Cobaloxime complexes gained attention for their intrinsic ability of catalytic H₂ production despite their initial emergence as a vitamin B12 model. The simple, robust, and synthetically manoeuvrable cobaloxime core represents a model catalyst molecule for the investigation of optimal conditions for both photo- and electrocatalytic H₂ production catalytic assemblies. Cobaloxime is one of the rare catalysts that finds equal applications in the analysis of homogeneous and heterogeneous catalytic conditions. However, the poor aqueous solubility and long-term instability of cobaloximes have severely impeded their growth. Lately, interest in the cobaloxime-based catalysts has been resuscitated with the rational use of extended enzymatic features. This unique enzyme-inspired catalyst design strategy has instigated the formation of a new genre of cobaloxime molecules that exhibit enhanced photo- and electrocatalytic H₂ evolution with improved aqueous and air stability.

The photo- and electrocatalytic H ₂ production by the cobaloxime core improves in the presence of a primary amine group in the periphery.