Spontaneous generation of hydrogen from water using modified dodecaborate ions

Efficient hydrogen production from water is a key requirement for a successful hydrogen economy. The dodecaborate anion [B₁₂H₁₂]^2- and its derivatives [B₁₂X₁₂]^2- (X = F, Cl, Br, I, CN), known for their enhanced stability, have catalytic potential for activating small molecules, such as NH₃, CO₂, and N₂, once a ligand is removed. In this work, we computationally explored the electronic structures of [B₁₂X_n]^q (X = Br, I, CN; n = 11, 10; q = 2-, 1-, 0) and the thermodynamics of their interaction with water. We show that, among these, [B₁₂X₁₀]^-˙ (X = Br, I) are the most suitable for spontaneous hydrogen generation. A detailed description of the catalytic mechanism is presented.