Journal
ENVIRONMENTAL POLLUTION
Volume 222, Issue -, Pages 331-337Publisher
ELSEVIER SCI LTD
DOI: 10.1016/j.envpol.2016.12.030
Keywords
PBDE; Debromination pathway; H-atom transfer; n-ZVI; Bimetal; Mulliken charge
Categories
Funding
- National Natural Science Foundation of China [41573091, U1501234]
- Guangdong Natural Science Funds for Distinguished Young Scholar [2015A030306005]
- Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program [2015TQ01Z233]
- Science and Technology Program of Guangdong Province [2014A020216004]
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The relative significance of H-atom transfer versus electron transfer in the dehalogenation of halogenated organic compounds (HOCs) in bimetallic systems has long been debated. In this study, we have investigated this question through the case study of the debromination of 2, 2', 4, 4'-tetrabromodiphenyl ether (BDE-47). The debromination rates of isomer products of BDE-47 by palladized nano zero-valent iron (n-ZVI/Pd) in the same reactor were compared. The results confirmed a shift in the debromination pathway of BDE-47 when treated with unpalladized nano zero-valent iron (n-ZVI) vs. treatment with n-ZVI/Pd. Study showed that BDE5 could be rapidly debrominated in a palladium-H2 system, and the debromination pathway in this system is the same as that in the n-ZVI/Pd system. These results suggest that the H-atom species adsorbed on the surface of palladium are responsible for the enhanced reaction rates and the shift of the debromination pathway in the n-ZVI/Pd system. The Mulliken charges, calculated with density functional theory, on bromine atoms of PBDEs were directly correlated with the susceptibility to the e-transfer pathway in the n-ZVI system and inversely correlated with the susceptibility to the H-transfer pathway in n-ZVI/Pd system. These experimentally verified correlations in BDE47 permit the prediction of the dominant debromination pathway in other BDE5. (C) 2016 Elsevier Ltd. All rights reserved.
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