Dimethyl carbonate synthesis from CO2 and methanol over CeO2: elucidating the surface intermediates and oxygen vacancy-assisted reaction mechanism

Journal article (2023)

Authors

Dragos Stoian University Rovira i Virgili, Barcelona Institute of Science and Technology (BIST), European Synchrotron Radiation Facility
Toshiyuki Sugiyama Hokkaido University
Atul Bansode , Barcelona Institute of Science and Technology (BIST)
Francisco Medina University Rovira i Virgili
Wouter van Beek European Synchrotron Radiation Facility
Jun-ya Hasegawa Hokkaido University
Akira Nakayama University of Tokyo, Hokkaido University
A. Urakawa Barcelona Institute of Science and Technology (BIST),
Copyright: © 2023 Dragos Stoian, Toshiyuki Sugiyama, Atul Bansode, Francisco Medina, Wouter van Beek, Jun-ya Hasegawa, Akira Nakayama, A. Urakawa
DOI: https://doi.org/10.1039/D3SC04466A
More Info
expand_more

Published Date

2023

Language

English

Abstract

Surface intermediate species and oxygen vacancy-assisted mechanism over CeO2 catalyst in the direct dimethyl carbonate (DMC) synthesis from carbon dioxide and methanol are suggested by means of transient spectroscopic methodologies in conjunction with multivariate spectral analysis. How the two reactants, i.e. CO2 and methanol, interact with the CeO2 surface and how they form decisive surface intermediates leading to DMC are unraveled by DFT-based molecular dynamics simulation by precise statistical sampling of various configurations of surface states and intermediates. The atomistic simulations and uncovered stability of different intermediate states perfectly explain the unique DMC formation profile experimentally observed upon transient operations, strongly supporting the proposed oxygen vacancy-assisted reaction mechanism.