A novel PbO(2) electrode with a high oxygen evolution potential (OEP) and excellent electrochemical oxidation performance is prepared to improve the traditional PbO(2) electrode, which is modified by changing the microstructure and wetting ability. A middle layer of TiO(2) nanotubes (NTs) with a large surface area is introduced on Ti substrate, and a small amount of Cu is predeposited at the bottom of TiO(2)-NTs. The modification will improve the electrochemical performance by enhancing the loading capacity of PbO(2) and the combination between PbO(2) and Ti substrate. The hydrophilic surface becomes highly hydrophobic by adding fluorine resin. The improved PbO(2) electrode exhibits a similar morphology, surface wetting ability, high OEP, and electrochemical performance with boron-doped diamond film (BDD) electrode. However, the physical resistance of the PbO(2) electrode is much lower than that of BDD, exhibiting higher conductivity. The hydroxyl radical utilization is significantly enhanced, resulting in a higher oxidation rate and higher removal for 2,4-dichlorophenoxyacetic acid.

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A green hydrothermally enhanced electrochemical oxidation (HTEO) technique is developed to treat the high concentration refractory perfluorooctanoic acid (PFOA) wastewater on boron-doped diamond (BDD) film electrode. Results show that HTEO can demonstrate higher degradation efficiency for PFOA than the normal electrochemical oxidation (EO) process, with the removal of PFOA, total organic carbon (TOC), and organic fluorine in the HTEO process increasing by 1.1, 1.8, and 2.1 times, respectively. The kinetics study indicates that the degradation of PFOA follows a first-order reaction in the HTEO process with the apparent reaction rate constant 3.1 times higher than that in the EO process. The higher degradation efficiency of PFOA is due to the hydrothermal enhancement in electrochemical properties of the electrode and solution. Compared with EO, during the HTEO process, the conductivity and ionic migration rate of the solution is improved by 540% and 60%, respectively. In addition, the Tafel slope is increased to 343 from 279 mV dec(-1), indicating an inhibition effect of oxygen evolution reaction and a more effective oxidation of PFOA. In particular, the hydrothermal condition promotes a high formation rate of hydroxyl radical with the concentration almost 2 times of that in EO, which is considered the inner factor leading to the higher degradation efficiency. The density functional theory simulations demonstrate that the nonterminal C-C bonds in the main carbon chain can be easily destructed in the hydrothermal condition, as confirmed by the experimental detection of intermediates of C(5)F(11)COOH, C(4)F(9)COOH, C(3)F(7)COOH, C(2)F(5)COOH, CF(3)COOH, and some dicarboxylic acids. As a result, a reaction pathway is tentatively proposed.

Aqueous aromatic hydrocarbons are chemically stable, high toxic refractory pollutants that can only be oxidized to phenols and quinone on either Pt or traditional PbO(2) electrodes. In this study, a novel method for the electrochemical incineration of benzene homologues on superhydrophobic PbO(2) electrode (hydrophobic-PbO(2)) was proposed under mild conditions. Hydrophobic-PbO(2) can achieve the complete mineralization of aromatic hydrocarbons and exhibit high removal effect, rapid oxidation rate, and low energy consumption. The kinetics of the electrochemical incineration was also investigated, and the results revealed that the cleavage of the benzene ring is a key factor affecting the incineration efficiency. Moreover, on hydrophobic-PbO(2), the decay of intermediates was rapid, and low concentrations of aromatics were accumulated during the reaction. The removal of the initial pollutants and the effects of oxidative cleavage were related to the number of methyl groups on the benzene ring. Specifically, the results of physical experiments and quantum calculations revealed that the charge density of carbon atoms increases with an increase in the number of methyl groups, which promotes the electrophilic attack of ·OH.

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