%0 Conference Paper
%A Zhang, Yufan
%A Binninger, Tobias
%A Huang, Jun
%A Eikerling, Michael
%T Entanglement of Electronic Interactions and Double-Layer Charging for Supported Electrocatalyst Nanoparticles Revealed by Density-Potential Functional Theory
%M FZJ-2024-00737
%D 2023
%X Metal nanoparticles (NPs) on solid substrates are widely used as (electro)catalysts. Electron transfer between the catalyst NP and support material can strongly influence the catalytic activity, a phenomenon referred to as electronic metal-support interactions (EMSI) [1]. In situ X-ray absorption spectroscopy (XAS) provides a mean to probe the charging of catalyst NPs [2,3]. However, several key questions remained unclear, including the spatial distribution of transferred electrons and their actual impact on the NP’s catalytically active surface in contact with the electrolyte [4]. In addition, the charging characteristics of the electric double-layer (EDL) around the NP are affected by support and neighboring NPs [5]. Therefore, computer simulations are required to reveal the interrelation between electronic and double-layer effects, which is crucial for improving the catalytic activity of supported NPs.In this study, we use the recently developed framework of density-potential functional theory (DPFT) which combines orbital-free density functional theory and modified Poisson-Boltzmann theory to address solid and electrolyte phases simultaneously under constant potentials [6]. Our approach considers electronic phenomena like electron spillover, which is beyond the scope of traditional double-layer models. We also study the EDL of nanometer-scale particles, which is typically beyond the capability of DFT calculations.The effects of NP size, proximity, and support work function probed by in situ spectroscopy have sparked some controversies. Our model offers a rationale for these controversies by uncovering the interplay of electronic interactions and double-layer charging under constant potential conditions. Specifically, local reaction conditions, such as the local electric field and cation concentration, are regulated.Our model is relevant to experimental groups as it assists in the interpretation of in situ spectroscopy data regarding the distribution and catalytic consequences of transferred electrons. For the community of DFT-calculation-based materials screening, our model helps identify relevant descriptors for the catalytic properties of supported catalyst systems.
%B Annual meeting of international society of electrochemistry
%C 3 Sep 2023 - 8 Sep 2023, Lyon (France)
Y2 3 Sep 2023 - 8 Sep 2023
M2 Lyon, France
%F PUB:(DE-HGF)24
%9 Poster
%R 10.34734/FZJ-2024-00737
%U https://juser.fz-juelich.de/record/1021441