Earth-Abundant Metal Oxides as Oxygen Evolution Electrocatalysts in 1 M H2SO4

Abstract

Water splitting is a very hot research topic as a preferred source for green hydrogen, as a key vector to facilitate a transition into an environmentally friendly and sustainable energy economy in the mid-term. But it is still far from being economically competitive with respect to current hydrogen production technologies based on fossil fuels. One of the major economic hurdles to reduce electrolysis costs is the lack of low-cost catalysts for hydrogen evolution and, more importantly, for oxygen evolution. The water oxidation process is considered the main bottleneck in the advancement of water splitting devices, since it is the rate limiting process, and the main cause of poor long-term performance.Most recent advances in the field of water oxidation catalysis are based on transition metal oxides, operating exclusively in alkaline electrolysis conditions. Unfortunately, these excellent oxygen evolution catalysts in basic pH ( > 13) rapidly lose their activity when the pH is lowered, and are far away from the performance exhibited by noble metals in acid solution. McCrory et al. established in 2013 1a benchmarking protocol to identify the potential of new OER electrocatalysts (and extended in 2015 2 to HER) comparing the initial activity and stability of the materials as a function of pH and showed how no other known catalysts at that time came close to the performance of IrOx-based materials.A simple processing technique using a partially hydrophobic binder has been proved to stabilize Co oxide, resulting in electrodes able to reach high current densities (> 10 mA cm-2) at competitive overpotentials and with long term stability for acidic OER catalysis3. Following this strategy, we have been able to conduct an extensive survey of the activity and stability of monometallic, binary and ternary earth-abundant transition metal oxides during electrocatalytic OER in 1 M H2SO4. Our results confirm the general validity of the strategy in using a partially hydrophobic electrode to confer high stability to common metal oxides under these harsh conditions.[1] C.C.L. McCrory, S. Jung, J.C. Peters, T.F. Jaramillo, Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction, J. Am. Chem. Soc. 135 (2013) 16977–16987.[2] C.C.L. McCrory, S. Jung, I.M. Ferrer, S.M. Chatman, J.C. Peters, T.F. Jaramillo, Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices, J. Am. Chem. Soc. 137 (2015) 4347–4357.[3] J. Yu, F.A. Garcés-Pineda, J. González-Cobos, M. Peña-Díaz, C. Rogero, S. Giménez, M.C. Spadaro, J. Arbiol, S. Barja, J.R. Galán-Mascarós, Sustainable oxygen evolution electrocatalysis in aqueous 1 M H2SO4 with earth abundant nanostructured Co3O4, Nat. Commun. 13 (2022) 4341. Figure 1