Two-Dimensional-Hexagonal Periodic Mesoporous Polymer Resin Thin Films by Soft Templating

Schuster, Jörg; Köhn, Ralf; Keilbach, Andreas; Döblinger, Markus; Amenitsch, Heinz; Bein, Thomas

doi:10.1021/cm901163t

Cited by 64 publications

(54 citation statements)

References 27 publications

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“…This is related to a restricted shrinkage behavior in contrast to thin films, in which uniaxial shrinkage of around 50 % occurs. [15] From 400 to 600 8C ( Figure 1C), only small peak shifts to higher angles are visible, whereas no further shrinkage to 1000 8C can be observed. Even at 1000 8C ( Figure 1D), the SAXS pattern shows intense peaks and higher-order reflections.…”

Section: Resultsmentioning

confidence: 95%

“…Further progress concerning high thermal stability or easier synthesis conditions for bulk materials was achieved by Wang et al [13] and Lu et al [14] A soft-templating pathway that led to thin films with face-centered orthorhombic (Fmmm) symmetry was reported by Tanaka et al [9] Recently we reported a soft-templating method for highly ordered mesoporous polymer resin thin films with a 2D-hexagonal order (P6mm). [15] Mesoporous phases within the pores of anodic alumina membranes (AAM) were first achieved with mesoporous silica. In 2003, Yang et al [16] synthesized a circular hexagonal mesoporous silica phase, in which the mesopores form circles around the axis of the columnar AAM pores (or the membrane normal).…”

Section: Introductionmentioning

confidence: 99%

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Cubic and Hexagonal Mesoporous Carbon in the Pores of Anodic Alumina Membranes

Schuster¹,

Keilbach²,

Köhn³

et al. 2011

Chemistry A European J

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Cubic and circular hexagonal mesoporous carbon phases in the confined environment of the pores of anodic alumina membranes (AAM) were obtained by organic-organic self-assembly of a preformed oligomeric resol precursor and the triblock copolymer templates Pluronic F127 or P123, respectively. Casting and solvent evaporation were followed by self-assembly and the formation of a condensed wall material by thermopolymerization of the precursor oligomers, thus resulting in mesostructured phenolic resin phases. Subsequent thermal decomposition of the surfactant and carbonization were achieved through thermal treatment at temperatures up to 1000 °C under an inert atmosphere. The resulting hierarchical mesoporous composite materials were characterized by small-angle X-ray scattering and nitrogen-sorption measurements. The structural features were directly imaged in TEM cross-sections of the composite membranes. For both structures, the AAM pores were completely filled and no shrinkage was observed due to strong adhesion of the carbon-wall material to the AAM pore walls. As a consequence, the pore size of the mesophase system stays almost constant even after thermal treatment at 1000 °C.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Cubic and Hexagonal Mesoporous Carbon in the Pores of Anodic Alumina Membranes

Schuster¹,

Keilbach²,

Köhn³

et al. 2011

Chemistry A European J

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“…The film thickness is around 200 nm after thermopolymerization for all samples. 14 The incident angle of the GISAXS setup was relatively high (0.3°) as compared to Bang et al, 40 thus the X-rays should penetrate the full film thickness. Doubling of reflections in z-direction arises from diffraction of the reflected incident beam.…”

Section: ■ Characterizationmentioning

confidence: 90%

In Situ SAXS Study on a New Mechanism for Mesostructure Formation of Ordered Mesoporous Carbons: Thermally Induced Self-Assembly

et al. 2012

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A new mechanism for mesostructure formation of ordered mesoporous carbons (OMCs) was investigated with in situ small-angle X-ray scattering (SAXS) measurements: thermally induced self-assembly. Unlike the well-established evaporation-induced self-assembly (EISA), the structure formation for organic-organic self-assembly of an oligomeric resol precursor and the block-copolymer templates Pluronic P123 and F127 does not occur during evaporation but only by following a thermopolymerization step at temperatures above 100 °C. The systems investigated here were cubic (Im3m), orthorhombic Fmmm) and 2D-hexagonal (plane group p6mm) mesoporous carbon phases in confined environments, as thin films and within the pores of anodic alumina membranes (AAMs), respectively. The thin films were prepared by spin-coating mixtures of the resol precursor and the surfactants in ethanol followed by thermopolymerization of the precursor oligomers. The carbon phases within the pores of AAMs were made by imbibition of the latter solutions followed by solvent evaporation and thermopolymerization within the solid template. This thermopolymerization step was investigated in detail with in situ grazing incidence small-angle X-ray scattering (GISAXS, for films) and in situ SAXS (for AAMs). It was found that the structural evolution strongly depends on the chosen temperature, which controls both the rate of the mesostructure formation and the spatial dimensions of the resulting mesophase. Therefore the process of structure formation differs significantly from the known EISA process and may rather be viewed as thermally induced self-assembly. The complete process of structure formation, template removal, and shrinkage during carbonization up to 1100 °C was monitored in this in situ SAXS study.

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“…The resulting material was black, consistent with the expected carbon residue. 28,69,71,72,101,102 This compression complicates SAXS analysis since the orientation of the powdered sample was unknown and thus the longest real-space d 10 dimension from the elliptical scattering pattern was assumed to coincide with the lm normal and was thus used for comparison. S2a †).…”

Section: Mesoporous Materialsmentioning

confidence: 99%

Ordered mesoporous titania from highly amphiphilic block copolymers: tuned solution conditions enable highly ordered morphologies and ultra-large mesopores

et al. 2015

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Crystalline transition metal oxides with controlled mesopore architectures are in increasing demand to enhance the performance of energy conversion and storage devices. Solution based block copolymer self-assembly routes to achieve ordered mesoporous and crystalline titania have been studied for more than a decade, but have so far mostly been limited to water and alcohol dispersible polymers. This constraint has limited the accessible morphology space as well as structural dimensions. Moreover, synthetic approaches are mostly performed in a trial-and-error fashion using chemical intuition rather than being based on well-defined design parameters. We present solubility design guidelines that facilitate coassembly with highly amphiphilic block copolymers, enabling the formation of ordered structures with diverse length scales (d 10 ¼ 13.8-63.0 nm) and bulk-type morphologies. Thus, highly ordered and crystalline titania with the largest reported pores (d ¼ 32.3 nm) was demonstrated for such a coassembly approach without the use of pore-expanders. Furthermore, the use of an ABC triblock terpolymer system led to a 3D ordered network morphology. In all cases, subsequent calcination treatments, such as the CASH procedure, enabled the formation of highly crystalline mesoporous materials while preserving the mesostructure.

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Two-Dimensional-Hexagonal Periodic Mesoporous Polymer Resin Thin Films by Soft Templating

Cited by 64 publications

References 27 publications

Cubic and Hexagonal Mesoporous Carbon in the Pores of Anodic Alumina Membranes

Cubic and Hexagonal Mesoporous Carbon in the Pores of Anodic Alumina Membranes

In Situ SAXS Study on a New Mechanism for Mesostructure Formation of Ordered Mesoporous Carbons: Thermally Induced Self-Assembly

Ordered mesoporous titania from highly amphiphilic block copolymers: tuned solution conditions enable highly ordered morphologies and ultra-large mesopores

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