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Effects of Reduced Sulfur Compounds on Pd-catalytic Hydrodechlorination of TCE in Groundwater by Cathodic H2 under Electrochemically-induced Oxidizing Conditions

机译:电化学诱导氧化条件下还原性硫化合物对阴极H2催化钯对地下水中三氯乙烯催化加氢脱氯的影响

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摘要

Reduced sulfur compounds (RSCs) poison Pd catalysts for catalytic hydrodechlorination of contaminants in anoxic groundwater. This study investigates the effects of RSCs on Pd-catalytic hydrodechlorination of trichloroethylene (TCE) in oxic groundwater. Water electrolysis in an undivided electrolytic cell is used to produce H2 for TCE hydrodechlorination under oxidizing conditions. TCE is efficiently hydrodechlorinated to ethane, with significant accumulation of H2O2 under acidic conditions. Presence of sulfide at concentrations less than 93.8 μM moderately inhibits TCE hydrodechlorination and H2O2 production. Presence of sulfite at low concentrations (≤ 1 mM) significantly enhances TCE decay, while at high concentration (3 mM) inhibits initially and enhances afterwards when sulfite concentration declines to less than 1 mM. Using radical scavenging experiments and electron spin resonance assay, SO3•− which is generated from sulfite under oxidizing conditions is validated as the new reactive species contributing to the enhancement. This study reveals a distinct mechanism of effect of sulfite on TCE hydrodechlorination by Pd and H2 in oxic groundwater and presents an alternative approach to increasing resistance of Pd to RSCs poisoning.
机译:还原性硫化合物(RSC)会毒害Pd催化剂,以催化将缺氧地下水中的污染物进行加氢脱氯。本研究调查了RSC对含氧地下水中Pd催化三氯乙烯(TCE)加氢脱氯的影响。在不分隔的电解池中进行水电解可在氧化条件下产生用于TCE加氢脱氯的H2。 TCE有效地加氢脱氯为乙烷,在酸性条件下会大量积聚H2O2。浓度低于93.8μM的硫化物会适度抑制TCE加氢脱氯和H2O2的产生。低浓度(≤1 mM)的亚硫酸盐的存在显着增强了TCE的衰减,而高浓度(3 mM)的亚硫酸盐的存在先受到抑制,然后在亚硫酸盐浓度降至1 mM以下时增强。通过自由基清除实验和电子自旋共振分析,验证了亚硫酸盐在氧化条件下生成的SO3 •-是有助于增强反应的新反应物种。这项研究揭示了亚硫酸盐对含氧地下水中Pd和H2对TCE加氢脱氯作用的独特机理,并提出了增加Pd对RSCs中毒抵抗力的替代方法。

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