Nickel Iron Diselenide for Highly Efficient and Selective Electrocatalytic Conversion of Methanol to Formate

The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni_{1- x} Fe_x Se₂ nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, Ni_0.75 Fe_0.25 Se₂ , this diselenide is able to produce 0.47 mmol cm^-2 h^-1 of formate at 50 mA cm^-2 with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm^-2 and 2.2 A mg^-1 in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals.