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

Abstract 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 Se 2 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 Se 2 , 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.