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.