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

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 (TiO₂ ) 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 TiO₂ 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.