Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films

T. Lunkenbein, M.M.G. Kamperman, Z. Li, C. Bojer, M. Drechsler, S. Forster, U. Wiesner, A. Muller, J. Breu

Research output: Contribution to journalArticleAcademicpeer-review

40 Citations (Scopus)

Abstract

Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices.
Original languageEnglish
Pages (from-to)12685-12692
Number of pages8
JournalJournal of the American Chemical Society
Volume134
Issue number30
DOIs
Publication statusPublished - 2012

Fingerprint

Nanocomposites
Nanocomposite films
Block copolymers
Composite films
Coulomb interactions
X ray scattering
Butadiene
Self assembly
Evaporation
Negative ions
Transmission electron microscopy
Acids
Static Electricity
Transmission Electron Microscopy
Anions
X-Rays
Equipment and Supplies
polyoxometalate I
poly(2-(dimethylamino)ethyl methacrylate)
phosphododecamolybdate

Keywords

  • surfactant-encapsulated polyoxometalate
  • block-copolymer surfactants
  • transition-metal oxides
  • lyotropic phases
  • catalysis
  • nanoparticles
  • composites
  • complexes
  • chemistry
  • clusters

Cite this

Lunkenbein, T., Kamperman, M. M. G., Li, Z., Bojer, C., Drechsler, M., Forster, S., ... Breu, J. (2012). Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films. Journal of the American Chemical Society, 134(30), 12685-12692. https://doi.org/10.1021/ja304073t
Lunkenbein, T. ; Kamperman, M.M.G. ; Li, Z. ; Bojer, C. ; Drechsler, M. ; Forster, S. ; Wiesner, U. ; Muller, A. ; Breu, J. / Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 30. pp. 12685-12692.
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abstract = "Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices.",
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author = "T. Lunkenbein and M.M.G. Kamperman and Z. Li and C. Bojer and M. Drechsler and S. Forster and U. Wiesner and A. Muller and J. Breu",
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Lunkenbein, T, Kamperman, MMG, Li, Z, Bojer, C, Drechsler, M, Forster, S, Wiesner, U, Muller, A & Breu, J 2012, 'Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films', Journal of the American Chemical Society, vol. 134, no. 30, pp. 12685-12692. https://doi.org/10.1021/ja304073t

Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films. / Lunkenbein, T.; Kamperman, M.M.G.; Li, Z.; Bojer, C.; Drechsler, M.; Forster, S.; Wiesner, U.; Muller, A.; Breu, J.

In: Journal of the American Chemical Society, Vol. 134, No. 30, 2012, p. 12685-12692.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films

AU - Lunkenbein, T.

AU - Kamperman, M.M.G.

AU - Li, Z.

AU - Bojer, C.

AU - Drechsler, M.

AU - Forster, S.

AU - Wiesner, U.

AU - Muller, A.

AU - Breu, J.

PY - 2012

Y1 - 2012

N2 - Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices.

AB - Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices.

KW - surfactant-encapsulated polyoxometalate

KW - block-copolymer surfactants

KW - transition-metal oxides

KW - lyotropic phases

KW - catalysis

KW - nanoparticles

KW - composites

KW - complexes

KW - chemistry

KW - clusters

U2 - 10.1021/ja304073t

DO - 10.1021/ja304073t

M3 - Article

VL - 134

SP - 12685

EP - 12692

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 30

ER -