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@INPROCEEDINGS{Zhang:1021441,
author = {Zhang, Yufan and Binninger, Tobias and Huang, Jun and
Eikerling, Michael},
title = {{E}ntanglement of {E}lectronic {I}nteractions and
{D}ouble-{L}ayer {C}harging for {S}upported
{E}lectrocatalyst {N}anoparticles {R}evealed by
{D}ensity-{P}otential {F}unctional {T}heory},
reportid = {FZJ-2024-00737},
year = {2023},
abstract = {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.},
month = {Sep},
date = {2023-09-03},
organization = {Annual meeting of international
society of electrochemistry, Lyon
(France), 3 Sep 2023 - 8 Sep 2023},
subtyp = {Other},
cin = {IEK-13},
cid = {I:(DE-Juel1)IEK-13-20190226},
pnm = {1231 - Electrochemistry for Hydrogen (POF4-123)},
pid = {G:(DE-HGF)POF4-1231},
typ = {PUB:(DE-HGF)24},
doi = {10.34734/FZJ-2024-00737},
url = {https://juser.fz-juelich.de/record/1021441},
}