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In-situ construction of Co(OH)2 nanoparticles decorated urchin-like WO3 for highly efficient degradation of sulfachloropyridazine via peroxymonosulfate activation: Intermediates and DFT calculation
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。

更新日期:2020-04-23
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