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Title: Nanoalloy electrocatalysis: Simulating cyclic voltammetry from configurational thermodynamics with adsorbates

We simulate the adsorption isotherms for alloyed nanoparticles (nanoalloys) with adsorbates to determine cyclic voltammetry (CV) during electrocatalysis. The effect of alloying on nanoparticle adsorption isotherms is provided by a hybrid-ensemble Monte Carlo simulation that uses the cluster expansion method extended to non-exchangeable coupled lattices for nanoalloys with adsorbates. Exemplified here for the hydrogen evolution reaction, a 2-dimensional CV is mapped for Pd–Pt nanoalloys as a function of both electrochemical potential and the global Pt composition, and shows a highly non-linear alloying effect on CV. Detailed features in CV arise from the interplay among the H-adsorption in multiple sites that is closely correlated with alloy configurations, which are in turn affected by the H-coverage. The origins of specific features in CV curves are assigned. As a result, the method provides a more complete means to design nanoalloys for electrocatalysis.
 [1] ;  [2] ;  [1]
  1. Iowa State Univ., Ames, IA (United States)
  2. Institute of High Performance Computing, Singapore (Singapore)
Publication Date:
Report Number(s):
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:
AC02-07CH11358; DMR012448; DMR0325939
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 17; Journal Issue: 42; Journal ID: ISSN 1463-9076
Royal Society of Chemistry
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
Country of Publication:
United States
77 NANOSCIENCE AND NANOTECHNOLOGY; cluster expansion; first-principles; nanoalloy; Pd; Pt; H; alloyed nanoparticle
OSTI Identifier: