Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2020-04-23 , DOI: 10.1016/j.cej.2020.125186 Xi Tao , Poyueh Pan , Taobo Huang , Long Chen , Haodong Ji , Juanjuan Qi , Fengbin Sun , Wen Liu
Sulfachloropyridazine (SCP) was commonly used as a broad-spectrum sulfonamide antibiotic and hard to be removed through traditional sewage treatment process. In this study, we developed a simple and controllable strategy to realize in-situ construction of Co(OH)2 nanoparticles decorated urchin-like WO3 (Co(OH)2/WO3), which could efficiently remove SCP through peroxymonosulfate (PMS) activation. Some tiny nanoparticles of Co(OH)2 decorated on the spines/nanorods or surfaces of urchin-like WO3 by transmission electron microscopy (TEM) analysis. The obtained 10 wt% Co(OH)2/WO3 realized completely removal of SCP (degradation efficiency 100 %) with a high reaction rate constant (k1) of 0.88 min-1 within 3 min at optimal pH 7. That was because the urchin-like WO3 with numerous adsorption functional groups on its surface (e.g., W=O and –OH bonds) could adsorb the Co2+ easily to form CoOH+, which was perceived the rate-limiting step for PMS activation and generating radicals. Radical quenching experiments indicated that SO4• – played a more significant role than HO• radicals. Density functional theory (DFT) calculation revealed that the atoms of SCP with high Fukui index (f –) were active sites, which preferred to be attacked by the electrophilic SO4• – and HO• radicals. The toxicity of the intermediates by SCP degradation was evaluated by quantitative structure-activity relationship (QSAR) prediction through Toxicity Estimation Software Tool (T.E.S.T.). The possible degradation pathway and catalytic mechanism for SCP removal were proposed. Considering the good catalytic properties of Co(OH)2/WO3-PMS, the material will show great application potential in the removal of emerging contaminants in water.
中文翻译:
Co(OH)2纳米颗粒的原位构建装饰了类似顽童的WO 3,可通过过一硫酸盐活化来高效降解磺胺氯哒嗪:中间体和DFT计算
磺胺氯哒嗪(SCP)通常用作广谱磺酰胺类抗生素,很难通过传统的污水处理工艺去除。在这项研究中,我们开发了一种简单且可控的策略,以实现原位构建装饰有顽童状WO 3(Co(OH)2 / WO 3)的Co(OH)2纳米颗粒,该纳米颗粒可通过过一硫酸盐(PMS)有效去除SCP )激活。通过透射电子显微镜(TEM)分析,在棘突/纳米节或类顽童WO 3的表面上装饰了一些微小的Co(OH)2纳米颗粒。所获得的10重量%的Co(OH)2 / WO 3实现了在最佳pH值为3的情况下在3分钟内以0.88 min -1的高反应速率常数(k 1)完全清除SCP(降解效率100%)的原因。这是因为在其上具有许多吸附官能团的类似海胆的WO 3表面(例如W = O和–OH键)可以轻松吸附Co 2+形成CoOH +,这被认为是PMS活化和产生自由基的限速步骤。自由基猝灭实验表明,SO 4 •-的作用比HO •自由基更重要。密度泛函理论(DFT)计算表明,具有高福井指数的SCP原子(f –)是活性位点,更倾向于被亲电子的SO 4 •–和HO •自由基攻击。通过毒性估算软件工具(TEST)通过定量构效关系(QSAR)预测评估了SCP降解中间体的毒性。提出了去除SCP的可能的降解途径和催化机制。考虑到Co(OH)2 / WO 3 -PMS的良好催化性能,该材料在去除水中新兴污染物方面将显示出巨大的应用潜力。