School of Chemical Science and Engineering, Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University , Shanghai 200092, China.
College of Science, Xi'an University of Architecture and Technology , Xi'an, Shaanxi 710055, China.
Environ Sci Technol. 2017 Jul 18;51(14):8067-8076. doi: 10.1021/acs.est.7b00393. Epub 2017 Jul 6.
To improve selectivity of electrocatalytic degradation of toxic, odorous mercaptans, the fractal-structured dendritic Au/BDD (boron-doped diamond) anode with molecular recognition is fabricated through a facile replacement method. SEM and TEM characterizations show that the gold dendrites are single crystals and have high population of the Au (111) facet. The distinctive structure endows the electrode with advantages of low resistivity, high active surface area, and prominent electrocatalytic activity. To evaluate selectivity, the dendritic Au/BDD is applied in degrading two groups of synthetic wastewater containing thiophenol/2-mercaptobenzimidazole (targets) and phenol/2-hydroxybenzimidazole (interferences), respectively. Results show that targets removals reach 91%/94%, while interferences removals are only 58%/48% in a short time. The corresponding degradation kinetic constants of targets are 3.25 times and 4.1 times that of interferences in the same group, demonstrating modification of dendritic gold on BDD could effectively enhance electrocatalytic target-selectivity. XPS and EXAFS further reveal that the selective electrocatalytic degradation derives from preferential recognition and fast adsorption to thiophenol depending on strong Au-S bond. The efficient, selective degradation is attributed to the synergetic effects between accumulative behavior and outstanding electrochemical performances. This work provides a new strategy for selective electrochemical degradation of contaminants for actual wastewater treatment.
为提高有毒、恶臭巯基的电催化降解选择性,通过简便的置换法制备了具有分子识别能力的分形结构树枝状 Au/BDD(掺硼金刚石)阳极。SEM 和 TEM 表征表明,金树枝晶为单晶,具有高比例的 Au(111)面。独特的结构使电极具有低电阻率、高有效表面积和突出的电催化活性等优点。为了评估选择性,将树枝状 Au/BDD 用于分别降解两组含有噻吩/2-巯基苯并咪唑(目标物)和苯酚/2-羟基苯并咪唑(干扰物)的合成废水。结果表明,在短时间内,目标物的去除率达到 91%/94%,而干扰物的去除率仅为 58%/48%。相应的目标物降解动力学常数在同组中分别是干扰物的 3.25 倍和 4.1 倍,表明 BDD 上修饰树枝状金可以有效增强电催化目标物的选择性。XPS 和 EXAFS 进一步揭示,选择性电催化降解源于对噻吩的优先识别和快速吸附,这依赖于强 Au-S 键。高效、选择性的降解归因于累积行为和优异电化学性能的协同作用。这项工作为实际废水处理中污染物的选择性电化学降解提供了一种新策略。