以四环素为代表的抗生素对于人类的生产和生活至关重要，而四环素类抗生素在环境中不断被检出，这表明四环素类抗生素污染治理迫在眉睫。相较于生物处理法和物化处理法所面临的处理效率低和易二次污染等问题，以太阳能驱动分子氧活化的深度处理工艺可以实现对抗生素的绿色高效去除。受限于活性物种的寿命和传质距离，如何快速与目标污染物有效接触成为了关键，因此构建吸附耦合光催化的抗生素降解体系具有重要意义。本文以溴氧铋基材料为基础，通过调控改性，制备了强化吸附耦合光催化的功能材料。在强化对污染物吸附富集的同时，促进分子氧的活化，实现了对四环素类抗生素的有效去除。

针对高效分子氧活化对能带结构的需求，利用理论计算验证了富铋策略调控溴氧铋能带结构的可能性，并通过碱性水热法成功制备了富铋材料Bi₃O₄Br。相较于BiOBr，富铋策略在缩短禁带宽度的同时，将导带位置由原来的-0.34 eV上移到了-0.43 eV，使得导带电子具有更强的还原能力。富铋策略抑制了光生电子和空穴的复合，促进了电荷转移，使得更多的电子迁移至表面与分子氧发生反应。通过电子自旋共振测试、探针实验和淬灭实验，表明富铋策略可以提高活性物种的生成效率，产生更多的∙O2-和¹O₂，从而将四环素的去除率由原来的35.4%提高到了77.7%。

针对溴氧铋材料对四环素的特征吸附，通过吸附过程中Br^-浓度变化规律和外加NaBr对吸附的抑制效果，明确了溴氧铋对四环素基于水解反应耦合脱水反应的离子交换吸附机制。氧空位的引入促进了四环素的吸附与分子氧的活化。吸附实验和理论计算表明，氧空位将脱水反应的反应能降低了0.26 eV，从而实现了对四环素吸附的增强，在暗反应阶段吸附率提高到了33.1%。氧空位也是分子氧活化的活性位点，促进了电荷的转移，增强对分子氧的活化。在材料表面吸附所形成的表面复合物可以通过促进电荷分离增强光催化活性。电子自旋共振测试、探针实验和淬灭实验表明氧空位的引入可以生成更多的∙O2-、¹O₂和∙OH用于污染物降解。

以能带结构更加合适的Bi₃O₄Br为基础，探究富铋材料对四环素的吸附机制。通过分析吸附实验中Br^-的释放和NaBr对吸附的影响，明确了富铋材料与溴氧铋存在相似的特性，均可以对四环素实现离子交换吸附。为了进一步探究分子氧活化与金属活性位点的构效关系，利用水热法将Fe引入到富铋材料Bi₃O₄Br，制备了一系列Fe-Bi₃O₄Br材料。当Fe与Bi的原子比为1:30时，具有最佳的吸附与降解效率。铁的掺杂扩大了材料的比表面积，为吸附与催化提供更多的活性位点。理论计算和XPS表明引入的Fe可以充当光生电子的贮存中心和分子氧活化的反应中心，抑制了光生电子和空穴的重组，促进了电荷向材料表面的迁移。通过电子自旋共振测试、探针实验和淬灭实验证明Fe的掺杂取代，可以将分子氧活化成更多的∙O2-和¹O₂，对四环素的去除率提高到了84.9%。

基于富铋材料对四环素的离子交换吸附机制，利用表面羟基对材料进行修饰，制备了Bi₃O₄Br-OH系列材料。通过与原始Bi₃O₄Br材料在吸附过程中Br^-浓度对比，发现吸附效率高的改性材料2-Bi₃O₄Br-OH反而释放较少的Br^-，证明表面羟基修饰可以使得材料减少水解反应的过程，直接与四环素分子发生脱水反应完成吸附，使其吸附率提高到43.0%。同时表面羟基的引入可以强化光生电子与空穴的高效分离，从而实现对分子氧的有效活化。电子自旋共振测试、淬灭实验和探针实验的实验结果表明表面羟基修饰可以促进分子氧活化产生更多的∙O2-和¹O₂。在表面羟基修饰的作用下，通过强化吸附富集耦合分子氧活化将四环素的降解率提高到了89.8%。

本文对铋基材料进行调控优化，构筑了吸附耦合光催化的四环素绿色降解体系。通过提高导带电子还原能力，提高对可见光的利用效率，促进光生电子和空穴的高效分离，引入金属活性位点，强化对分子氧的吸附与活化，实现了活性物种生成效率的提高。在基于水解反应耦合脱水反应的离子交换吸附四环素的基础上，通过降低脱水反应能，提高比表面积和省略水解反应等方式，促进了对四环素的吸附富集。污染物分子与活性物种的有效接触提高了活性物种的利用效率，促进了污染物的降解。同时对四环素吸附耦合降解的去除机理与影响因素进行了深入研究，对污染物吸附与光催化降解的相互作用进行了分析，为基于吸附富集耦合光催化分子氧活化降解污染物提供了参考。

Tetracycline is a typical type of antibiotics, which is crucial for human production and life. However, the continuous detection of tetracycline antibiotics in the environment indicates that the control of tetracycline antibiotic pollution is urgent. The traditional method like biological treatment and physicochemical treatment face problems such as low efficiency and secondary pollution. Light driven molecular oxygen activation can achieve green and efficient antibiotics removal via efficient active species. Due to the limited lifetime and mass transfer distance of active species, how to quickly and effectively contact target pollutants has become a key issue. Therefore, it is of great significance to construct an adsorption coupled photocatalytic antibiotic removal system. In this paper, based on modified bismuth oxybromide based materials, the functional materials with intensification adsorption coupled photocatalysis were prepared. It enhanced the adsorption of pollutants and promoted the activation of molecular oxygen, which achieved the effective removal of tetracycline antibiotics.

