Structure-tailored superlattice Bi7Ti4NbO21: Coupling octahedral tilting and rotation induced high ferroelectric polarization for efficient piezo-photocatalytic CO2 reduction
Jingren Ni, Rufang Zhao, Chendi Shi, Yuanyuan Ji, Aize Hao, Aiting Xie, Hongjian Yu, Siew Kheng Boong, Hiang Kwee Lee, Chuanqiang Zhou, Jie Han
Abstract
Intergrowth ferroelectric semiconductors with excellent spontaneous polarization field, are highly promising piezo-photocatalytic candidate materials. In addition, developing structural design and revealing polarization enhancement in-depth mechanism are top priorities. Herein, we introduce the intergrowth ferroelectrics Bi 7 Ti 4 NbO 21 thin-layer nanosheets for piezo-photocatalytic CO 2 reduction. Density functional theory (DFT) calculations indicate that interlayer lattice mismatch leads to increased tilting and rotation angle of Ti/NbO 6 octahedra on perovskite-like layers, serving as the main reason for increased polarization. Furthermore, the tilting and rotation angle of the interlayer octahedron further increase under stress, suggesting a stronger driving force generated to facilitate charge carrier separation efficiency. Meanwhile, Bi 7 Ti 4 NbO 21 nanosheets provide abundant active sites to effectively adsorb CO 2 and acquire sensitive stress response, thereby presenting synergistically advanced piezo-photocatalytic CO 2 reduction activity with a high CO generation rate of 426.97 μmol g −1 h −1 . Our work offers new perspectives and directions for initiating and investigating the mechanisms of high-performance intergrowth piezo-photocatalysts. Intergrowth ferroelectric Bi 7 Ti 4 NbO 21 thin-layer nanosheets (BT-BTN-S), with strong ferroelectric polarization and excellent mechanical force sensitivity, are developed as piezo-photocatalyst for CO 2 reduction. The octahedron in BT-BTN exhibits self-tilting and self-rotation to adapt to lattice mismatch, resulting in stronger spontaneous polarization electric field. When ultrasonic vibration is applied, BT-BTN-S generates a super-strong piezoelectric polarization to facilitate charge carrier separation efficiency. • Mild synthesis of intergrowth Bi 7 Ti 4 NbO 21 with strong ferroelectric polarization • Synergistically piezo-photocatalysis for CO 2 reduction performance • Strong piezoelectric field promotes charge separation/transfer and conversion of CO 2