From molecular adsorption to decomposition of methanol on various ZnO facets: A periodic DFT study

Methanol is an interesting and important molecule to study because of its potential to replace existing fuels. It is also a prominent hydrogen source which can be used to generate hydrogen in-situ. ZnO is widely used as catalyst in synthesis of methanol from CO 2 at industrial scale. In this work, we demonstrate that the same catalyst could be used for MeOH decomposition. We have investigated interaction of methanol with various flat and stepped facets of ZnO by employing Density Functional Theory (DFT). Two flat [(10 1 ¯ 0) and (11 2 ¯ 0)] and two stepped [(10 1 ¯ 3) and (11 2 ¯ 2)] facets are studied in detail for methanol adsorption. Chemisorption of MeOH with varying strength is common to all four facets. Most importantly spontaneous dissociation of O-H bond of methanol is observed on all facets except (11 2 ¯ 0). Our DFT calculations reveal that molecular adsorption is favored on flat facets, while dissociation is favored on step facets. Also, (10 1 ¯ 0) facet undergoes substantial reconstruction upon MeOH adsorption. Activation of C-H bond along with strengthening of C-O bond on ZnO facets suggest partial oxidation of methanol. With our DFT investigations, we dig deeper into the underlying electronic structure of various facets of ZnO and provide rationale for the observed facet dependent interaction of ZnO with MeOH. • Interaction of Methanol with the most prominent facets of ZnO has been studied. • Flat facets favor molecular adsorption while stepped facets favor dissociation of MeOH. • (10 1 ¯ 0) shows significant surface reconstruction upon MeOH adsorption. • Reduction of C-O bond-length indicates partial oxidation of methanol on ZnO facets. • Electronic structure calculations explain the surface dependent reactivity of ZnO towards MeOH.