Theory of Electro-Ionic Perturbations at Supported Electrocatalyst Nanoparticles

Physical Review Letters, vol. 134, pp. 066201

Abstract

Nanoscopic heterogeneities in composition and structure are quintessential for the properties of electrocatalyst materials. Here, we present a semiclassical model to study the electrochemical properties of supported electrocatalyst nanoparticles (NP). The model captures the correlated electronic and ionic equilibration across NP, support, and electrolyte. It reveals peculiar trends in surface charging of the supported NP, validated by comparison with first-principles calculations. Support-induced perturbations in electronic and ionic charge densities at the NP's active surface manifest as distinct potentials of zero local electronic and ionic charges that could differ by more than 0.5 V in the studied system.

Authors 4

1. Yufan Zhang Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering

   Forschungszentrum Jülich · RWTH Aachen University

   Affiliation as printed

   Forschungszentrum Jülich GmbH

   RWTH Aachen University

   Chair of Theory and Computation of Energy Materials, Faculty of Georesources and Materials Engineering, RWTH Aachen University, 52062 Aachen, Germany

2. Tobias Binninger

   Forschungszentrum Jülich

   Affiliation as printed

   Forschungszentrum Jülich GmbH

3. Jun Zh. Huang Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering

   Forschungszentrum Jülich · RWTH Aachen University

   Affiliation as printed

   Forschungszentrum Jülich GmbH

   RWTH Aachen University

   Chair of Theory and Computation of Energy Materials, Faculty of Georesources and Materials Engineering, RWTH Aachen University, 52062 Aachen, Germany

4. Michael Hermann Eikerling Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Engineering

   Forschungszentrum Jülich · RWTH Aachen University

   Affiliation as printed

   Forschungszentrum Jülich GmbH

   RWTH Aachen University

   Chair of Theory and Computation of Energy Materials, Faculty of Georesources and Materials Engineering, RWTH Aachen University, 52062 Aachen, Germany