Co and Pt Dual‐Single‐Atoms with Oxygen‐Coordinated Co–O–Pt Dimer Sites for Ultrahigh Photocatalytic Hydrogen Evolution Efficiency

Abstract The platinum single‐atom‐catalyst is verified as a very successful route to approach the size limit of Pt catalysts, while how to further improve the catalytic efficiency of Pt is a fundamental scientific question and is challenging because the size issue of Pt is approached at the ultimate ceiling as single atoms. Here, a new route for further improving Pt catalytic efficiency by cobalt (Co) and Pt dual‐single‐atoms on titanium dioxide (TiO 2 ) surfaces, which contains a fraction of nonbonding oxygen‐coordinated Co–O–Pt dimers, is reported. These Co–Pt dimer sites originate from loading high‐density Pt single‐atoms and Co single‐atoms, with them anchoring randomly on the TiO 2 substrate. This dual‐single‐atom catalyst yields 13.4% dimer sites and exhibits an ultrahigh and stable photocatalytic activity with a rate of 43.467 mmol g −1 h −1 and external quantum efficiency of ≈83.4% at 365 nm. This activity far exceeds those of equal amounts of Pt single‐atom and typical Pt clustered catalysts by 1.92 and 1.64 times, respectively. The enhancement mechanism relies on the oxygen‐coordinated Co–O–Pt dimer coupling, which can mutually optimize the electronic states of both Pt and Co sites to weaken H* binding. Namely, the “mute” Co single‐atom is activated by Pt single‐atom and the activity of the Pt atom is further enhanced through the dimer interaction. This strategy of nonbonding interactive dimer sites and the oxygen‐mediated catalytic mechanisms provide emerging rich opportunities for greatly improving the catalytic efficiency and developing novel catalysts with creating new electronic states.