Preparation, characterization, and surface modification of periodic mesoporous silicon-aluminum-carbon-nitrogen frameworks

O. Majoulet, C. Salameh, M. E. Schuster, U. B. Demirci, Yoshiyuki Sugahara, S. Bernard, P. Miele

    Research output: Contribution to journalArticle

    23 Citations (Scopus)

    Abstract

    Periodic mesoporous silicon-aluminum-carbon-nitrogen (Si/Al/C/N) frameworks with P6mm hexagonal symmetry were synthesized by a solvent nanocasting route using mesoporous carbon (CMK-3) as hard template and preceramic polymers containing both -[R1R2Si-N(R3)]n- and -[R4Al-N(R5)]n- backbones (with R 1 = R2 = R3 = R4 = H and R 5 = CH2CH3) as ceramic precursors. The preceramic polymers are prepared through a simple and cost-effective procedure by blending poly(perhydropolysilazane) and poly(ethyliminoalane) as precursors of silicon nitride/silicon (Si3N4/Si) and carbon-containing aluminum nitride (Al/C/N), respectively. The blended polymers with various and controlled Al:Si ratios were infiltrated into the porous structure of CMK-3, followed by a pyrolysis-template removal cycle performed under nitrogen at 1000 C (2 h, ceramic conversion), then in an ammonia atmosphere at 1000 C (5 h, template removal). This procedure resulted in the formation of periodic mesoporous Si/Al/C/N frameworks with surface areas of 182-326 m2 g-1, a pore size distribution of 4.1-5.9 nm, and pore volumes in the range of 0.51-0.65 cm3 g-1. The uniformity of the mesopores and periodicity of the obtained amorphous micrometer-size powders, studied by transmission electron microscopy (TEM), small-angle X-ray diffraction (SA-XRD), and N2 sorption, are affected by the Al:Si ratio. Amorphous materials did not exhibit weight change up to 1400-1470 C in flowing nitrogen, and their behavior in air, up to 1000 C (with dwelling time of 5 h), is dependent on the proportion of AlN and Si 3N4 phases. The as-obtained powders then were decorated with Pt (nano)particles by impregnation to form supported catalysts. The as-formed catalysts showed attractive reactivity and robustness in our probe reaction, namely, the hydrolysis of an alkaline solution of sodium borohydride at 80 C. Our main results are reported therein.

    Original languageEnglish
    Pages (from-to)3957-3970
    Number of pages14
    JournalChemistry of Materials
    Volume25
    Issue number20
    DOIs
    Publication statusPublished - 2013

    Fingerprint

    Silicon
    Aluminum
    Surface treatment
    Polymers
    Nitrogen
    Carbon
    Powders
    Aluminum nitride
    Silicon nitride
    Ammonia
    Catalyst supports
    Impregnation
    Pore size
    Sorption
    Hydrolysis
    Pyrolysis
    Sodium
    Transmission electron microscopy
    X ray diffraction
    Catalysts

    Keywords

    • hydrogen production
    • ordered mesoporosity
    • platinum nanoparticles
    • polyaluminosilazane
    • silicon-aluminum-carbon-nitrogen

    ASJC Scopus subject areas

    • Materials Chemistry
    • Chemical Engineering(all)
    • Chemistry(all)

    Cite this

    Preparation, characterization, and surface modification of periodic mesoporous silicon-aluminum-carbon-nitrogen frameworks. / Majoulet, O.; Salameh, C.; Schuster, M. E.; Demirci, U. B.; Sugahara, Yoshiyuki; Bernard, S.; Miele, P.

    In: Chemistry of Materials, Vol. 25, No. 20, 2013, p. 3957-3970.

    Research output: Contribution to journalArticle

    Majoulet, O. ; Salameh, C. ; Schuster, M. E. ; Demirci, U. B. ; Sugahara, Yoshiyuki ; Bernard, S. ; Miele, P. / Preparation, characterization, and surface modification of periodic mesoporous silicon-aluminum-carbon-nitrogen frameworks. In: Chemistry of Materials. 2013 ; Vol. 25, No. 20. pp. 3957-3970.
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    abstract = "Periodic mesoporous silicon-aluminum-carbon-nitrogen (Si/Al/C/N) frameworks with P6mm hexagonal symmetry were synthesized by a solvent nanocasting route using mesoporous carbon (CMK-3) as hard template and preceramic polymers containing both -[R1R2Si-N(R3)]n- and -[R4Al-N(R5)]n- backbones (with R 1 = R2 = R3 = R4 = H and R 5 = CH2CH3) as ceramic precursors. The preceramic polymers are prepared through a simple and cost-effective procedure by blending poly(perhydropolysilazane) and poly(ethyliminoalane) as precursors of silicon nitride/silicon (Si3N4/Si) and carbon-containing aluminum nitride (Al/C/N), respectively. The blended polymers with various and controlled Al:Si ratios were infiltrated into the porous structure of CMK-3, followed by a pyrolysis-template removal cycle performed under nitrogen at 1000 C (2 h, ceramic conversion), then in an ammonia atmosphere at 1000 C (5 h, template removal). This procedure resulted in the formation of periodic mesoporous Si/Al/C/N frameworks with surface areas of 182-326 m2 g-1, a pore size distribution of 4.1-5.9 nm, and pore volumes in the range of 0.51-0.65 cm3 g-1. The uniformity of the mesopores and periodicity of the obtained amorphous micrometer-size powders, studied by transmission electron microscopy (TEM), small-angle X-ray diffraction (SA-XRD), and N2 sorption, are affected by the Al:Si ratio. Amorphous materials did not exhibit weight change up to 1400-1470 C in flowing nitrogen, and their behavior in air, up to 1000 C (with dwelling time of 5 h), is dependent on the proportion of AlN and Si 3N4 phases. The as-obtained powders then were decorated with Pt (nano)particles by impregnation to form supported catalysts. The as-formed catalysts showed attractive reactivity and robustness in our probe reaction, namely, the hydrolysis of an alkaline solution of sodium borohydride at 80 C. Our main results are reported therein.",
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    AU - Salameh, C.

