Electrocatalytic hydrogenation reactions (ECH) receive growing attention due to their sustainable potential. Our innovative one-step protocol creates carbon-supported silver electrodes, finely tunable for morphology and catalytic activity. Achieving 93 % current efficiency in ECH for the vitamin synthon 2-methyl-3-butyn-2-ol, even at higher current densities and reduced metal loadings, we successfully converted a library of 17 diverse substrates. More information can be found in the Research Article by U.-P. Apfel, D. Siegmund and co-workers (DOI: https://doi.org/10.1002/chem.202303808).

Abstract

Electrocatalytic hydrogenations (ECH) enable the reduction of organic substrates upon usage of electric current and present a sustainable alternative to conventional processes if green electricity is used. Opposed to most current protocols for electrode preparation, this work presents a one-step binder- and additive-free production of silver- and copper-electroplated electrodes. Controlled adjustment of the preparation parameters allows for the tuning of catalyst morphology and its electrochemical properties. Upon optimization of the deposition protocol and carbon support, high faradaic efficiencies of 93 % for the ECH of the Vitamin A- and E-synthon 2-methyl-3-butyn-2-ol (MBY) are achieved that can be maintained at current densities of 240 mA cm⁻² and minimal catalyst loadings of 0.2 mg cm⁻², corresponding to an unmatched production rate of 1.47 kg_MBE g_cat ⁻¹ h⁻¹. For a continuous hydrogenation process, the protocol can be directly transferred into a single-pass operation mode giving a production rate of 1.38 kg_MBE g_cat ⁻¹ h⁻¹. Subsequently, the substrate spectrum was extended to a total of 17 different C−C−, C−O− and N−O−unsaturated compounds revealing the general applicability of the reported process. Our results lay an important groundwork for the development of electrochemical reactors and electrodes able to directly compete with the palladium-based thermocatalytic state of the art.