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

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 micromol 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.