Hebei Province Collaborative Innovation Center for Sustainable Utilization of Water Resources and Optimization of Industrial Structure, Hebei Province Key Laboratory of Sustained Utilization & Development of Water Recourse, School of Water Resource and Environment, Hebei Geo University, Shijiazhuang 050031, China.
School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China.
Molecules. 2023 Jun 13;28(12):4727. doi: 10.3390/molecules28124727.
In this study, a Z-Scheme WO/CoO p-n heterojunction with a 0D/3D structure was designed and prepared via a simple solvothermal approach to remove the combined pollution of tetracycline and heavy metal Cr(VI) in water. The 0D WO nanoparticles adhered to the surface of the 3D octahedral CoO to facilitate the construction of Z-scheme p-n heterojunctions, which could avoid the deactivation of the monomeric material due to agglomeration, extend the optical response range, and separate the photogenerated electronhole pairs. The degradation efficiency of mixed pollutants after a 70 min reaction was significantly higher than that of monomeric TC and Cr(VI). Among them, a 70% WO/CoO heterojunction had the best photocatalytic degradation effect on the mixture of TC and Cr(VI) pollutants, and the removing rate was 95.35% and 70.2%, respectively. Meanwhile, after five cycles, the removal rate of the mixed pollutants by the 70% WO/CoO remained almost unchanged, indicating that the Z-scheme WO/CoO p-n heterojunction has good stability. In addition, for an active component capture experiment, ESR and LC-MS were employed to reveal the possible Z-scheme pathway under the built-in electric field of the p-n heterojunction and photocatalytic removing mechanism of TC and Cr(VI). These results offer a promising idea for the treatment of the combined pollution of antibiotics and heavy metals by a Z-scheme WO/CoO p-n heterojunction photocatalyst, and have broad application prospects: boosted tetracycline and Cr(VI) simultaneous cleanup over a Z-scheme WO/CoO p-n heterojunction with a 0D/3D structure under visible light.
在这项研究中，通过一种简单的溶剂热方法设计并制备了 Z 型 WO/CoO 型 p-n 异质结，具有 0D/3D 结构，用于去除水中四环素和重金属 Cr(VI)的复合污染。0D WO 纳米颗粒附着在 3D 八面体 CoO 的表面上，有利于构建 Z 型 p-n 异质结，这可以避免由于聚集而导致的单体材料失活，扩展光学响应范围，并分离光生电子空穴对。经过 70 分钟反应后，混合污染物的降解效率明显高于单体 TC 和 Cr(VI)。其中，70%WO/CoO 异质结对 TC 和 Cr(VI)污染物混合物的光催化降解效果最好，去除率分别为 95.35%和 70.2%。同时，经过五次循环后，70%WO/CoO 对混合污染物的去除率几乎不变，表明 Z 型 WO/CoO p-n 异质结具有良好的稳定性。此外，通过活性成分捕获实验，利用 ESR 和 LC-MS 揭示了内置电场下 p-n 异质结的可能 Z 型途径以及 TC 和 Cr(VI)的光催化去除机制。这些结果为 Z 型 WO/CoO p-n 异质结光催化剂处理抗生素和重金属的复合污染提供了一个有前途的思路，具有广阔的应用前景：在可见光下，具有 0D/3D 结构的 Z 型 WO/CoO p-n 异质结协同去除四环素和 Cr(VI)。
