Mo single atoms in the Cu(111) surface as improved catalytic active centers for deoxygenation reactions

Deoxygenation processes are key in the transformation of bio-sourced molecules to sustainable fuels, a field where heterogeneous catalysis plays a central role. A recent study suggested a link between deoxygenation intermediates and metathesis initiator sites on Mo2C surfaces through alkylidene formation from ketones and aldehydes. There, in a density functional theory (DFT) analysis of experimental data, isolated Mo atoms were found to be active sites for carbonyl bond scission, and surface carbon was found to bond to the alkylidene intermediate. By extension, the present DFT study explores the single-atom alloy (SAA) approach for carbonyl bond dissociation steps when Mo is embedded in a Cu(111) surface. The study finds that the doped-Mo Cu(111) SAA breaks the Bronsted-Evans-Polanyi linear relation, displaying both a low activation energy for carbonyl bond scission and moderate adsorption energy of the resulting alkylidene. The findings point towards new horizons in SAA design through using highly reactive early transition metals as single-atom dopants.