Thermally Methanol Oxidation via the Mn1@Co3O4(111) Facet: Non-CO Reaction Pathway.

Abstract

Co3O4, as the support of single-atom catalysts, is effective in electron-structure modulation to get distinct methanol adsorption behaviors and adjustable reaction pathways for the methanol oxidation reaction. Herein, we considered the facets that constitute a Co vacancy of the Co3O4(111) facet and a foreign metal atom M (M = Fe, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mn) leading to single-atom catalysts. The Mn1@Co3O4(111) facet is the facet considered the most favorable among all of the possible terminations. Oxygen adsorption, decomposition, and its co-adsorption with methanol are the vital steps of methanol oxidation at the exposed Mn1@Co3O4(111) facet, giving rise to the stable configuration: two O* and one CH3OH* adsorbates. Then, the Mn1@Co3O4(111) facet activates the O-H and C-H bonds within CH3OH*, advances CH3O* → H2CO* → HCOO* → COO*, and releases the products H2, H2O, and CO2 consecutively.