Spatial Tailoring of Pt Clusters and Co Single Atoms Over TiO 2 Nanosheets Achieves Directed Charge Separation for Boosted Methanol Photoreforming

Efficient methanol photoreforming requires the coupling of methanol oxidative dehydrogenation and proton reduction, yet these half‐reactions demand distinct active‐site configurations. Here, acid‐etching‐assisted dual‐site engineering enables the synergistic integration of Pt clusters (Pt C ) and Co single atoms (Co SA ) on TiO 2 nanosheets (TNS). Experimental results and theoretical calculations reveal that the electronic interaction between Pt C and Co SA upshifts the d‐band center of Co SA to enhance the adsorption and activation of methanol‐derived intermediates, while downshifting the d‐band center of Pt C to weaken proton adsorption and facilitate H 2 desorption. Furthermore, compared with isolated Pt single atoms (Pt SA ), Pt C reduces the proton migration energy barrier and apparent activation energy, thereby facilitating efficient H 2 evolution. More importantly, the nanosheet structure of TNS accelerates the migration of holes toward Co SA and electrons toward Pt C , effectively suppressing charge recombination and establishing a directional redox pathway. Consequently, spatial tailoring of the reactive active sites enables Pt C Co SA /TNS to deliver an H 2 evolution rate of 117.8 mmol g −1 h −1 , approximately 2 times that of Pt SA Co SA /TNS, together with an apparent quantum yield of 66.4% at 365 nm. This work provides a novel strategy for the controlled fabrication of active sites on photocatalysts and efficient methanol photoreforming.