Exploring Direct Electrochemical Fischer–Tropsch Chemistry of C1–C7 Hydrocarbons via Perimeter Engineering of Au–SrTiO3 Catalyst

Abstract Traditionally, Fischer–Tropsch (FT) synthesis is performed using thermal catalysts and syngas (CO and H 2 ) under high‐pressure and high‐temperature conditions. However, this study introduces an approach that relies on FT chemistry assisted by electrochemistry, referred to here as direct electrochemical (EC) FT chemistry, under ambient conditions. A series of CH 4 , C n H 2n , and C n H 2n+2 hydrocarbons (n = 1–7) is successfully produced over gold (Au) nanoparticle‐loaded perovskite strontium titanate (SrTiO 3 ) nanostructures grown on rutile TiO 2 supported on Ti. Au (1.0 nm)–SrTiO 3 shows the best interface formation, with the highest Faradaic efficiency for C 2+ hydrocarbons. This direct EC‐FT process proceeds via a C─C coupling chain growth reaction at the Au‐SrTiO 3 interface as evidenced by the hydrocarbon weight distribution analysis and density functional theory calculations. The robust combination of experimental and computational findings reveals that optimum conditions for producing surface hydrogenation and C─C coupling polymerization, initiated by surface * CO and * H are achieved by controlling the undercoordinated Au at the perimeter sites of supported Au nanoparticles and by ensuring a harmonized density of states between Au and SrTiO 3 . This EC‐FT process opens a promising avenue for the direct conversion of CO 2 and H 2 O into value‐added long‐chain hydrocarbons.