Yuan Jie, Feng Wenhui, Zhang Yongfan, Xiao Jianyu, Zhang Xiaoyan, Wu Yinting, Ni Wenkang, Huang Hongwei, Dai Wenxin
State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou, 350116, P. R. China.
Hunan Province Key Laboratory of Applied Environmental Photocatalysis, Changsha University, Changsha, 410022, P. R. China.
Adv Mater. 2024 Feb;36(5):e2303845. doi: 10.1002/adma.202303845. Epub 2023 Dec 5.
Piezo-photocatalysis is a frontier technology for converting mechanical and solar energies into crucial chemical substances and has emerged as a promising and sustainable strategy for N fixation. Here, for the first time, defects and piezoelectric field are synergized to achieve unprecedented piezo-photocatalytic nitrogen reduction reaction (NRR) activity and their collaborative catalytic mechanism is unraveled over BaTiO with tunable oxygen vacancies (OVs). The introduced OVs change the local dipole state to strengthen the piezoelectric polarization of BaTiO , resulting in a more efficient separation of photogenerated carrier. Ti sites adjacent to OVs promote N chemisorption and activation through d-π back-donation with the help of the unpaired d-orbital electron. Furthermore, a piezoelectric polarization field could modulate the electronic structure of Ti to facilitate the activation and dissociation of N , thereby substantially reducing the reaction barrier of the rate-limiting step. Benefitting from the synergistic reinforcement mechanism and optimized surface dynamics processes, an exceptional piezo-photocatalytic NH evolution rate of 106.7 µmol g h is delivered by BaTiO with moderate OVs, far surpassing that of previously reported piezocatalysts/piezo-photocatalysts. New perspectives are provided here for the rational design of an efficient piezo-photocatalytic system for the NRR.
压电光催化是一种将机械能和太阳能转化为关键化学物质的前沿技术，已成为一种有前景的可持续固氮策略。在此，首次实现了缺陷与压电场的协同作用，以实现前所未有的压电光催化氮还原反应（NRR）活性，并在具有可调氧空位（OVs）的BaTiO上揭示了它们的协同催化机制。引入的氧空位改变了局部偶极子状态，增强了BaTiO的压电极化，导致光生载流子更有效地分离。与氧空位相邻的Ti位点借助未配对的d轨道电子通过d-π反馈促进N的化学吸附和活化。此外，压电极化场可以调节Ti的电子结构，以促进N的活化和解离，从而大幅降低限速步骤的反应势垒。受益于协同增强机制和优化的表面动力学过程，具有适度氧空位的BaTiO实现了106.7 μmol g⁻¹ h⁻¹的优异压电光催化NH₃析出速率，远远超过先前报道的压电催化剂/压电光催化剂。本文为合理设计用于NRR的高效压电光催化系统提供了新的视角。
