Heterolytic hydrogenations are a key reaction class that includes CO2 reduction to formate and NADH regeneration, yet the mechanism remains unclear. Now it has been shown that this class of thermochemical reactions proceeds through an electrochemical mechanism, with polarization-driven, interfacial hydride transfer as the rate-determining step.

Hydride transfer is an essential elementary reaction across the chemical value chain, but there are limited methods available for quantifying thermodynamic hydricity (ΔGH–), particularly among main gr...

Interfacial polarization influences catalytic reactions occurring at solid–liquid interfaces, but its measurement was previously limited to conductive materials. Now redox-active molecules enable elec...