Simulations of the Electrochemical Oxidation of Pt Nanoparticles of Various Shapes

TL;DR

This paper introduces GREG, a simulation routine for studying electrochemical stability of platinum nanoparticles with various shapes, revealing how shape influences oxidation behavior and onset potentials.

Contribution

The work presents a novel grand-canonical simulation method using reactive force fields to model nanoparticle oxidation processes as a function of electrochemical potential.

Findings

Onset potentials vary with nanoparticle shape.

Shape influences oxidation behavior and stability.

Electrochemical phase diagrams are constructed for different shapes.

Abstract

The activity and stability of a platinum nanoparticle (NP) is not only affected by its size but additionally depends on its shape. To this end, simulations can identify structure-property relationships to make a priori decisions on the most promising structures. While activity is routinely probed by electronic structure calculations on simplified surface models, modeling the stability of NP model systems in electrochemical reactions is challenging due to the long timescale of relevant processes such as oxidation beyond the point of reversibility. In this work, a routine for simulating electrocatalyst stability is presented. The procedure is referred to as GREG after its main ingredients - a grand-canonical simulation approach using reactive force fields to model electrochemical reactions as a function of the galvanic cell potential. The GREG routine is applied to study the oxidation of 3 nm octahedral, cubic, dodecahedral, cuboctahedral, spherical, and tetrahexahedral platinum NPs. The oxidation process is analyzed using adsorption isobars as well as interaction energy heat maps that provide the basis for constructing electrochemical phase diagrams. Onset potentials for surface oxidation increase in the sequence cube ~= dodecahedron <= octahedron <= tetrahexahdron < sphere < cuboctahedron, establishing a relationship between oxidation behavior and surface facet structure. The electrochemical results are rationalized using structural and electronic analysis.