State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875, PR China.
Water Res. 2012 May 1;46(7):2281-9. doi: 10.1016/j.watres.2012.01.053. Epub 2012 Feb 16.
Electrochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) in aqueous solution was investigated over Ti/SnO(2)-Sb, Ti/SnO(2)-Sb/PbO(2), and Ti/SnO(2)-Sb/MnO(2) anodes. The degradation of PFOA followed pseudo-first-order kinetics. The degradation ratios on Ti/SnO(2)-Sb, Ti/SnO(2)-Sb/PbO(2), and Ti/SnO(2)-Sb/MnO(2) anodes achieved 90.3%, 91.1%, and 31.7%, respectively, after 90 min electrolysis at an initial 100 mg/L PFOA concentration at a constant current density of 10 mA/cm(2) with a 10 mmol/L NaClO(4) supporting electrolyte solution. The defluorination rates of PFOA on these three anodes were 72.9%, 77.4%, 45.6%, respectively. The main influencing factors on electrochemical decomposition of PFOA over Ti/SnO(2)-Sb anode were evaluated, including current density (5-40 mA/cm(2)), initial pH value (3-11), plate distance (0.5-2.0 cm), and initial concentration (5-500 mg/L). The results indicated that PFOA (100 mL of 100 mg/L) degradation ratio and defluorination ratio achieved 98.8% and 73.9%, respectively, at the optimal conditions after 90 min electrolysis. Under this optimal condition, the degradation rate constant and the degradation half-life were 0.064 min(-1) and 10.8 min, respectively. The intermediate products including short-chain perfluorinated carboxylic acids (PFCAs, C(2) ≈ C(6)) and perfluorocarbons (C(2) ≈ C(7)) were detected by electrospray ionization (ESI) mass spectrum. A possible electrochemical degradation mechanism of PFOA including electron transfer, Kolbe decarboxylation, radical reaction, decomposition, and hydrolysis was proposed. The electrochemical technique could be employed to degrade PFOA from contaminated wastewater as well as to reduce the toxicity of PFOA.
在 Ti/SnO(2)-Sb、Ti/SnO(2)-Sb/PbO(2) 和 Ti/SnO(2)-Sb/MnO(2) 阳极上研究了环境持久性全氟辛酸 (PFOA) 在水溶液中的电化学分解。PFOA 的降解遵循准一级动力学。在初始 PFOA 浓度为 100mg/L、电流密度为 10mA/cm(2)、恒定电流密度下,90min 后,在 10mmol/L NaClO(4)支持电解质溶液中,Ti/SnO(2)-Sb、Ti/SnO(2)-Sb/PbO(2) 和 Ti/SnO(2)-Sb/MnO(2) 阳极的降解率分别为 90.3%、91.1%和 31.7%。这些阳极上 PFOA 的脱氟率分别为 72.9%、77.4%和 45.6%。评估了电流密度(5-40mA/cm(2))、初始 pH 值(3-11)、极板间距(0.5-2.0cm)和初始浓度(5-500mg/L)等因素对 Ti/SnO(2)-Sb 阳极上 PFOA 电化学分解的主要影响。结果表明,在最优条件下,经过 90min 电解,PFOA(100mL,浓度为 100mg/L)的降解率和脱氟率分别达到 98.8%和 73.9%。在此最佳条件下,降解速率常数和半衰期分别为 0.064min(-1)和 10.8min。通过电喷雾电离(ESI)质谱检测到包括短链全氟羧酸(PFCAs,C(2)≈C(6))和全氟碳(C(2)≈C(7))在内的中间产物。提出了 PFOA 的电化学降解机理,包括电子转移、科尔贝脱羧、自由基反应、分解和水解。电化学技术可用于降解受污染废水中的 PFOA,以及降低 PFOA 的毒性。