Opening Direct Electrochemical Fischer–Tropsch Synthesis Path by Interfacial Engineering of Cu Electrode with P-Block Elements

The electrochemical synthesis of syngas (CO and H 2 ) has garnered considerable attention in the context of Fischer–Tropsch (FT) synthesis employing thermal catalysts. Nonetheless, the need for a novel, cost-effective technique persists. In this investigation, we introduce a direct electrochemical (dEC) approach for FT synthesis that functions under ambient conditions by utilizing a p-block element (Sn and In) overlaid Cu electrode. Surface *CO and H* species were obtained in an electrolytic medium through the CO 2 + H + + e – → HOOC ad → *CO (or direct CO adsorption) and H + + e – → H* reactions, respectively. We have observed C 2–7 long-chain hydrocarbons with a C n H 2 n +2 /C n H 2 n ratio of 1–3, and this observation can be explained through the process of C–C coupling chain growth of the conventional FT synthesis, based on the linearity of the Anderson-Schulz–Flory equation plots. Thick Sn and In overlayers resulted in the dominant production of formate, while CO and C 2 H 4 production were found to be proportional and inversely correlated to H 2, C 2 H 6, and C 3–7 hydrocarbon production. The EC CO 2 /CO reduction used in dEC FT synthesis offers valuable insights into the mechanism of C 2+ production and holds promise as an eco-friendly approach to producing long-chain hydrocarbons for energy and environmental purposes.