Methanol synthesis on ZnO from molecular dynamics

Abstract

AbstractThis paper reviews our efforts to simulate methanol synthesis from CO and H2 on defective ZnO surfaces using advanced molecular dynamics techniques. This apparently simple chemical reaction occurring on a seemingly well‐defined surface appears to be astonishingly complex. First of all, the preferred oxidation state of F centers at the polar oxygen terminated surface is found to be dictated by the chemical composition and the thermodynamic properties of the gas phase in contact with ${\rm ZnO}(000\overline {1} )$. Secondly, reaction intermediates and pathways along the catalytic cycle taking place at or close to these defects are found to depend in a sensitive way on their oxidation state. Thirdly, it is seen that the gas phase close to the catalytic surface might be transiently involved in some of the reaction steps in a non‐trivial manner. Last but not least, the scenario is found to be greatly enriched upon involving copper clusters on polar ZnO surfaces in view of utmost strong metal‐support interactions (SMSIs), which are directly related to the polar nature of ${\rm ZnO}(000\overline {1} )$. Taken together, an unexpectedly rich picture is unveiled by the molecular dynamics approach to computational heterogeneous catalysis when applied to methanol synthesis on bare ZnO.