Coassembly of metal and titanium dioxide nanocrystals directed by monolayered block copolymer inverse micelles for enhanced photocatalytic performance

Himadri Acharya, Jinwoo Sung, Insung Bae, Taehee Kim, Dong Ha Kim, Cheolmin Park

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Functional nanostructures of self-assembled block copolymers (BCPs) incorporated with various inorganic nanomaterials have received considerable attention on account of their many potential applications. Here we demonstrate the two-dimensional self-assembly of anisotropic titanium dioxide (TiO 2) nanocrystals (NCs) and metal nanoparticles (NPs) directed by monolayered poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymer inverse micelles. The independent position-selective assembly of TiO 2 NCs and silver nanoparticles (AgNPs) preferentially in the intermicelle corona regions and the core of micelles, respectively, for instance, was accomplished by spin-coating a mixture solution of PS-b-P4VP and ex situ synthesized TiO 2 NCs, followed by the reduction of Ag salts coordinated in the cores of micelles into AgNPs. Hydrophobic TiO 2 NCs with a diameter and length of approximately 3 nm and 20-30 nm, respectively, were preferentially sequestered in the intermicelle nonpolar PS corona regions energetically favorable with the minimum entropic packing penalty. Subsequent high-temperature annealing at 550 °C not only effectively removed the block copolymer but also transformed the TiO 2 NCs into connected nanoparticles, thus leading to a two-dimensionally ordered TiO 2 network in which AgNPs were also self-organized. The enhanced photocatalytic activity of the AgNP-decorated TiO 2 networks by approximately 27 and 44 % over that of Ag-free TiO 2 networks and randomly deposited TiO 2 nanoparticles, respectively, was confirmed by the UV degradation property of methylene blue. Of micelles and metals: Coassembly of anisotropic TiO 2 nanocrystals and Ag nanoparticles was achieved in the corona and core regions of monolayered block copolymer micelles, respectively (see figure). Thermal heating removed the block copolymer and the resulting TiO 2 network nanostructure with Ag nanoparticles decorating its pores exhibited excellent photocatalytic performance.

Original languageEnglish
Pages (from-to)14695-14701
Number of pages7
JournalChemistry - A European Journal
Volume18
Issue number46
DOIs
Publication statusPublished - 2012 Nov 12

Fingerprint

Micelles
Titanium dioxide
Nanocrystals
Block copolymers
Metals
Nanoparticles
Styrene
Nanostructures
Metal nanoparticles
Methylene Blue
Spin coating
Silver
Nanostructured materials
Self assembly
titanium dioxide
Copolymers
Salts
Annealing
Heating
Degradation

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

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title = "Coassembly of metal and titanium dioxide nanocrystals directed by monolayered block copolymer inverse micelles for enhanced photocatalytic performance",
abstract = "Functional nanostructures of self-assembled block copolymers (BCPs) incorporated with various inorganic nanomaterials have received considerable attention on account of their many potential applications. Here we demonstrate the two-dimensional self-assembly of anisotropic titanium dioxide (TiO 2) nanocrystals (NCs) and metal nanoparticles (NPs) directed by monolayered poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymer inverse micelles. The independent position-selective assembly of TiO 2 NCs and silver nanoparticles (AgNPs) preferentially in the intermicelle corona regions and the core of micelles, respectively, for instance, was accomplished by spin-coating a mixture solution of PS-b-P4VP and ex situ synthesized TiO 2 NCs, followed by the reduction of Ag salts coordinated in the cores of micelles into AgNPs. Hydrophobic TiO 2 NCs with a diameter and length of approximately 3 nm and 20-30 nm, respectively, were preferentially sequestered in the intermicelle nonpolar PS corona regions energetically favorable with the minimum entropic packing penalty. Subsequent high-temperature annealing at 550 °C not only effectively removed the block copolymer but also transformed the TiO 2 NCs into connected nanoparticles, thus leading to a two-dimensionally ordered TiO 2 network in which AgNPs were also self-organized. The enhanced photocatalytic activity of the AgNP-decorated TiO 2 networks by approximately 27 and 44 {\%} over that of Ag-free TiO 2 networks and randomly deposited TiO 2 nanoparticles, respectively, was confirmed by the UV degradation property of methylene blue. Of micelles and metals: Coassembly of anisotropic TiO 2 nanocrystals and Ag nanoparticles was achieved in the corona and core regions of monolayered block copolymer micelles, respectively (see figure). Thermal heating removed the block copolymer and the resulting TiO 2 network nanostructure with Ag nanoparticles decorating its pores exhibited excellent photocatalytic performance.",
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Coassembly of metal and titanium dioxide nanocrystals directed by monolayered block copolymer inverse micelles for enhanced photocatalytic performance. / Acharya, Himadri; Sung, Jinwoo; Bae, Insung; Kim, Taehee; Kim, Dong Ha; Park, Cheolmin.

