Reaction Parameters Influencing Cobalt Hydride Formation Kinetics: Implications for Benchmarking H2-Evolution Catalysts

The need for benchmarking hydrogen evolution catalysts has increasingly been recognized. The influence of acid choice on activity is often reduced to the overpotential for catalysis. Through the study of a stable cobalt hydride complex, we demonstrate the influence of acid choice, beyond K-p(a), on the kinetics of hydride formation. A linear free energy relationship between acid plc and second-order rate constants is observed for weaker acids. For stronger acids, however, further increases in plc do not correlate to increases in rate constants. Further, steric bulk around the acidic proton is shown to influence rate constants dramatically. Together, these observations reveal the complex factors dictating catalyst performance.