Opening the pathway towards a scalable electrochemical semi-hydrogenation of alkynols earth-abundant metal chalcogenides.

Electrosynthetic methods are crucial for a future sustainable transformation of the chemical industry. Being an integral part of many synthetic pathways, the electrification of hydrogenation reactions gained increasing interest in recent years. However, for the large-scale industrial application of electrochemical hydrogenations, low-resistance zero-gap electrolysers operating at high current densities and high substrate concentrations, ideally applying noble-metal-free catalyst systems, are required. Because of their conductivity, stability, and stoichiometric flexibility, transition metal sulfides of the pentlandite group have been thoroughly investigated as promising electrocatalysts for electrochemical applications but were not investigated for electrochemical hydrogenations of organic materials. An initial screening of a series of first row transition metal pentlandites revealed promising activity for the electrochemical hydrogenation of alkynols in water. The most active catalyst within the series was then incorporated into a zero-gap electrolyser enabling the hydrogenation of alkynols at current densities of up to 240 mA cm, Faraday efficiencies of up to 75%, and an alkene selectivity of up to 90%. In this scalable setup we demonstrate high stability of catalyst and electrode for at least 100 h. Altogether, we illustrate the successful integration of a sustainable catalyst into a scalable zero-gap electrolyser establishing electrosynthetic methods in an application-oriented manner.