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Kinetic analysis and isotope experiments combined with density functional theory (DFT) calculations indicate that the nitrogen vacancies in CeN can activate both N2 and H2 during the reaction, which accounts for the much higher catalytic performance than other reported nonloaded catalysts for ammonia synthesis.Carbon homologation reactions occur within the well-known Fischer-Tropsch process, usually mediated by transition metal catalysts at high temperature. Here we report the low-temperature, heavy-metal-free homologation of a carbon chai