Modulating Ti t2g Orbital Bonding in Dual‐Channeled TiO2/rGO Hybrid Architecture for Stable Photocatalytic Methanol to Hydrogen

Carbon materials are commonly integrated with TiO2 to achieve high carrier mobility and excellent photocatalytic performance, and the chemical bond between TiO2 − C is considered as a significant strategy to enhance efficiency. Nevertheless, few analyses have elucidated the formation mechanism of Ti3 + − C bonds and the underlying reasons for the performance enhancement. To address these issues, this study conducts an in‐depth investigation into the electronic structure of TiO2 − C and demonstrates that the charge in the nonbonding molecular orbital t2g of Ti3 + is transferred to the unoccupied 2p energy level of C through the formation of 1π and 2π bonds, i.e., (Ti 3dxz ‐ C 2py) and (Ti 3dxy ‐ C 2px). The hybridization of t2g‐2p orbitals endows the Ti3 + − C bond with higher carrier mobility and a stronger binding force, thereby contributing to stable photocatalytic H2 production. Inspired by this scenario, the NSTiO2/rGO hybrid architecture, featuring the {101}/{001} surface heterojunction and the Ti3 + − C interfacial chemical bond, has been constructed. As a result, the hybrid catalyst exhibited excellent photocatalytic cycling stability of 92.9%$92.9 \,\%$ and an H2 evolution rate of 33.4 mmolh−1g−1. This work proposes a strategy for designing efficient photocatalyst by regulating orbitals to achieve high‐performance photocatalytic methanol splitting. This study demonstrates that the charge in the nonbonding molecular orbital t2g of Ti3 + is transferred to the unoccupied energy level 2p of C through the effective modulation of t2g − 2p orbital hybridization. The significant overlap between t2g and 2p orbitals endows the Ti3 +‐C bond with higher carrier mobility and a stronger binding force, contributing to the stable photocatalytic H2 production.