Photocatalytic oxidation processes (PCO processes) are a promising technology for controlling the pollution of working environments, namely, the low concentrations of volatile organic compounds (VOCs) generated in industrial processes, and improving the efficiency of this process is an important issue. In this study, the photocatalytic oxidation of gas-phase benzene was carried out with TiO₂ microspheres with a sea-urchin-like structure, and the effect of Ti³⁺ self-doping on the catalytic performance of TiO₂ was investigated in detail. The structures and properties were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance spectroscopy, electron spin resonance, scanning electron microscopy, and high-resolution transmission electron microscopy. Ti³⁺ ions were formed in TiO₂ microspheres by heating under vacuum, which improved the catalytic performance of TiO₂ for the complete oxidation of benzene to CO₂ and CO. The photoelectrochemical measurements showed that the incorporation of Ti³⁺ into TiO₂ microspheres reduced electron-hole recombination and increased the light absorption capacity, which contributed to improving the photocatalytic activity. In situ FTIR spectroscopic studies revealed that in the benzene oxidation process, Ti³⁺ self-doped TiO₂ microspheres suppressed the formation of strongly bound byproduct compounds on the TiO₂ surface, which affected the rate of benzene oxidation. Thus, the Ti³⁺ self-doped TiO₂ microspheres are effective catalysts for efficient use of UV light and suppression of catalyst deactivation during benzene oxidation.

光催化氧化工艺（PCO工艺）是一种有前途的技术，可用于控制工作环境的污染，即工业工艺中产生的低浓度挥发性有机化合物（VOC），提高此工艺的效率是一个重要的问题。本研究采用海胆状结构的TiO ₂微球对气相苯进行光催化氧化，Ti ³⁺自掺杂对TiO ₂催化性能的影响被详细调查。通过X射线衍射，X射线光电子能谱，紫外可见漫反射光谱，电子自旋共振，扫描电子显微镜和高分辨率透射电子显微镜对结构和性能进行了表征。通过真空加热在TiO ₂微球中形成Ti ³⁺离子，这改善了TiO ₂对苯完全氧化为CO ₂和CO的催化性能。光电化学测量表明Ti ³⁺掺入TiO _2中微球减少了电子-空穴的重组并增加了光吸收能力，这有助于提高光催化活性。原位FTIR光谱研究表明，在苯氧化过程中，Ti ³⁺自掺杂TiO ₂微球抑制了TiO ₂表面上牢固结合的副产物的形成，从而影响了苯的氧化速率。因此，Ti ³⁺自掺杂的TiO ₂微球是有效利用紫外线并抑制苯氧化过程中催化剂失活的有效催化剂。