The development and comprehensive understanding of nickel chalcogenides are critical since they constitute a class of efficient electro(pre)catalysts for the oxygen evolution reaction (OER) and value-added organic oxidations. This study introduces a knowledge-based facile approach to analogous NiE (E = S, Se, Te) phases, originating from molecular β-diketiminato [Ni2E2] complexes and their application for OER and organic oxidations. The recorded activity trends for both target reactions follow the order NiSe > NiS > NiTe. Notably, NiSe displayed efficient performance for both OER and the selective oxidation of benzyl alcohol and 5-hydroxymethylfurfural, exhibiting stability in OER for 11 days under industrially pertinent conditions. Comprehensive analysis, including quasi in situ X-ray absorption and Raman spectroscopy, in combination with several ex situ techniques, revealed a material reconstruction process under alkaline OER conditions, involving chalcogen leaching. While NiS and NiSe experienced full chalcogen leaching and reconstruction into NiIII/IV oxyhydroxide active phases with intercalated potassium ions, the transformation of NiTe is incomplete. This study highlights the structure–activity relationship of a whole series of analogous nickel chalcogenides, directly linking material activity to the availability of active sites for catalysis. Such findings hold great promise for the development of efficient electrocatalysts for a wide range of applications, impacting various industrial processes and sustainable energy solutions.