Considering the band structure for efficient molecular oxygen activation, theoretical calculations demonstrated the possibility of bismuth rich strategy controlling energy bands, and bismuth rich material Bi₃O₄Br was prepared by alkaline hydrothermal method. Compared to BiOBr, the bismuth-rich strategy reduced the band gap and shifted up the conducted band from -0.34 eV to -0.43 eV, suggesting a stronger reduction ability. The bismuth-rich strategy suppressed the recombination of electrons and holes while more charges migrated to the surface for molecular oxygen activation. ESR tests, probe experiments, and quenching experiments indicated bismuth-rich strategy generated more ∙O2- and ¹O₂ for tetracycline degradation, increasing the removal efficiency from the original 35.4% to 77.7%.

For the characteristic adsorption of tetracycline on bismuth oxybromide, the results of Br^- concentration variation and significant inhibition adsorption with NaBr indicated the mechanism of adsorption in the form of ion exchange (hydrolysis reaction coupling dehydration reaction). Oxygen vacancy promoted the adsorption efficiency of tetracycline and activation of molecular oxygen. ∆E of dehydration reaction was reduced by 0.26 eV due to oxygen vacancy, which achieved better adsorption (33.1%). Oxygen vacancies were also the active sites for molecular oxygen activation, promoting charge transfer and enhancing the activation of molecular oxygen. Surface complex due to the better adsorption enhanced photocatalytic activity via better charge separation. Combined with ESR tests, probe experiments, and quenching experiments, there were more products of molecular oxygen activation including ∙O2-, ¹O₂, and ∙OH in BiOBr-OV system for better degradation.

Bi₃O₄Br with more suitable band structure was employed to analyze the adsorption mechanism of bismuth rich materials for tetracycline. The release of Br^- and the inhibition of adsorption by NaBr confirmed the ion exchange adsorption, which was similar with BiOBr. In order to further explore the structure-activity relationship between molecular oxygen activation and metal active sites, a series of Fe-Bi₃O₄Br materials were prepared by introducing Fe into Bi₃O₄Br via hydrothermal method. When the atomic ratio of Fe to Bi was 1:30, it had the best adsorption and degradation efficiency. The doping of Fe increased the specific surface area of the materials, providing more active sites for adsorption and catalysis. Theoretical calculations and XPS showed that the introduced Fe acted as the reaction center for molecular oxygen activation and the enrichment center for photogenerated electrons, which inhibited the recombination of electrons and holes and promoted the migration of charge to the surface of materials. According to the ESR tests, probe experiments, and quenching experiments, more ∙O2- and ¹O₂ were generated via molecular oxygen activation which improved the removal efficiency to 84.9%.

Based on the ion exchange adsorption mechanism of bismuth rich materials for tetracycline, a series of Bi₃O₄Br-OH materials were prepared by modifying the materials with surface hydroxyl groups. 2-Bi₃O₄Br-OH exhibited a better adsorption performance (adsorption rate: 43.0%) with lower Br^- release content compared with Bi₃O₄Br, which indicated surface hydroxyl modification could reduce the hydrolysis reaction process and dehydrated with tetracycline molecules directly. Meanwhile, surface hydroxyl groups promoted the effective separation of photogenerated electrons and holes, achieving effective activation of molecular oxygen. The results of ESR tests, probe experiments, and quenching experiments suggested more ∙O2- and ¹O₂ were produced due to surface hydroxyl. With the action of surface hydroxyl modification, the degradation efficiency of tetracycline increased to 89.8% by enhancing adsorption enrichment coupled with molecular oxygen activation.

In this paper, the green system based on adsorption coupled molecular oxygen activation was constructed for tetracycline removal with the control and optimization of bismuth-based materials. By improving the conduction band reduction ability, enhancing the utilization rate of visible light, intensification the separation efficiency of photogenerated electron hole pairs, introducing metal active sites, promoting the adsorption and activation of molecular oxygen, the efficiency of active species generation has been improved. On the basis of ion exchange adsorption of tetracycline (hydrolysis reaction coupling dehydration reaction), adsorption and enrichment of tetracycline were strengthened by reducing dehydration reaction energy, increasing specific surface area, and omitting hydrolysis reactions. Effective contact between pollutant molecules and active species was achieved, which improved the utilization efficiency of active species. At the same time, in-depth research was conducted on the removal mechanism and influencing factors of tetracycline adsorption coupled degradation, and the interaction between pollutant adsorption and photocatalytic degradation was analyzed, which provided a reference for the removal of pollutants based on adsorption enrichment coupled photocatalytic degradation.