Boparai Hardiljeet Kaur, El-Sharnouby Omneya, O'Carroll Denis M
Department of Civil and Environmental Engineering, Western University, 1151 Richmond Rd, London, ON, N6A 5B8, Canada.
Department of Civil and Mineral Engineering, University of Toronto, 35 St. George Street, Toronto, ON, M5S 1A4, Canada.
Sci Rep. 2023 Jul 23;13(1):11883. doi: 10.1038/s41598-023-38678-6.
Aqueous-phase catalyzed reduction of organic contaminants via zerovalent copper nanoparticles (nCu), coupled with borohydride (hydrogen donor), has shown promising results. So far, the research on nCu as a remedial treatment has focused mainly on contaminant removal efficiencies and degradation mechanisms. Our study has examined the effects of Cu/Cu ratio, surface poisoning (presence of chloride, sulfides, humic acid (HA)), and regeneration of Cu sites on catalytic dechlorination of aqueous-phase 1,2-dichloroethane (1,2-DCA) via nCu-borohydride. Scanning electron microscopy confirmed the nano size and quasi-spherical shape of nCu particles. X-ray diffraction confirmed the presence of Cu and CuO and x-ray photoelectron spectroscopy also provided the Cu/Cu ratios. Reactivity experiments showed that nCu was incapable of utilizing H from borohydride left over during nCu synthesis and, hence, additional borohydride was essential for 1,2-DCA dechlorination. Washing the nCu particles improved their Cu/Cu ratio (1.27) and 92% 1,2-DCA was removed in 7 h with k = 0.345 h as compared to only 44% by unwashed nCu (0.158 h) with Cu/Cu ratio of 0.59, in the presence of borohydride. The presence of chloride (1000-2000 mg L), sulfides (0.4-4 mg L), and HA (10-30 mg L) suppressed 1,2-DCA dechlorination; which was improved by additional borohydride probably via regeneration of Cu sites. Coating the particles decreased their catalytic dechlorination efficiency. 85-90% of the removed 1,2-DCA was recovered as chloride. Chloroethane and ethane were main dechlorination products indicating hydrogenolysis as the major pathway. Our results imply that synthesis parameters and groundwater solutes control nCu catalytic activity by altering its physico-chemical properties. Thus, these factors should be considered to develop an efficient remedial design for practical applications of nCu-borohydride.
通过零价铜纳米颗粒(nCu)与硼氢化物(氢供体)耦合进行水相催化还原有机污染物已显示出有前景的结果。到目前为止,关于nCu作为一种修复处理方法的研究主要集中在污染物去除效率和降解机制上。我们的研究考察了Cu/Cu比、表面中毒(存在氯离子、硫化物、腐殖酸(HA))以及Cu位点再生对通过nCu-硼氢化物催化水相1,2-二氯乙烷(1,2-DCA)脱氯的影响。扫描电子显微镜证实了nCu颗粒的纳米尺寸和准球形形状。X射线衍射证实了Cu和CuO的存在,X射线光电子能谱也提供了Cu/Cu比。反应性实验表明,nCu无法利用nCu合成过程中剩余的硼氢化物中的氢,因此,额外的硼氢化物对于1,2-DCA脱氯至关重要。洗涤nCu颗粒提高了它们的Cu/Cu比(1.27),在硼氢化物存在的情况下,7小时内92%的1,2-DCA被去除,k = 0.345 h⁻¹,相比之下,未洗涤的nCu(Cu/Cu比为0.59,k = 0.158 h⁻¹)在7小时内仅去除了44%。氯离子(1000 - 2000 mg L⁻¹)、硫化物(0.4 - 4 mg L⁻¹)和HA(10 - 30 mg L⁻¹)的存在抑制了1,2-DCA脱氯;额外的硼氢化物可能通过Cu位点的再生改善了这种情况。包覆颗粒降低了它们的催化脱氯效率。85 - 90%去除的1,2-DCA以氯离子形式回收。氯乙烷和乙烷是主要的脱氯产物,表明氢解是主要途径。我们的结果表明,合成参数和地下水溶质通过改变其物理化学性质来控制nCu的催化活性。因此,在开发用于nCu-硼氢化物实际应用的高效修复设计时应考虑这些因素。