Dimethyl carbonate synthesis from CO2 and methanol over CeO2: elucidating the surface intermediates and oxygen vacancy-assisted reaction mechanism
Dragos Stoian (European Synchrotron Radiation Facility, Barcelona Institute of Science and Technology (BIST), University Rovira i Virgili)
Toshiyuki Sugiyama (Hokkaido University)
Atul Bansode (TU Delft - ChemE/Catalysis Engineering, 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 (Hokkaido University, University of Tokyo)
A. Urakawa (TU Delft - ChemE/Catalysis Engineering, Barcelona Institute of Science and Technology (BIST))
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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.
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