Precisely tailoring Lewis pairs in polyoxotitanium clusters for efficient photocatalytic production of hydrogen peroxide†

Hydrogen peroxide (H₂O₂) is a vital chemical with promising potential as an energy carrier. Photocatalytic H₂O₂ production has emerged as a sustainable and environmentally friendly approach. However, current photocatalysts often exhibit low catalytic efficiency and limited tunability of their electronic structures. Herein, we demonstrate a Lewis pair-dependent strategy for photocatalytic H₂O₂ generation using two N-based polyoxotitanium clusters. Photocatalytic experiments reveal that the Ti₃Co cluster achieves an exceptional H₂O₂ production rate of 1140 μmol g⁻¹ h⁻¹, exceeding that of the Ti₃Mn cluster by more than threefold. Theoretical investigations confirm that functional modifications of the metal–nitrogen Lewis pair in polyoxotitanium clusters induce asymmetric charge distribution and narrow band gap structures. These effects significantly enhance surface charge separation and transfer, leading to improved H₂O₂ yields. This work underscores the potential of atomic-level catalyst design and offers a promising pathway for advancing polyoxotitanium cluster-based photocatalysis.