Titania‐Supported Ni2P/Ni Catalysts for Selective Solar‐Driven CO Hydrogenation

Abstract Solar‐driven Fischer–Tropsch synthesis (FTS) holds great potential for the sustainable production of fuels from syngas and solar energy. However, the selectivity toward multi‐carbon products (C 2+ ) is often hampered by the difficulty in the regulation of transition metals acting as both light absorption units and active sites. Herein, a partial phosphidation strategy to prepare titania supported Ni 2 P/Ni catalysts for photothermal FTS is demonstrated. Under Xenon lamp or concentrated sunlight irradiation, the optimized catalyst shows a C 2+ selectivity of 70% at a CO conversion of >20%. Conversely, nickel metal in the absence of Ni 2 P delivers negligible C 2+ products (≈1%) with methane being the major product (>90%). Structural characterization and density functional theory calculation reveal that the partial phosphidation allows exposed metallic Ni to be active for CO adsorption and activation, while the existence of Ni 2 P/Ni interface is responsible to inhibit CO methanation and promote C–C coupling of adsorbed *CH intermediates. This work introduces a novel phosphidation strategy for nickel‐based photothermal catalysts in efficiently harnessing solar energy, and regulating the reaction pathways for CO hydrogenation to deliver high value products.