Black Ti³⁺ self-doping TiO₂ nanotubes (BTNT) have attracted widespread attention due to their abilities to enhance visible light response and photo-generated electron-hole separation without introducing impurity particles. However, due to the poor stability of Ti³⁺, the doping of a large amount of Ti³⁺ is a huge challenge. In this work, we have taken a different approach, and the black Ti³⁺ self-doping TNT-Ag-WO₃ (BAW) photocatalyst was prepared. The BAW Z-scheme photocatalytic (PC) system was successfully constructed. Compared with TNT's PC system (degrade 40.56%), BAW Z-scheme PC system can degrade 97.67% with 20 mg/L MB wastewater after 120 min. By introducing a large number of Ti³⁺ and O vacancies, the inherent active group is mainly converted from the holes and.OH on the WO₃ valence band and.O₂⁻ on the TiO₂ conduction band, which improved the stability of O vacancies.Before and after the reaction, the reduction of Ti³⁺ in BTNT is about 30 times that of Ti³⁺ in BAW. This work provides a reference and basis for constructing Z-scheme heterojunction on BTNT, and also provides new ideas for improving the stability of Ti³⁺and O vacancies in self-doped TiO₂.

Black Ti ³⁺自掺杂TiO ₂纳米管（BTNT）因其在不引入杂质颗粒的情况下增强可见光响应和光生电子-空穴分离的能力而受到广泛关注。然而，由于Ti ³⁺稳定性差，大量的Ti ³⁺掺杂是一个巨大的挑战。在这项工作中，我们采取了不同的方法，将黑色 Ti ³⁺自掺杂 TNT-Ag-WO ₃(BAW) 光催化剂的制备。BAW Z-scheme光催化（PC）系统构建成功。与 TNT 的 PC 系统（降解 40.56%）相比，BAW Z-scheme PC 系统在 20 mg/L MB 废水 120 分钟后可以降解 97.67%。通过引入大量的Ti ³⁺和O空位，固有活性基团主要由WO ₃价带上的空穴和.OH和TiO ₂导带上的.O ₂ ^-转化，提高了O的稳定性vacancies.Before和在反应后，将Ti的还原³⁺在BTNT为约30倍的Ti ³⁺在 BAW。该工作为在BTNT上构建Z-scheme异质结提供了参考和依据，也为提高自掺杂TiO ₂中Ti ³⁺和O空位的稳定性提供了新思路。