Degradation mechanisms of perfluorooctanoic acid by FeCu@NBC bimetallic composite system
KONG Yi-fan1, TANG Zheng1, CHEN Xiao-qian2, LIU Min2, SHEN Lu2, QIN Yan1, GAO Pin1
1. College of Environmental Science and Engineering, Donghua University, Shanghai 201620, China; 2. Bioassay and Safety Assessment Laboratory, Shanghai Academy of Public Measurement, Shanghai 201203, China
Abstract：The nitrogen-doped biochar-supported Fe and Cu bimetallic composite (FeCu@NBC) was synthesized by a one-step pyrolysis, and its catalytic degradation efficiency and influencing factors on PFOA were investigated. Then, the degradation mechanisms and potential pathways of PFOA were analyzed by free radical detection and quenching experiments, as well as the time-of-flight mass spectrometry (TOF-MS) and density functional theory (DFT) calculation. The results show that Fe and Cu on the surface of FeCu@NBC mainly existed in the form of zero-valent single element, which could achieve a favorable removal performance of PFOA under a neutral condition. As its dosage was 1g/L and the initial PFOA concentration was 100mg/L, the removal efficiency of PFOA reached 92.1% within 6h of reaction, which was significantly higher than that of Fe@NBC (28.5%) and Cu@NBC (66.8%), indicating that the synergistic effect of Fe0 and Cu0 can enhance PFOA decomposition. The free radical quenching experiments and ESR measurements suggest that the free electron (e-) was the main factor affecting the decomposition of PFOA. Furthermore, the results of TOF-MS and DFT calculation show that the potential degradation pathway of PFOA followed firstly decarboxylation to generate unstable C7F15·, then hydrolysis to gradually generate short-chain perfluoroalkyl carboxylic acid, and finally achieved the effective decomposition of PFOA.
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