale surfaces.. United States: N. p., 2007. Web. doi:10.1038/nmat1840.
Stamenkovic, V. R., Mun, B. S., Arenz, M., Mayrhofer, K. J. J., Lucas, C. A., Wang, G., Ross, P. N., Markovic, N. M., Materials Science Division, Lawrence Berkeley Nat. Lab., Technical Univ. Munich, Univ. of Liverpool, & Univ. of South Carolina. Trends in electrocatalysis : from extended to nanoscale surfaces.. United States. doi:10.1038/nmat1840.
Stamenkovic, V. R., Mun, B. S., Arenz, M., Mayrhofer, K. J. J., Lucas, C. A., Wang, G., Ross, P. N., Markovic, N. M., Materials Science Division, Lawrence Berkeley Nat. Lab., Technical Univ. Munich, Univ. of Liverpool, and Univ. of South Carolina. Mon . "Trends in electrocatalysis : from extended to nanoscale surfaces.". United States. doi:10.1038/nmat1840.
@article{osti_962549,
title = {Trends in electrocatalysis : from extended to nanoscale surfaces.},
author = {Stamenkovic, V. R. and Mun, B. S. and Arenz, M. and Mayrhofer, K. J. J. and Lucas, C. A. and Wang, G. and Ross, P. N. and Markovic, N. M. and Materials Science Division and Lawrence Berkeley Nat. Lab. and Technical Univ. Munich and Univ. of Liverpool and Univ. of South Carolina},
abstractNote = {One of the key objectives in fuel-cell technology is to improve and reduce Pt loading as the oxygen-reduction catalyst. Here, we show a fundamental relationship in electrocatalytic trends on Pt{sub 3}M (M=Ni, Co, Fe, Ti, V) surfaces between the experimentally determined surface electronic structure (the d-band centre) and activity for the oxygen-reduction reaction. This relationship exhibits 'volcano-type' behavior, where the maximum catalytic activity is governed by a balance between adsorption energies of reactive intermediates and surface coverage by spectator (blocking) species. The electrocatalytic trends established for extended surfaces are used to explain the activity pattern of Pt{sub 3}M nanocatalysts as well as to provide a fundamental basis for the catalytic enhancement of cathode catalysts. By combining simulations with experiments in the quest for surfaces with desired activity, an advanced concept in nanoscale catalyst engineering has been developed.},
doi = {10.1038/nmat1840},
journal = {Nature Mater.},
number = 3 ; 2007,
volume = 6,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • One of the key objectives in fuel-cell technology is to improve and reduce Pt loading as the oxygen-reduction catalyst. Here, we show a fundamental relationship in electrocatalytic trends on Pt{sub 3}M (M=Ni, Co, Fe, Ti, V) surfaces between the experimentally determined surface electronic structure (the d-band centre) and activity for the oxygen-reduction reaction. This relationship exhibits 'volcano-type' behavior, where the maximum catalytic activity is governed by a balance between adsorption energies of reactive intermediates and surface coverage by spectator (blocking) species. The electrocatalytic trends established for extended surfaces are used to explain the activity pattern of Pt{sub 3}M nanocatalysts asmore » well as to provide a fundamental basis for the catalytic enhancement of cathode catalysts. By combining simulations with experiments in the quest for surfaces with desired activity, an advanced concept in nanoscale catalyst engineering has been developed.« less
  • No abstract prepared.
  • The classic models of metal electrode-electrolyte interfaces generally focus on either covalent interactions between adsorbates and solid surfaces or on long-range electrolyte-metal electrostatic interactions. Here we demonstrate that these traditional models are insufficient. To understand electrocatalytic trends in the oxygen reduction reaction (ORR), the hydrogen oxidation reaction (HOR) and the oxidation of methanol on platinum surfaces in alkaline electrolytes, non-covalent interactions must be considered. We find that non-covalent interactions between hydrated alkali metal cations M{sup +}(H{sub 2}O){sub x} and adsorbed OH (OH{sub ad}) species increase in the same order as the hydration energies of the corresponding cations (Li{sup +} >>more » Na{sup +} > K{sup +} > Cs{sup +}) and also correspond to an increase in the concentration of OH{sub ad}-M{sup +}(H{sub 2}O){sub x} clusters at the interface. These trends are inversely proportional to the activities of the ORR, the HOR and the oxidation of methanol on platinum (Cs{sup +} > K{sup +} > Na{sup +} >> Li{sup +}), which suggests that the clusters block the platinum active sites for electrocatalytic reactions.« less