Inverse ZrO x –Ni Interfaces Enable Ambient-Pressure CO Hydrogenation to Long-Chain Hydrocarbons

Abstract Steering inexpensive nickel-based catalysts from methanation toward chain growth in CO hydrogenation offers a low-pressure route for sustainable carbon utilization. Here, we engineer an inverse ZrO2/Ni catalyst containing abundant ZrOx–Ni interfacial sites, which markedly enhances CO hydrogenation activity and promotes C5+ hydrocarbon formation. Under ambient pressure at 220 °C, the optimized catalyst achieves approximately 80% selectivity toward long-chain alkanes, with an activity of 0.16 molCO gNi–1 h–1, more than 50 times higher than that of SiO2-supported Ni particles. In situ infrared spectroscopy combined with transient kinetic analysis shows that ZrOx–Ni interfaces enhance CO adsorption capacity and create a CO-rich surface environment that limits excessive hydrogen coverage, directing a high-CO-coverage-dependent chain-growth pathway. Isotope-switching experiments further indicate that formate species are kinetically relevant intermediates closely associated with hydrocarbon formation. These interfacial effects redirect the intrinsic methanation tendency of Ni toward the production of long-chain hydrocarbons. This work establishes an interface-engineering strategy for controlling activity and selectivity in CO hydrogenation under mild conditions.