Can we steer selectivity away from OER and HER in Electrochemistry?

Electrochemical oxidation in water requires a formation of reactive oxygen species to be able to oxidize organic compounds to ketones, aldehydes and epoxides. These reactions, broadly classified as alternative oxidation reactions (AOR), directly compete with prevalent oxygen evolution reaction (OER). In my first work [1], I will discuss how in heterogeneous catalysis of metal oxides the Oxo-Wall principle applies, but a meta-stable oxo preferentially coordinates with lattice oxygen to form a more stable surface peroxo intermediate on the other side of this wall. Such peroxo species then gives rise to a new region of oxygen reactivity relevant for AOR where we predict a selective oxidation of the unsaturated C-C bonds to occur instead of OER.

Next, Biological N2 reduction to NH3 by the metalloenzyme nitrogenase is the only known natural route to synthesize ammonia under ambient conditions. However, accurate quantum mechanical description of this process remains unclear due to inaccurate energetics from DFT. In this high precision study [2], we benchmark density functional theory with localization corrections against highly accurate quantum Monte Carlo calculations to correct for these errors. Our revised thermodynamics identifies *N2 protonation to *N2H as the main bottleneck of N2 reduction reaction (N2RR), while adiabatically extracted barriers show that the nitrogenase cofactor kinetically suppresses hydrogen evolution reaction (HER) over N2RR. 

These works collectively open up the new opportunities for designing improved electro and thermal catalysts by steering and suppressing the prevalent OER and HER reactions.