Low temperature CO oxidation: Effects of support, composition and structure
Doctoral thesis, 2023

Carbon monoxide is a tasteless, colorless and in-odorous toxic gas, which is formed during incomplete combustion. Due to its toxicity, efficient methods for CO oxidation to CO2 are required. One of the most active catalysts for this reaction is platinum, and the technological catalyst is generally based on nanosized platinum, yielding a high atom efficiency.
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.

PJ salen
Opponent: Veronica Ganduglia Pirovano Institute of Catalysis and Petrochemistry

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

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

More information

Latest update

5/1/2023 9