In: Chemistry - A European Journal, Vol. 18, No. 46, 12.11.2012, p. 14695-14701.

Research output: Contribution to journalArticle

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T1 - Coassembly of metal and titanium dioxide nanocrystals directed by monolayered block copolymer inverse micelles for enhanced photocatalytic performance

AU - Acharya, Himadri

AU - Sung, Jinwoo

AU - Bae, Insung

AU - Kim, Taehee

AU - Kim, Dong Ha

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N2 - Functional nanostructures of self-assembled block copolymers (BCPs) incorporated with various inorganic nanomaterials have received considerable attention on account of their many potential applications. Here we demonstrate the two-dimensional self-assembly of anisotropic titanium dioxide (TiO 2) nanocrystals (NCs) and metal nanoparticles (NPs) directed by monolayered poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymer inverse micelles. The independent position-selective assembly of TiO 2 NCs and silver nanoparticles (AgNPs) preferentially in the intermicelle corona regions and the core of micelles, respectively, for instance, was accomplished by spin-coating a mixture solution of PS-b-P4VP and ex situ synthesized TiO 2 NCs, followed by the reduction of Ag salts coordinated in the cores of micelles into AgNPs. Hydrophobic TiO 2 NCs with a diameter and length of approximately 3 nm and 20-30 nm, respectively, were preferentially sequestered in the intermicelle nonpolar PS corona regions energetically favorable with the minimum entropic packing penalty. Subsequent high-temperature annealing at 550 °C not only effectively removed the block copolymer but also transformed the TiO 2 NCs into connected nanoparticles, thus leading to a two-dimensionally ordered TiO 2 network in which AgNPs were also self-organized. The enhanced photocatalytic activity of the AgNP-decorated TiO 2 networks by approximately 27 and 44 % over that of Ag-free TiO 2 networks and randomly deposited TiO 2 nanoparticles, respectively, was confirmed by the UV degradation property of methylene blue. Of micelles and metals: Coassembly of anisotropic TiO 2 nanocrystals and Ag nanoparticles was achieved in the corona and core regions of monolayered block copolymer micelles, respectively (see figure). Thermal heating removed the block copolymer and the resulting TiO 2 network nanostructure with Ag nanoparticles decorating its pores exhibited excellent photocatalytic performance.

AB - Functional nanostructures of self-assembled block copolymers (BCPs) incorporated with various inorganic nanomaterials have received considerable attention on account of their many potential applications. Here we demonstrate the two-dimensional self-assembly of anisotropic titanium dioxide (TiO 2) nanocrystals (NCs) and metal nanoparticles (NPs) directed by monolayered poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymer inverse micelles. The independent position-selective assembly of TiO 2 NCs and silver nanoparticles (AgNPs) preferentially in the intermicelle corona regions and the core of micelles, respectively, for instance, was accomplished by spin-coating a mixture solution of PS-b-P4VP and ex situ synthesized TiO 2 NCs, followed by the reduction of Ag salts coordinated in the cores of micelles into AgNPs. Hydrophobic TiO 2 NCs with a diameter and length of approximately 3 nm and 20-30 nm, respectively, were preferentially sequestered in the intermicelle nonpolar PS corona regions energetically favorable with the minimum entropic packing penalty. Subsequent high-temperature annealing at 550 °C not only effectively removed the block copolymer but also transformed the TiO 2 NCs into connected nanoparticles, thus leading to a two-dimensionally ordered TiO 2 network in which AgNPs were also self-organized. The enhanced photocatalytic activity of the AgNP-decorated TiO 2 networks by approximately 27 and 44 % over that of Ag-free TiO 2 networks and randomly deposited TiO 2 nanoparticles, respectively, was confirmed by the UV degradation property of methylene blue. Of micelles and metals: Coassembly of anisotropic TiO 2 nanocrystals and Ag nanoparticles was achieved in the corona and core regions of monolayered block copolymer micelles, respectively (see figure). Thermal heating removed the block copolymer and the resulting TiO 2 network nanostructure with Ag nanoparticles decorating its pores exhibited excellent photocatalytic performance.

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