Roy, S.Devaraj, N.Tarafder, K.Chakraborty, C.Roy, S.2026-02-042022New Journal of Chemistry, 2022, 46, 14, pp. 6539-654811440546https://doi.org/10.1039/d2nj00219ahttps://idr.nitk.ac.in/handle/123456789/22628The oxygen evolution reaction over oxide vacancy-induced spinel Co<inf>3</inf>O<inf>4</inf> is a topic of tremendous scientific attention owing to the favourable adsorption of water, as also shown here through DFT calculations. However, the inclusion of an optimum amount of oxygen-ion vacancies at the surface and in the bulk of Co<inf>3</inf>O<inf>4</inf> remains a synthetic challenge in order to enhance the efficacy of the oxygen evolution reaction. Here, we have attempted a single-step scalable approach of solution combustion synthesis to incorporate the oxide ion vacancies in high-surface-area Co<inf>3</inf>O<inf>4</inf>. To benchmark the catalyst, we also synthesized Co<inf>3</inf>O<inf>4</inf> using elevated-temperature calcination routes. Detailed structural and surface analyses revealed the significant presence of oxide ion vacancies in the combustion-synthesized material. The solution combustion synthesized Co<inf>3</inf>O<inf>4</inf> due to the presence of oxygen-ion vacancies exhibited an excellent oxygen evolution reactivity with a lower overpotential and higher current density compared with the other Co<inf>3</inf>O<inf>4</inf> materials synthesized using calcination routes. Tafel slope calculations indicated that the formation of surface hydroxyl species through water dissociation over the oxide ion vacancies is the rate-determining step of the overall reaction. The mechanistic role of the oxygen-ion vacancies in the oxygen evolution reaction was further explored via DFT studies. © 2022 The Royal Society of ChemistryCalcinationCombustion synthesisIonsOxygen vacanciesAdsorption of waterDFT calculationHigh surface areaIon vacancyOxide ionsOxygen ionsScalable approachSingle-stepSolution combustion synthesisSynthesisedCobalt compoundscobalt derivativehydroxyl groupnitrateoxideoxygenwateradsorptionArticlecalcination temperaturecatalystchemical reactioncombustioncontrolled studycurrent densitydensity functional theorydissociationoxygen evolutionstructure analysissurface areasurface propertysynthesis