Using earth abundant materials for the catalytic evolution of hydrogen from electron-coupled proton buffers

Hydrogen has a large array of uses throughout the chemical and energy industries, yet is largely produced through the reformation of fossil fuels. Renewable production of hydrogen, via electrolytic water splitting, could be key to moving beyond fossil fuel reliance, but research has mainly focused on maximising efficiency to increase the performance of the electrolysis process. Access to cheap, renewable earth abundant materials to produce hydrogen could be argued to be of equal importance. Electron-coupled proton buffers (ECPBs) have been shown to separate the oxygen and hydrogen evolution reactions of water electrolysis (OER and HER) in space and time, but have previously relied on precious metal catalysts to produce H2. Herein, we report the use of four earth abundant catalysts capable of spontaneously evolving hydrogen from reduced ECPBs. The hydrogen production rate was found to be influenced by both the onset potential of the HER for a particular catalyst, and the redox potential of the ECPB used. The catalysts were shown to evolve hydrogen at rates up to 9.4 mmol H2 per h per mg catalyst and up to 60% of the theoretical maximum hydrogen capacity of the ECPBs.