The role of surface oxidation and Fe–Ni synergy in Fe–Ni–S catalysts for CO2 hydrogenation

Abstract

Increasing carbon dioxide (CO₂) emissions, resulting in climate change, have driven the motivation to achieve the effective and sustainable conversion of CO₂ into useful chemicals and fuels. Taking inspiration from biological processes, synthetic iron–nickel-sulfides have been proposed as suitable catalysts for the hydrogenation of CO₂. In order to experimentally validate this hypothesis, here we report violarite (Fe,Ni)₃S₄ as a cheap and economically viable catalyst for the hydrogenation of CO₂ into formate under mild, alkaline conditions at 125 °C and 20 bar (CO₂ : H₂ = 1 : 1). Calcination of violarite at 200 °C resulted in excellent catalytic activity, far superior to that of Fe-only and Ni-only sulfides. We further report first principles simulations of the CO₂ conversion on the partially oxidised (001) and (111) surfaces of stoichiometric violarite (FeNi₂S₄) and polydymite (Ni₃S₄) to rationalise the experimentally observed trends. We have obtained the thermodynamic and kinetic profiles for the reaction of carbon dioxide (CO₂) and water (H₂O) on the catalyst surfaces via substitution and dissociation mechanisms. We report that the partially oxidised (111) surface of FeNi₂S₄ is the best catalyst in the series and that the dissociation mechanism is the most favourable. Our study reveals that the partial oxidation of the FeNi₂S₄ surface, as well as the synergy of the Fe and Ni ions, are important in the catalytic activity of the material for the effective hydrogenation of CO₂ to formate.