Light-Induced Structural Dynamic Evolution of Pt Single Atoms for Highly Efficient Photocatalytic CO2 Reduction

Revealing the structural evolution of the real active site during photocatalysis is very important for understanding the catalytic mechanism, but it remains a great challenge. By employing single atoms (SAs) as the mechanism research platform, we investigated the variation of the SA structure under light and the corresponding reaction pathway controlment mechanism. In particular, taking the defect anchoring strategy, Pt SAs are anchored on the metal ion vacancy-rich ZnNiTi layered double hydroxide-etched (ZnNiTi-LDHs-E) support. It is proved by CO-Fourier transform infrared and X-ray absorption fine structure characterization methods that the Pt SAs could gain photoelectrons to form cationic Pt(IV), electron-rich Pt(II), and near-neutral Pt^δ+ species at different light intensities. By in situ inducing the above different Pt SAs in photocatalytic CO₂ reduction, a dramatic product distribution is observed: (1) under weak light, Pt(IV) SAs cannot activate CO, so CO cannot be further transformed into hydrocarbons; (2) under the moderate light, electron-rich Pt(II) SAs could cooperate with adjacent LDH surface sites (Ni²⁺/Ti⁴⁺) to open up the C-C coupling route for C₂H₆ generation; and (3) Pt SAs in the state of near-neutral Pt^δ+ could directly hydrogenate CO into CH₄. This work reveals the structural evolution of Pt SAs in photocatalysis and the corresponding effect on catalytic performance, which provides a new idea for the construction of highly efficient photocatalysts.