Residual antibiotic in ecosystems are an environmental problem that urgently needs to be solved. Developing efficient and green photocatalysts is an attractive option for the removal of antibiotics. In this work, a titanium metal organic framework (Ti-MOF) was calcined in an air atmosphere to obtain Ti³⁺- and oxygen vacancy (Ov)-doped anatase and rutile heterojunction TiO₂ (A/R-TiO₂) distributed in a carbon matrix. Through XPS, UV–Vis, ESR and other characterizations, it is proven that Ti³⁺ and Ov exist in heterojunction TiO₂. And the characterization results that Ti³⁺- and Ov-doped A/R-TiO₂ exhibits expanded visible light absorption and enhanced separation of charge carries. The photocatalytic degradation efficiency of tetracycline (TC) by the optimal Ti-MOF derived materials reaches 87.03% and the degradation rate of chlortetracycline (CTC) reaches 78.91% in 60 min. When studying the effect of water matrix on the removal of TC, it was found river water has the highest removal rate of TC (70.76%), followed by tap water (66.37%), lake water (61.19%), and hospital wastewater (52.68%). This shows that the carbon coated Ti³⁺- and Ov-doped A/R-TiO₂ is effective for the degradation of antibiotics. In addition, the carbon coating formed by the pyrolysis of the Ti-MOF as a barrier layer can prevent the oxidation of Ti³⁺ and Ov, which make the prepared materials have good stability and repeatability. In this work, hole (h⁺) and superoxide radical (•O₂⁻) are the active substances that play a major role in the degradation system, while the effect of hydroxyl radicals (•OH) is small. Finally, a possible mechanism of carbon coated Ti³⁺- and Ov-doped TiO₂ for photocatalytic degradation is proposed.

生态系统中抗生素残留是一个亟待解决的环境问题。开发高效、绿色的光催化剂是去除抗生素的一个有吸引力的选择。在这项工作中，钛金属有机骨架 (Ti-MOF) 在空气气氛中煅烧以获得 Ti ³⁺ - 和氧空位 (Ov) 掺杂的锐钛矿和金红石异质结 TiO ₂ (A/R-TiO ₂ ) 分布在碳基质。通过XPS、UV-Vis、ESR等表征，证明异质结TiO _{2 中}存在Ti ³⁺和Ov 。Ti ³⁺ - 和Ov掺杂的A/R-TiO ₂表征结果表现出扩大的可见光吸收和增强的电荷载体分离。优化的Ti-MOF衍生材料光催化降解四环素(TC)的效率达到87.03%，60 min内降解金霉素(CTC)的速率达到78.91%。研究水基质对TC去除的影响发现，河水对TC的去除率最高（70.76%），其次是自来水（66.37%）、湖水（61.19%）和医院废水（ 52.68%）。这表明碳包覆的Ti ³⁺ - 和Ov 掺杂的A/R-TiO ₂对抗生素的降解是有效的。此外，Ti-MOF热解形成的碳涂层作为阻挡层可以防止Ti ³⁺的氧化和Ov，使制备的材料具有良好的稳定性和重复性。在这项工作中，空穴（h ⁺）和超氧自由基（•O ₂ ^-）是在降解系统中起主要作用的活性物质，而羟基自由基（•OH）的影响很小。最后，提出了碳包覆Ti ³⁺ - 和Ov 掺杂TiO ₂光催化降解的可能机制。