A Multitechnique Study of C<sub>2</sub>H<sub>4</sub> Adsorption on a Model Single-Atom Rh<sub>1</sub> Catalyst

Author(s)
Chunlei Wang, Panukorn Sombut, Lena Puntscher, Manuel Ulreich, Jiri Pavelec, David Rath, Jan Balajka, Matthias Meier, Michael Schmid, Ulrike Diebold, Cesare Franchini, Gareth S. Parkinson
Abstract

Single-atom catalysts are potentially ideal model systems to investigate structure-function relationships in catalysis if the active sites can be uniquely determined. In this work, we study the interaction of C2H4 with a model Rh/Fe3O4(001) catalyst that features 2-, 5-, and 6-fold coordinated Rh adatoms, as well as Rh clusters. Using multiple surface-sensitive techniques in combination with calculations of density functional theory (DFT), we follow the thermal evolution of the system and disentangle the behavior of the different species. C2H4 adsorption is strongest at the 2-fold coordinated Rh1 with a DFT-determined adsorption energy of −2.26 eV. However, desorption occurs at lower temperatures than expected because the Rh migrates into substitutional sites within the support, where the molecule is more weakly bound. The adsorption energy at the 5-fold coordinated Rh sites is predicated to be −1.49 eV, but the superposition of this signal with that from small Rh clusters and additional heterogeneity leads to a broad C2H4 desorption shoulder in TPD above room temperature.

Organisation(s)
Computational Materials Physics
External organisation(s)
Technische Universität Wien, University of Bologna
Journal
Journal of Physical Chemistry C
Volume
128
Pages
15404-15411
No. of pages
8
ISSN
1932-7447
DOI
https://doi.org/10.1021/acs.jpcc.4c03588
Publication date
09-2024
Peer reviewed
Yes
Austrian Fields of Science 2012
103020 Surface physics, 103043 Computational physics, 104017 Physical chemistry
ASJC Scopus subject areas
Electronic, Optical and Magnetic Materials, General Energy, Physical and Theoretical Chemistry, Surfaces, Coatings and Films
Portal url
https://ucrisportal.univie.ac.at/en/publications/e879e7cf-53c6-4e56-ab6d-d2cb035e9ae3