Surface Selenium Coating Promotes Selective Methanol-to-Formate Electrooxidation on Ni3Se4 Nanoparticles

In the quest to replace fossil fuels and reduce carbon dioxide emissions, developing energy technologies based on clean catalytic processes is fundamental. However, the cost-effectiveness of these technologies strongly relies on the availability of efficient catalysts made of abundant elements. Herein, this study presents a one-step hydrothermal method to obtain a series of Ni3Se4 nanoparticles with a layer of amorphous selenium on their surface. When employed as electrocatalysts for the methanol oxidation reaction (MOR), the optimized proper surface Se-coated Ni3Se4 nanoparticles exhibit a high current density of 160 mA cm–2 at 1.6 V, achieving a high methanol-to-formate Faradaic efficiency above 97.8% and excellent stability with less than 20% current decay after an 18 h chronoamperometry test. This excellent performance is rationalized using density functional theory calculations, which unveil that the electrochemical recombination of SeOx results in a reduction of the energy barrier for the dehydrogenation of methanol during the MOR process.