High-performance light-driven heterogeneous CO2 catalysis with near-unity selectivity on metal phosphides

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO2 hydrogenation. Selected as an archetype, Ni12P5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni12P5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 96012mmolg(cat)(-1)h(-1), near 100% selectivity and long-term stability. Successful extension of this idea to Co2P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO2 catalysis. There exists an urgent need to develop new materials to convert CO2 to useful products. Here, authors demonstrate metal phosphide nanoparticles to enable light-driven CO2 hydrogenation with high activities and near-unity selectivity.