Low temperature CO oxidation: Effects of support, composition and structure
Doctoral thesis, 2023
In this thesis, density functional theory (DFT) calculations, mean field micro kinetic models and kinetic Monte Carlo (kMC) simulations are used to investigate the reaction energetics and kinetics on model systems, to understand and enhance the low temperature reaction regime.
Experimental evidence of CO disproportionation stimulated the study of CO dissociation as a possible competing reaction to oxidation at low temperature. Our results show that dissociation of CO is facilitated at high coverages by a Boudouard reaction path at under-coordinated sites.
To study the reaction kinetics over nanoparticles, a complete description of the energy landscape is necessary. In order to reduce the computational cost, it is possible to describe the energy landscape through scaling relations like the Brønsted-Evans-Polanyi and structure sensitive relations that link the adsorption energy of the reactants with a chosen descriptor. The sensitivity of scaling relations and sticking coefficient on CO oxidation is investigated, showing that varying the slope of the scaling relations results only in minor modifications of the reaction kinetics.
It is known that reducible oxides like ceria can increase the reaction's activity at low temperatures, by allowing for a Mars-van Krevelen (MVK) path. The effect of Mars-van Krevelen reaction steps for CO oxidation over Pt/CeO2 is explored. Our results show that the high activity for CO oxidation at low temperatures is due to the possibility of following the MVK mechanism at low temperatures and not to overall lower reaction barriers. The nature of oxygen vacancies in ceria is furthermore investigated, and we show that the common assignment of XPS spectra shifts for the O 1s to the formation of oxygen vacancies might need reconsideration. Such shift could be instead due to the presence of adsorbed OH groups on the surface. More on the fundamental description of CO oxidation, we investigate the possibility of predicting reaction paths from the experimental measurements of reaction orders. Exploring different reaction pathways by mean field simulations shows that reaction orders alone do not reveal the reaction mechanism. Lastly, we investigate CO oxidation on dilute Pt-Au alloy nanoparticles.
Author
Noemi Bosio
Chalmers, Physics, Chemical Physics
Interface Reactions Dominate Low-Temperature CO Oxidation Activity over Pt/CeO<inf>2</inf>
Journal of Physical Chemistry C,;Vol. 126(2022)p. 16164-16171
Journal article
Can oxygen vacancies in ceria surfaces be measured by O1s photoemission spectroscopy?
Journal of physics. Condensed matter : an Institute of Physics journal,;Vol. 34(2022)
Journal article
On the signatures of oxygen vacancies in O1s core level shifts
Surface Science,;Vol. 705(2021)
Journal article
Interplay between CO Disproportionation and Oxidation: On the Origin of the CO Reaction Onset on Atomic Layer Deposition-Grown Pt/ZrO2Model Catalysts
ACS Catalysis,;Vol. 11(2021)p. 208-214
Journal article
Sensitivity of Monte Carlo Simulations to Linear Scaling Relations
Journal of Physical Chemistry C,;Vol. 124(2020)p. 11952-11959
Journal article
Reaction orders for CO oxidation over Pt: Influence of reaction mechanism and adsorbate-adsorbate interactions M. Di, N. Bosio, E. Dietze, M. Skoglundh, H. Grönbeck and P.-A. Carlsson
CO oxidation over dilute alloys studied by kinetic Monte Carlo N. Bosio and H. Grönbeck
Driving Forces
Sustainable development
Subject Categories
Physical Sciences
Chemical Sciences
Infrastructure
C3SE (Chalmers Centre for Computational Science and Engineering)
Areas of Advance
Materials Science
Doktorsavhandlingar vid Chalmers tekniska högskola. Ny serie: 0346-718X
Publisher
Chalmers
PJ salen
Opponent: Veronica Ganduglia Pirovano Institute of Catalysis and Petrochemistry