High-performance light-driven heterogeneous CO 2 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 CO ₂ hydrogenation. Selected as an archetype, Ni ₁₂ P ₅ 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, Ni ₁₂ P ₅ is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960 ± 12 mmol g _cat ^-1  h ^-1 , near 100% selectivity and long-term stability. Successful extension of this idea to Co ₂ P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO ₂ catalysis.