Solar light driven degradation of norfloxacin using as-synthesized Bi3+ and Fe2+ co-doped ZnO with the addition of HSO5−: Toxicities and degradation pathways investigation
Solar light driven degradation of norfloxacin using as-synthesized Bi3+ and Fe2+ co-doped ZnO with the addition of HSO5−: Toxicities and degradation pathways investigation
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DOI：
10.1016/j.cej.2018.06.111
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发表时间：
2018-11
影响因子：
15.1
通讯作者：
N. S. Shah;J. Khan;M. Sayed;Zia Ul Haq Khan;A. Rizwan;N. Muhammad;G. Boczkaj;B. Murtaza;
中科院分区：
文献类型：
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作者：
N. S. Shah;J. Khan;M. Sayed;Zia Ul Haq Khan;A. Rizwan;N. Muhammad;G. Boczkaj;B. Murtaza;
在本研究中，合成了太阳光响应型 Bi3+ 和 Fe2+ 掺杂 ZnO，并将其用于光催化降解诺氟沙星 (NOR)（一种新兴的水污染物）。傅里叶变换红外光谱 (FTIR)、X 射线衍射 (XRD)、场发射扫描电子显微镜 (FESEM)、透射电子显微镜 (TEM)、高分辨率透射电子显微镜 (HRTEM)、选区电子衍射 (SAED) 和紫外可见漫反射光谱 (DRS) 的分析证实了掺杂剂（即 Bi3+ 和 Fe2+）或共掺杂剂（Bi3+/Fe2+）与 ZnO 的耦合，并表明小而窄的尺寸以及高度掺杂 ZnO 的晶体和多孔性质。金属离子掺杂降低了带隙能并抑制了合成的 ZnO 中电子-空穴对的复合。因此，BiFe-ZnO 显示出增强的光催化活性和可重复使用性，在 120 分钟的反应时间内，NOR 的去除率达到 80%，而未掺杂的 ZnO 的去除率为 36%。光致发光 (PL) 技术分析证实，与 Bi-ZnO、Fe-ZnO 和 ZnO 相比，BiFe-ZnO 太阳光活化产生的自由基 dotOH 产率较高。所制备的光催化剂的性能随着 HSO5− 的添加而提高，并随着 [HSO5−]0 的增加而提高。添加了 HSO5− 的 BiFe-ZnO 对 NOR 的降解是由于自由基 dotOH 和 SO4 自由基点−，并且 NOR 显示出与自由基 dotOH 和 SO4 自由基点− 的高反应性。使用自由基点OH和SO4自由基点清除剂抑制NOR的去除效率。添加 HSO5− 的合成光催化剂的光催化活性高度依赖于 [NOR]0、[pH]0、共存离子和天然有机物。根据 NOR 降解模式和确定的转化产物建议了降解途径。 NOR 的矿化以及无毒最终产物的形成表明，添加 HSO5 的共掺杂 ZnO 是处理抗生素污染水的潜在技术。
In this study, solar light responsive Bi3+and Fe2+doped ZnO were synthesized and used for photocatalytic degradation of norfloxacin (NOR), an emerging water pollutant. Analysis with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and UV–vis diffuse reflectance spectroscopy (DRS) confirmed coupling of dopants (i.e., Bi3+and Fe2+) or co-dopants (Bi3+/Fe2+) with ZnO and suggested small narrow size as well as highly crystalline and porous nature of the doped ZnO. Metal ions doping lowered band gap energy and inhibited recombination of electron-hole pair in the as-synthesized ZnO. Consequently, BiFe-ZnO showed enhanced photocatalytic activity and reusability, giving 80% removal of NOR as compared to 36% by un-doped ZnO at a reaction time of 120 min. The analysis with photoluminescence (PL) technique verified high yield ofradical dotOH from solar light activation of BiFe-ZnO compared to Bi-ZnO, Fe-ZnO and ZnO. Performance of the as-prepared photocatalysts was promoted with the added HSO5−and increased with increasing [HSO5−]0. Degradation of NOR by BiFe-ZnO with the added HSO5−was due toradical dotOH and SO4radical dot−and NOR showed high reactivity withradical dotOH and SO4radical dot−. The removal efficiency of NOR was inhibited usingradical dotOH and SO4radical dot−scavengers. Photocatalytic activity of the as-synthesized photocatalysts with the added HSO5−was highly dependent on [NOR]0, [pH]0, co-existing ions, and natural organic matter. Degradation pathways were suggested from the pattern of NOR degradation and identified transformation products. The mineralization of NOR as well as formation of non-toxic end product suggests co-doped ZnO with added HSO5−to be a potential technology for treating antibiotics contaminated water.