Electrocatalytic CO Reduction to Produce Long‐chain Products Through Fischer‐Tropsch Pathway

Abstract Electrocatalytic CO reduction (COR) is a promising approach for converting C 1 feedstock into valuable multi‐carbon fuels using renewable electricity. At ambient temperature, COR, particularly on Cu‐based catalysts, typically produces C 2 chemicals as the dominant products, with long‐chain hydrocarbons containing more than five carbon atoms rarely forming. In contrast, Fischer‐Tropsch synthesis (FTS), a thermocatalytic process converting CO and H 2 , selectively generates long‐chain hydrocarbons. In this study, we utilized Ru nanoparticles for electrochemical COR under elevated conditions (423 K and 2.8 MPa). Long‐chain products with up to 21 carbon atoms were detected, achieving a Faradaic efficiency of 32 % and a weight selectivity of 65 % for C 5+ products. We propose an FTS‐like pathway for this electrocatalytic process. Unlike thermocatalytic FTS, where adsorbed H atoms form via H 2 dissociation, in this electrocatalytic version, the H atoms are generated through the Volmer reaction from water. Subsequently, the chemisorbed and activated CO species are hydrogenated, forming CH x intermediates that propagate into long‐chain products.