Thermally Methanol Oxidation via the Mn(1)@Co(3)O(4)(111) Facet: Non-CO Reaction Pathway

[Image: see text] Co(3)O(4), 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 Co(3)O(4)(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 Mn(1)@Co(3)O(4)(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 Mn(1)@Co(3)O(4)(111) facet, giving rise to the stable configuration: two O* and one CH(3)OH* adsorbates. Then, the Mn(1)@Co(3)O(4)(111) facet activates the O–H and C–H bonds within CH(3)OH*, advances CH(3)O* → H(2)CO* → HCOO* → COO*, and releases the products H(2), H(2)O, and CO(2) consecutively.