    AU - Schuster, M. E.

    AU - Demirci, U. B.

    AU - Sugahara, Yoshiyuki

    AU - Bernard, S.

    AU - Miele, P.

    PY - 2013

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    N2 - Periodic mesoporous silicon-aluminum-carbon-nitrogen (Si/Al/C/N) frameworks with P6mm hexagonal symmetry were synthesized by a solvent nanocasting route using mesoporous carbon (CMK-3) as hard template and preceramic polymers containing both -[R1R2Si-N(R3)]n- and -[R4Al-N(R5)]n- backbones (with R 1 = R2 = R3 = R4 = H and R 5 = CH2CH3) as ceramic precursors. The preceramic polymers are prepared through a simple and cost-effective procedure by blending poly(perhydropolysilazane) and poly(ethyliminoalane) as precursors of silicon nitride/silicon (Si3N4/Si) and carbon-containing aluminum nitride (Al/C/N), respectively. The blended polymers with various and controlled Al:Si ratios were infiltrated into the porous structure of CMK-3, followed by a pyrolysis-template removal cycle performed under nitrogen at 1000 C (2 h, ceramic conversion), then in an ammonia atmosphere at 1000 C (5 h, template removal). This procedure resulted in the formation of periodic mesoporous Si/Al/C/N frameworks with surface areas of 182-326 m2 g-1, a pore size distribution of 4.1-5.9 nm, and pore volumes in the range of 0.51-0.65 cm3 g-1. The uniformity of the mesopores and periodicity of the obtained amorphous micrometer-size powders, studied by transmission electron microscopy (TEM), small-angle X-ray diffraction (SA-XRD), and N2 sorption, are affected by the Al:Si ratio. Amorphous materials did not exhibit weight change up to 1400-1470 C in flowing nitrogen, and their behavior in air, up to 1000 C (with dwelling time of 5 h), is dependent on the proportion of AlN and Si 3N4 phases. The as-obtained powders then were decorated with Pt (nano)particles by impregnation to form supported catalysts. The as-formed catalysts showed attractive reactivity and robustness in our probe reaction, namely, the hydrolysis of an alkaline solution of sodium borohydride at 80 C. Our main results are reported therein.

    AB - Periodic mesoporous silicon-aluminum-carbon-nitrogen (Si/Al/C/N) frameworks with P6mm hexagonal symmetry were synthesized by a solvent nanocasting route using mesoporous carbon (CMK-3) as hard template and preceramic polymers containing both -[R1R2Si-N(R3)]n- and -[R4Al-N(R5)]n- backbones (with R 1 = R2 = R3 = R4 = H and R 5 = CH2CH3) as ceramic precursors. The preceramic polymers are prepared through a simple and cost-effective procedure by blending poly(perhydropolysilazane) and poly(ethyliminoalane) as precursors of silicon nitride/silicon (Si3N4/Si) and carbon-containing aluminum nitride (Al/C/N), respectively. The blended polymers with various and controlled Al:Si ratios were infiltrated into the porous structure of CMK-3, followed by a pyrolysis-template removal cycle performed under nitrogen at 1000 C (2 h, ceramic conversion), then in an ammonia atmosphere at 1000 C (5 h, template removal). This procedure resulted in the formation of periodic mesoporous Si/Al/C/N frameworks with surface areas of 182-326 m2 g-1, a pore size distribution of 4.1-5.9 nm, and pore volumes in the range of 0.51-0.65 cm3 g-1. The uniformity of the mesopores and periodicity of the obtained amorphous micrometer-size powders, studied by transmission electron microscopy (TEM), small-angle X-ray diffraction (SA-XRD), and N2 sorption, are affected by the Al:Si ratio. Amorphous materials did not exhibit weight change up to 1400-1470 C in flowing nitrogen, and their behavior in air, up to 1000 C (with dwelling time of 5 h), is dependent on the proportion of AlN and Si 3N4 phases. The as-obtained powders then were decorated with Pt (nano)particles by impregnation to form supported catalysts. The as-formed catalysts showed attractive reactivity and robustness in our probe reaction, namely, the hydrolysis of an alkaline solution of sodium borohydride at 80 C. Our main results are reported therein.

    KW - hydrogen production

    KW - ordered mesoporosity

    KW - platinum nanoparticles

    KW - polyaluminosilazane

    KW - silicon-aluminum-carbon-nitrogen

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