The dehydrogenation of formate salts is a potentially viable chemical pathway for on-demand production of hydrogen. Formate salts have certain advantages over metal hydrides and liquid organic hydrogen carriers, including low cost, ease of storage, low toxicity, and mild reaction temperatures. Intriguingly, all common metals except Pd are essentially inactive for this reaction, which remains not understood. We present a density functional theory (DFT) based study to investigate the mechanistic disparities between representative catalytic metals including Pd, Pt, and Ni toward catalyzing formate dehydrogenation, with aqueous interface and charge effects taken into account. The findings are discussed in the more general context of formate/formic acid chemistries as well as recent experimental characterization of this catalytic reaction system. The theoretical insights are furthermore leveraged to screen for compositionally random multimetallic alloys capable of catalyzing this reaction using Korringa-Kohn-Rostoker Coherent Potential Approximation (KKR-CPA) and Virtual Crystal Approximation (VCA) calculations.
