Improving the Oxygen Evolution Reaction on Fe3O4(001) with Single-Atom Catalysts

by E. Bianchetti, D. Perilli and C. Di Valentin
ACS Catal. 2023, 13, 7, pp 4811–4823 View at Publisher
DOI: 10.1021/acscatal.3c00337


Doping magnetite surfaces with transition-metal atoms is a promising strategy to improve the catalytic performance toward the oxygen evolution reaction (OER), which governs the overall efficiency of water electrolysis and hydrogen production. In this work, we investigated the Fe3O4(001) surface as a support material for single-atom catalysts of the OER. First, we prepared and optimized models of inexpensive and abundant transition metal atoms, such as Ti, Co, Ni, and Cu, trapped in various configurations on the Fe3O4(001) surface. Then, we studied their structural, electronic, and magnetic properties through HSE06 hybrid functional calculations. As a further step, we investigated the performance of these model electrocatalysts toward the OER, considering different possible mechanisms, in comparison with pristine magnetite surface, on the basis of the computational hydrogen electrode model developed by Nørskov and co-workers. Cobalt-doped systems are found to be the most promising electrocatalytic systems among those considered in this work. Overpotential values (~0.35 V) were in the range of those experimentally reported for mixed Co/Fe oxide (0.2-0.5 V).