Metal oxide semiconductor nanomaterial for reductive debromination: Visible light degradation of polybrominated diphenyl ethers by Cu2O@Pd nanostructures

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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 languageEnglish (US)
Pages (from-to)147-154
Number of pages8
JournalApplied Catalysis B: Environmental
Volume213
DOIs
StatePublished - Sep 15 2017

Fingerprint

Halogenated Diphenyl Ethers
PBDE
Nanostructured materials
Ethers
Nanostructures
Metals
Degradation
degradation
Dehalogenation
Photocatalysis
Health risks
Photolysis
Photocatalysts
photolysis
Organic compounds
ether
Ether
reaction rate
health risk
Reaction rates

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

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title = "Metal oxide semiconductor nanomaterial for reductive debromination: Visible light degradation of polybrominated diphenyl ethers by Cu2O@Pd nanostructures",
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.",
keywords = "Metal oxide semiconductor, PBDE, Photocatalytic debromination, Photolysis, Polybrominated diphenyl ethers",
author = "Miller, {Edward B.} and Elsayed Zahran and Marc Knecht and Bachas, {Leonidas G}",
year = "2017",
month = "9",
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doi = "10.1016/j.apcatb.2017.05.020",
language = "English (US)",
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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

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KW - Photolysis

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