Four different porphyrinic zirconium-based metal–organic frameworks (Zr-MOFs) were comparatively studied to activate peroxydisulfate (PDS) for tetracycline hydrochloride (TCH) degradation. Results indicated NZVI@MOF-545 was the optimal catalyst and the NZVI@MOF-545/PDS system exhibited a high TCH (initial concentration of 100 mg L) removal efficiency of 95.9 %. The catalytic reaction conditions of NZVI@MOF-545/PDS were optimized using response surface methodology (RSM) and results showed that the TCH (initial concentration of 800 mg L) degradation rate of 90.34 ± 0.66 % was obtained under optimal conditions of 1.03 g L PDS, 0.84 g L NZVI@MOF-545 with the initial pH of 9.80, temperature of 45 °C, and rotation speed of 265 rpm. The high degradation rate was attributed to the reactive species generated by the carbon-containing functional groups and metal sites of NZVI@MOF-545, and the relative contribution was O > SO•>HO•>O•. Moreover, the LC-MS results suggested that TCH could be degraded into 15 intermediates through three potential degradation pathways. Toxicity evaluation demonstrated an alleviation in median lethal concentration at 96 h (LC-96 h), low bioaccumulation, significant reductions in developmental toxicity and mutagenicity for most intermediates. In brief, NZVI@MOF-545 possessed remarkable catalytic ability and acceptable reusability to active PDS for TCH degradation, and the toxicity of TCH could be significantly reduced after the degradation.

中文翻译：

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NZVI@MOF-545 复合物与过二硫酸盐增强催化降解盐酸四环素：性能和机理

对四种不同的卟啉锆基金属有机骨架（Zr-MOF）活化过二硫酸盐（PDS）以降解四环素（TCH）进行了比较研究。结果表明，NZVI@MOF-545 是最佳催化剂，NZVI@MOF-545/PDS 系统表现出高达 95.9% 的 TCH（初始浓度 100 mg·L）去除效率。采用响应面法（RSM）对NZVI@MOF-545/PDS的催化反应条件进行优化，结果表明，在1.03 g的最佳条件下，TCH（初始浓度800 mg·L）的降解率为90.34 ± 0.66 % L PDS，0.84 g·L NZVI@MOF-545，初始 pH 为 9.80，温度为 45 °C，转速为 265 rpm。高降解率归因于NZVI@MOF-545的含碳官能团和金属位点产生的活性物种，相对贡献为O > SO•>HO•>O•。此外，LC-MS 结果表明 TCH 可以通过三种潜在的降解途径降解为 15 种中间体。毒性评估表明，96 小时（LC-96 小时）的半数致死浓度有所减轻，生物蓄积性较低，大多数中间体的发育毒性和致突变性显着降低。总之，NZVI@MOF-545对活性PDS降解TCH具有显着的催化能力和良好的可重复使用性，并且降解后TCH的毒性可显着降低。