Wei Mingzhuo, Li Zhijun, Chen Peijiao, Sun Lei, Kang Shilin, Dou Tianwei, Qu Yang, Jing Liqiang
Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, International Joint Research Center for Catalytic Technology, Heilongjiang University, Harbin 150080, China.
Nanomaterials (Basel). 2022 May 5;12(9):1564. doi: 10.3390/nano12091564.
Nitrogen (N) doping is an effective strategy for improving the solar-driven photocatalytic performance of anatase TiO, but controllable methods for nitrogen-rich doping and associated defect engineering are highly desired. In this work, N-rich doped anatase TiO nanoparticles (4.2 at%) were successfully prepared via high-temperature nitridation based on thermally stable HPO-modified TiO. Subsequently, the associated deep-energy-level defects such as oxygen vacancies and Ti were successfully healed by smart photo-Fenton oxidation treatment. Under visible-light irradiation, the healed N-doped TiO exhibited a ~2-times higher activity of gas-phase acetaldehyde degradation than the non-treated one and even better than standard P25 TiO under UV-visible-light irradiation. The exceptional performance is attributed to the extended spectral response range from N-rich doping, the enhanced charge separation from hole capturing by N-doped species, and the healed defect levels with the proper thermodynamic ability for facilitating O reduction, depending on the results of ∙O radicals and defect measurement by electron spin resonance, X-ray photoelectron spectroscopy, atmosphere-controlled surface photovoltage spectra, etc. This work provides an easy and efficient strategy for the preparation of high-performance solar-driven TiO photocatalysts.
氮(N)掺杂是提高锐钛矿型TiO₂太阳能驱动光催化性能的有效策略,但目前非常需要富氮掺杂的可控方法及相关的缺陷工程。在这项工作中,基于热稳定的HPO修饰的TiO₂,通过高温氮化成功制备了富氮掺杂的锐钛矿型TiO₂纳米颗粒(4.2原子%)。随后,通过智能光芬顿氧化处理成功修复了相关的深能级缺陷,如氧空位和Ti³⁺。在可见光照射下,修复后的N掺杂TiO₂对气相乙醛降解的活性比未处理的TiO₂高约2倍,甚至在紫外-可见光照射下比标准P25 TiO₂表现更好。根据电子自旋共振、X射线光电子能谱、气氛控制表面光电压谱等对∙O自由基和缺陷的测量结果,这种优异的性能归因于富氮掺杂扩展了光谱响应范围、N掺杂物种捕获空穴增强了电荷分离以及修复后的缺陷能级具有促进O₂还原的适当热力学能力。这项工作为制备高性能太阳能驱动的TiO₂光催化剂提供了一种简便有效的策略。