Porous Hybrid Inorganic-Organic Silicophosphate Materials by
Non-Hydrolytic Sol-Gel Polycondensation and Their Use as Solid
Phosphoric Acid Catalyst

a 2015

Porous Hybrid Inorganic-Organic Silicophosphate Materials by Non-Hydrolytic Sol-Gel Polycondensation and Their Use as Solid Phosphoric Acid Catalyst

STÝSKALÍK, Aleš, David ŠKODA, Zdeněk MORAVEC, Jiří PINKAS, Craig E. BARNES et. al.

Basic information

Original name

Porous Hybrid Inorganic-Organic Silicophosphate Materials by Non-Hydrolytic Sol-Gel Polycondensation and Their Use as Solid Phosphoric Acid Catalyst

Authors

STÝSKALÍK, Aleš (203 Czech Republic, belonging to the institution), David ŠKODA (203 Czech Republic, belonging to the institution), Zdeněk MORAVEC (203 Czech Republic, belonging to the institution), Jiří PINKAS (203 Czech Republic, guarantor, belonging to the institution) and Craig E. BARNES (840 United States of America)

Edition

Fourth International Conference on Hybrid Materials, 9-13 March 2015 in Sitges, Spain, 2015

Other information

Language

English

Type of outcome

Konferenční abstrakt

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

Spain

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

RIV identification code

RIV/00216224:14310/15:00080913

Organization unit

Faculty of Science

Keywords in English

silicophosphate xerogels; hybrid materials; heterogeneous catalysis; solid phosphoric acid

Abstract

V originále

Non-hydrolytic sol-gel reactions are viable alternatives to classical aqueous techniques in the area of synthesis of multimetallic oxides and inorganic-organic hybrid materials in the form of xerogels, nanoparticles, and thin films. We developed non-hydrolytic sol-gel route based on acetic acid ester elimination providing phosphosilicate hybrid inorganic-organic materials. The polycondensation reactions between Si(OAc)4 and OP(OSiMe3)3 lead to microporous phosphosilicate xerogels with surface areas up to 568 m2 g-1. The structure of xerogels was built up exclusively from Si-O-P bonds and contained octahedrally coordinated silicon atoms, which are characteristic for crystalline silicon phosphates.1 We changed starting precursors to acetoxysilanes and phosphonic acid esters with bridging alkyl or aryl groups (AcO)3Si-(CH2)x-Si(OAc)3 (x = 1-3, 6), (Me3SiO)2P(O)-3R-P(O)(OSiMe3)2 (3R = C2H4, C6H4). Silicon in acetoxysilanes with bridging organic groups was not able to acquire hexacoordination in contrast to Si in Si(OAc)4. The change of the structure of the xerogels, which were in this case built up from SiO4 tetrahedrons, was accompanied by the modification of textural properties – the hybrid phosphosilicates displayed significant mesoporosity. The resulting samples were chemically modified with POCl3, water and methanol in order to introduce Broensted acidic P-OH groups onto the surface of xerogels. The products of chemical modification resembled solid phosphoric acid catalysts and were utilized in methylstyrene dimerization. The mesoporous silicophosphate samples with high number of P-OH groups on the surface provided excellent yields and selectivities in this catalytic test reaction. The prepared xerogels were characterized by solid-state 13C, 29Si, 31P NMR, IR, surface area analysis, TGA and XRD.

Links

ED1.1.00/02.0068, research and development project

Name: CEITEC - central european institute of technology

GAP207/11/0555, research and development project

Name: Oxidy a fosforečnany kovů jako formy jaderného odpadu: studium sonochemického srážení, tepelných přeměn a rozpustnosti (Acronym: OPNW)

Investor: Czech Science Foundation

LH11028, research and development project

Name: Nehydrolytické sol-gelové reakce pro přípravu křemičitanů a fosforečnanů s řízenou porozitou a funkčními skupinami na povrchu (Acronym: NHSGKNOX)

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

STÝSKALÍK, Aleš, David ŠKODA, Zdeněk MORAVEC, Jiří PINKAS and Craig E. BARNES. Porous Hybrid Inorganic-Organic Silicophosphate Materials by Non-Hydrolytic Sol-Gel Polycondensation and Their Use as Solid Phosphoric Acid Catalyst. In Fourth International Conference on Hybrid Materials, 9-13 March 2015 in Sitges, Spain. 2015.

