Unveiling the Electrocatalytic Activity of Cobaloxime Metallolinker in the UU-100(Co) Metal–Organic Framework toward the H₂ Evolution Reaction: A DFT Study

Developing an efficient electrocatalyst for water splitting is one of the leading and challenging tasks for modern renewable energy technology and sustainable fuels. Recently, porous materials have gathered acute scholarly interest as electrocatalysts due to their promising characteristics. Exploring nonprecious, highly efficient, and stable alternative catalysts for hydrogen evolution reaction (HER) is desirable. Here, we have studied the HER catalytic activity of the cobaloxime metallolinker of the UU-100(Co) metal–organic framework (MOF) using the hybrid-density functional theory with M06-L functional. The periodic DFT-D study shows that the cobaloxime linker in the UU-100(Co) MOF is a semiconducting material where the Co acts as an active metal site for efficient electrocatalysis. The existence of cobalt (Co) metal atoms in this UU-100(Co) model MOF has spurred a lot of attention due to its electron-withdrawing and accepting ability, and it performs as an electrocatalytic functional component during the HER. The electrochemical reaction mechanism with the HER pathway has been explored by considering a finite molecular model system. It has been found that the cobaloxime linker of the model UU-100(Co) in the DMF electrolyte has a low-energy barrier during the Volmer and Tafel reactions, about 36.12 and 34.10 kcal/mol, respectively, computed in the solvent phase. Due to this lower activation energy during the HER, the cobaloxime linker shows better catalytic activity. This study provides valuable insights into the HER process and highlights the capability of MOF as an emerging material for electrochemical reactions. These investigations open opportunities to design novel porous materials for industrial HER applications, energy technology, H2 production, and other renewable energy applications