Embodiments include metal catalyst compositions and methods of forming metal catalyst compositions. A metal catalyst composition can be formed by (a) contacting a supported metal catalyst surface with a ligand-containing alumina precursor for a predetermined contact time to form an intermediate layer having a plurality of aluminum moieties that chemically bond to the supported metal catalyst surface, optionally, contacting the intermediate layer of aluminum moieties with an inert gas for a predetermined intermediate stripping time to remove unreacted ligand-containing alumina precursors, (b) reacting the aluminum moieties with an oxidation reagent for a predetermined reaction time to convert at least a portion of the ligands to hydroxyl groups thereby forming a layer of the alumina over-coat on the supported metal catalyst surface or a previously formed layer of the alumina over-coat, (c) contacting the layer of the alumina over-coat formed in step (b) with an inert gas for a predetermined stripping time to remove unreacted oxidation reagents, replicating the sequential steps (a-c) to form an additional layer of the alumina over-coat, and (d) activating the alumina over-coat, after forming a final layer of the alumina over-coat, to form a plurality of pores therein.