@proceedings{1306728,
   author = {Stýskalík, Aleš and Škoda, David and Moravec, Zdeněk and Pinkas, Jiří and Barnes, Craig E.},
   booktitle = {Fourth International Conference on Hybrid Materials, 9-13 March 2015 in Sitges, Spain},
   keywords = {silicophosphate xerogels; hybrid materials; heterogeneous catalysis; solid phosphoric acid},
   language = {eng},
   title = {Porous Hybrid Inorganic-Organic Silicophosphate Materials by Non-Hydrolytic Sol-Gel Polycondensation and Their Use as Solid Phosphoric Acid Catalyst},
   url = {http://www.hybridmaterialsconference.com/resources/downloads/Hybridmaterials_Poster%20programme_V4_16%20Feb.pdf},
   year = {2015}
}

TY  - CONF
ID  - 1306728
AU  - Stýskalík, Aleš - Škoda, David - Moravec, Zdeněk - Pinkas, Jiří - Barnes, Craig E.
PY  - 2015
TI  - Porous Hybrid Inorganic-Organic Silicophosphate Materials by Non-Hydrolytic Sol-Gel Polycondensation and Their Use as Solid Phosphoric Acid Catalyst
KW  - silicophosphate xerogels
KW  - hybrid materials
KW  - heterogeneous catalysis
KW  - solid phosphoric acid
UR  - http://www.hybridmaterialsconference.com/resources/downloads/Hybridmaterials_Poster%20programme_V4_16%20Feb.pdf
L2  - http://www.hybridmaterialsconference.com/resources/downloads/Hybridmaterials_Poster%20programme_V4_16%20Feb.pdf
N2  - Non-hydrolytic sol-gel reactions are viable alternatives to classical aqueous techniques in the area of synthesis of multimetallic oxides and inorganic-organic hybrid materials in the form of xerogels, nanoparticles, and thin films. We developed non-hydrolytic sol-gel route based on acetic acid ester elimination providing phosphosilicate hybrid inorganic-organic materials. The polycondensation reactions between Si(OAc)4 and OP(OSiMe3)3 lead to microporous phosphosilicate xerogels with surface areas up to 568 m2 g-1. The structure of xerogels was built up exclusively from Si-O-P bonds and contained octahedrally coordinated silicon atoms, which are characteristic for crystalline silicon phosphates.1 We changed starting precursors to acetoxysilanes and phosphonic acid esters with bridging alkyl or aryl groups (AcO)3Si-(CH2)x-Si(OAc)3 (x = 1-3, 6), (Me3SiO)2P(O)-3R-P(O)(OSiMe3)2 (3R = C2H4, C6H4). Silicon in acetoxysilanes with bridging organic groups was not able to acquire hexacoordination in contrast to Si in Si(OAc)4. The change of the structure of the xerogels, which were in this case built up from SiO4 tetrahedrons, was accompanied by the modification of textural properties – the hybrid phosphosilicates displayed significant mesoporosity. The resulting samples were chemically modified with POCl3, water and methanol in order to introduce Broensted acidic P-OH groups onto the surface of xerogels. The products of chemical modification resembled solid phosphoric acid catalysts and were utilized in methylstyrene dimerization. The mesoporous silicophosphate samples with high number of P-OH groups on the surface provided excellent yields and selectivities in this catalytic test reaction. The prepared xerogels were characterized by solid-state 13C, 29Si, 31P NMR, IR, surface area analysis, TGA and XRD.
ER  -

STÝSKALÍK, Aleš, David ŠKODA, Zdeněk MORAVEC, Jiří PINKAS and Craig E. BARNES. Porous Hybrid Inorganic-Organic Silicophosphate Materials by Non-Hydrolytic Sol-Gel Polycondensation and Their Use as Solid Phosphoric Acid Catalyst. In \textit{Fourth International Conference on Hybrid Materials, 9-13 March 2015 in Sitges, Spain}. 2015.

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