Nanoclay‐Modulated Interfacial Chemical Bond and Internal Electric Field at the Co<sub>3</sub>O<sub>4</sub>/TiO<sub>2</sub> p‐n Junction for Efficient Charge Separation
Shilin Zhang, Qingjie Wang, Peng Zhang, Jie Wang, Yue Li, Chang Lu, Muhammad Tariq Sarwar, Xiongbo Dong, Qihang Zhao, Aidong Tang, Liangjie Fu, Huaming Yang
Abstract
Abstract To achieve a high separation efficiency of photogenerated carriers in semiconductors, constructing high‐quality heterogeneous interfaces as charge flow highways is critical and challenging. This study successfully demonstrates an interfacial chemical bond and internal electric field (IEF) simultaneously modulated 0D/0D/1D‐Co 3 O 4 /TiO 2 /sepiolite composite catalyst by exploiting sepiolite surface‐interfacial interactions to adjust the Co 2+ /Co 3+ ratio at the Co 3 O 4 /TiO 2 heterointerface. In situ irradiation X‐ray photoelectron spectroscopy and density functional theory (DFT) calculations reveal that the interfacial Co 2+ OTi bond (compared to the Co 3+ OTi bond) plays a major role as an atomic‐level charge transport channel at the p‐n junction. Co 2+ /Co 3+ ratio increase also enhances the IEF intensity. Therefore, the enhanced IEF cooperates with the interfacial Co 2+ OTi bond to enhance the photoelectron separation and migration efficiency. A coupled photocatalysis‐peroxymonosulfate activation system is used to evaluate the catalytic activity of Co 3 O 4 /TiO 2 /sepiolite. Furthermore, this work demonstrates how efficiently separated photoelectrons facilitate the synergy between photocatalysis and peroxymonosulfate activation to achieve deep pollutant degradation and reduce its ecotoxicity. This study presents a new strategy for constructing high‐quality heterogeneous interfaces by consciously modulating interfacial chemical bonds and IEF, and the strategy is expected to extend to this class of spinel‐structured semiconductors.