Abstract
Polybrominated diphenyl ethers (PBDEs), which have found extensive use as flame-retarding additives to many polymer materials, are now environmentally ubiquitous and persistent pollutants that present potential health risks to humans and wildlife. Herein, we report for the first time the use of metal oxide semiconductor nanostructures for photocatalytic reductive debromination of PBDEs using visible light. Well-defined cubic Cu2O crystals, surface-decorated with Pd nanoparticles, were prepared via a hydrothermal approach. The Cu2O@Pd demonstrated light-activated tandem photocatalysis, in which Cu2O produces H2 from H2O under visible light irradiation; the evolved H2 is subsequently activated by Pd to achieve the reductive hydrodehalogenation of the PBDE. Cu2O@Pd demonstrated effective debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), one of the PBDEs of greatest environmental concern, with initial pseudo-first-order rate constant of 0.21 h−1. It is shown that the reaction proceeds via a reductive mechanism with preferential debromination at the para positions. Reaction rates for various monobromo- and dibromo-congeners were evaluated, confirming that the debromination order of preference is para > meta >> ortho, which is opposite to the order reported for direct photolysis. We conclude that Cu2O@Pd is a promising photocatalyst for reductive dehalogenation of halogenated organic compounds.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 147-154 |
| Number of pages | 8 |
| Journal | Applied Catalysis B: Environmental |
| Volume | 213 |
| DOIs | |
| State | Published - Sep 15 2017 |
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Keywords
- Metal oxide semiconductor
- PBDE
- Photocatalytic debromination
- Photolysis
- Polybrominated diphenyl ethers
ASJC Scopus subject areas
- Catalysis
- Environmental Science(all)
- Process Chemistry and Technology
Cite this
Metal oxide semiconductor nanomaterial for reductive debromination : Visible light degradation of polybrominated diphenyl ethers by Cu2O@Pd nanostructures. / Miller, Edward B.; Zahran, Elsayed; Knecht, Marc; Bachas, Leonidas G.
In: Applied Catalysis B: Environmental, Vol. 213, 15.09.2017, p. 147-154.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Metal oxide semiconductor nanomaterial for reductive debromination
T2 - Visible light degradation of polybrominated diphenyl ethers by Cu2O@Pd nanostructures
AU - Miller, Edward B.
AU - Zahran, Elsayed
AU - Knecht, Marc
AU - Bachas, Leonidas G
PY - 2017/9/15
Y1 - 2017/9/15
N2 - Polybrominated diphenyl ethers (PBDEs), which have found extensive use as flame-retarding additives to many polymer materials, are now environmentally ubiquitous and persistent pollutants that present potential health risks to humans and wildlife. Herein, we report for the first time the use of metal oxide semiconductor nanostructures for photocatalytic reductive debromination of PBDEs using visible light. Well-defined cubic Cu2O crystals, surface-decorated with Pd nanoparticles, were prepared via a hydrothermal approach. The Cu2O@Pd demonstrated light-activated tandem photocatalysis, in which Cu2O produces H2 from H2O under visible light irradiation; the evolved H2 is subsequently activated by Pd to achieve the reductive hydrodehalogenation of the PBDE. Cu2O@Pd demonstrated effective debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), one of the PBDEs of greatest environmental concern, with initial pseudo-first-order rate constant of 0.21 h−1. It is shown that the reaction proceeds via a reductive mechanism with preferential debromination at the para positions. Reaction rates for various monobromo- and dibromo-congeners were evaluated, confirming that the debromination order of preference is para > meta >> ortho, which is opposite to the order reported for direct photolysis. We conclude that Cu2O@Pd is a promising photocatalyst for reductive dehalogenation of halogenated organic compounds.
AB - Polybrominated diphenyl ethers (PBDEs), which have found extensive use as flame-retarding additives to many polymer materials, are now environmentally ubiquitous and persistent pollutants that present potential health risks to humans and wildlife. Herein, we report for the first time the use of metal oxide semiconductor nanostructures for photocatalytic reductive debromination of PBDEs using visible light. Well-defined cubic Cu2O crystals, surface-decorated with Pd nanoparticles, were prepared via a hydrothermal approach. The Cu2O@Pd demonstrated light-activated tandem photocatalysis, in which Cu2O produces H2 from H2O under visible light irradiation; the evolved H2 is subsequently activated by Pd to achieve the reductive hydrodehalogenation of the PBDE. Cu2O@Pd demonstrated effective debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), one of the PBDEs of greatest environmental concern, with initial pseudo-first-order rate constant of 0.21 h−1. It is shown that the reaction proceeds via a reductive mechanism with preferential debromination at the para positions. Reaction rates for various monobromo- and dibromo-congeners were evaluated, confirming that the debromination order of preference is para > meta >> ortho, which is opposite to the order reported for direct photolysis. We conclude that Cu2O@Pd is a promising photocatalyst for reductive dehalogenation of halogenated organic compounds.
KW - Metal oxide semiconductor
KW - PBDE
KW - Photocatalytic debromination
KW - Photolysis
KW - Polybrominated diphenyl ethers
UR - http://www.scopus.com/inward/record.url?scp=85019181893&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85019181893&partnerID=8YFLogxK
U2 - 10.1016/j.apcatb.2017.05.020
DO - 10.1016/j.apcatb.2017.05.020
M3 - Article
AN - SCOPUS:85019181893
VL - 213
SP - 147
EP - 154
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
SN - 0926-3373
ER -