Abstract
Hydrogen is a clean fuel alternative to fossil fuels, and it is vital to develop catalysts for its efficient activation and production. We investigate the reaction mechanism of H(2) activation in an aqueous solution by the recently developed NiFe complex (Ogo et al. Sci. Adv. 2020, 6, eaaz8181) using density functional theory (DFT) calculation. Our computational results showed that H(2) is activated using frustrated Lewis pair. That is, H(2) binds to the Fe site of the NiFe complex, acting as a Lewis acid, while the added buffer, acting as Lewis base, abstracts protons to form a hydride complex. Furthermore, the higher basicity in the proton abstraction reaction characterises reaction more exergonic and lowers the reaction barrier. In addition, in the proton abstraction by the water molecule, the reaction barrier was lowered when anion such as Cl(-) is in the vicinity of the water. Understanding the chemical species that contribute to the catalytic process in cooperation with the metal catalyst at the atomic level should help to maximise the function of the catalyst.