Optimizing surface active sites via burying single atom into subsurface lattice for boosted methanol electrooxidation

The precise fabrication and regulation of the stable catalysts with desired performance still challengeable for single atom catalysts. Here, the Ru single atoms with different coordination environment in Ni₃FeN lattice are synthesized and studied as a typical case over alkaline methanol electrooxidation. The Ni₃FeN with buried Ru atoms in subsurface lattice (Ni₃FeN-Ru_buried) exhibits high selectivity and Faradaic efficiency of methanol to formate conversion. Meanwhile, operando spectroscopies reveal that the Ni₃FeN-Ru_buried exhibits an optimized adsorption of reactants along with an inhibited surface structural reconstruction. Additional theoretical simulations demonstrate that the Ni₃FeN-Ru_buried displays a regulated local electronic states of surface metal atoms with an optimized adsorption of reactants and reduced energy barrier of potential determining step. This work not only reports a high-efficient catalyst for methanol to formate conversion in alkaline condition, but also offers the insight into the rational design of single atom catalysts with more accessible surficial active sites.