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Debromination of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) by synthetic Pd/Fe0 and Cu/Fe0 in different protic solvents.

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Polybrominated diphenyl ethers (PBDEs) belong to a class of persistent organic pollutants (POPs), with potential toxicity to the liver, reproductive system, and development of mammals. The highly toxic and concentrated… Click to show full abstract

Polybrominated diphenyl ethers (PBDEs) belong to a class of persistent organic pollutants (POPs), with potential toxicity to the liver, reproductive system, and development of mammals. The highly toxic and concentrated congener, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), was chosen to investigate debromination mechanisms by the two synthetic iron-based bimetals (Pd/Fe0 and Cu/Fe0) in two protic solvents (water and ethanol). SEM, XPS, and BET analyses showed that the synthetic bimetals Pd/Fe0 and Cu/Fe0 were spherical with diameters of about 100 nm and loaded with ∼1% (wt%) of Pd and Cu, respectively. GC-MS was used for the analysis of degradation products and the chromatograms showed that both Pd/Fe0 and Cu/Fe0 bimetals had effective reducing properties in water solvent. In ethanol solvent, debromination of BDE-47 by Pd/Fe0 showed a similar high activity, but BDE-47 could be hardly degraded by Cu/Fe0. The dominant debromination products of BDE-47 by Pd/Fe0 and Cu/Fe0 were ortho-substituted and para-substituted BDEs, respectively. Active H-atomic transfer was found to play a key role in the debromination of BDE-47 by Pd/Fe0 in both, water and ethanol, with a preference for para-debromination along with the formation of dibenzo-p-furan (DF) as the by-product, mainly in water. In contrast, electron transfer with a preference for ortho-debromination was found to play a predominant role for Cu/Fe0 system in water. More importance should be provided to active H-atomic transfer for its high efficiency. In-depth study on the mechanism of formation of by-product DF would be significant for its higher toxicity, possibility of accumulation and migration in the environment.

Keywords: fe0; debromination; ether bde; tetrabromodiphenyl ether; water; fe0 fe0

Journal Title: Chemosphere
Year Published: 2018

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