Non-hydrolytic sol-gel synthesis of zirconium phosphonates with
controlled mesoporosity

J 2023

Non-hydrolytic sol-gel synthesis of zirconium phosphonates with controlled mesoporosity

MACHÁČ, Petr, Aleš STÝSKALÍK, Zdeněk MORAVEC and Jiří PINKAS

Basic information

Original name

Non-hydrolytic sol-gel synthesis of zirconium phosphonates with controlled mesoporosity

Authors

MACHÁČ, Petr (203 Czech Republic, belonging to the institution), Aleš STÝSKALÍK (203 Czech Republic, belonging to the institution), Zdeněk MORAVEC (203 Czech Republic, belonging to the institution) and Jiří PINKAS (203 Czech Republic, guarantor, belonging to the institution)

Edition

Microporous and Mesoporous Materials, Elsevier, 2023, 1387-1811

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

Netherlands

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 5.200 in 2022

RIV identification code

RIV/00216224:14310/23:00131672

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1016/j.micromeso.2023.112787

UT WoS

001074508200001

Keywords in English

Zirconium phosphonates; Non-hydrolytic; Sol-gel; Silylamine elimination; Mesoporous; Hybrid; Xerogel; Surface area; Catalysis; Epoxide opening

Abstract

V originále

We disclose the preparation of high-surface-area mesoporous zirconium phosphonates by the non-hydrolytic sol-gel reactions (NHSG) of Zr(NEt2)4 with trimethylsilylated phosphonates RP(O)(OSiMe3)2 (R = Me, tBu, Ph, OSiMe3), and bis-phosphonates (Me3SiO)2(O)P–X–P(O)(OSiMe3)2 (X = CH2, C6H4, CH2(C6H4)CH2, and CH2(C6H4)2CH2) in dry toluene under ambient pressure. Zirconium phosphonate xerogels are prepared by condensation reaction with the elimination of silylamine Me3SiNEt2. This irreversible reaction provides the amorphous xerogels and drives the formation of the porous structure. The influence of organic moieties bonded to phosphorus atoms on porosity was examined in this study. The final surface area of dried xerogels reached 720 m2 g−1 without any extra templating agent. Xerogels were characterized by 13C, 29Si, and 31P solid-state NMR to define atomic homogeneity and evidence the presence of organic phosphonate substituents and residual amido and trimethylsilyl groups. The amount of residual reactive groups was determined by gravimetric measurements and the thermal analysis (TG-DSC) method. These groups may be applied in post-synthetic surface modification, such as controlling the hydrophobic/hydrophilic properties. The catalytic properties of NHSG-prepared xerogels were tested on a model reaction of aminolysis of styrene oxide in a batch mode employing relatively bulky molecules. Products were identified and quantified by the 1H NMR spectroscopy. Catalyst performance parameters, such as selectivity, conversion, turnover frequency, and others, were exceeded compared to benchmark microporous layered zirconium phosphonate catalysts.

Links

GJ20-03636Y, research and development project

Name: Nové katalyzátory pro přípravu 1,3-butadienu z ethanolu

Investor: Czech Science Foundation

MUNI/A/1209/2022, interní kód MU

Name: Molekuly, komplexy, makrocykly a xerogely

Investor: Masaryk University, Molecules, complexes, macrocycles, and xerogels

MUNI/J/0007/2021, interní kód MU

Name: Tailored Catalysts for Carbon Dioxide Utilization

Investor: Masaryk University, MASH JUNIOR - MUNI Award In Science and Humanities JUNIOR

90110, large research infrastructures

Name: CzechNanoLab

90127, large research infrastructures

Name: CIISB II

Citovat

MACHÁČ, Petr, Aleš STÝSKALÍK, Zdeněk MORAVEC and Jiří PINKAS. Non-hydrolytic sol-gel synthesis of zirconium phosphonates with controlled mesoporosity. Microporous and Mesoporous Materials. Elsevier, 2023, vol. 362, December, p. 1-10. ISSN 1387-1811. Available from: https://dx.doi.org/10.1016/j.micromeso.2023.112787.

@article{2310124,
   author = {Macháč, Petr and Stýskalík, Aleš and Moravec, Zdeněk and Pinkas, Jiří},
   article_number = {December},
   doi = {http://dx.doi.org/10.1016/j.micromeso.2023.112787},
   keywords = {Zirconium phosphonates; Non-hydrolytic; Sol-gel; Silylamine elimination; Mesoporous; Hybrid; Xerogel; Surface area; Catalysis; Epoxide opening},
   language = {eng},
   issn = {1387-1811},
   journal = {Microporous and Mesoporous Materials},
   title = {Non-hydrolytic sol-gel synthesis of zirconium phosphonates with controlled mesoporosity},
   url = {https://doi.org/10.1016/j.micromeso.2023.112787},
   volume = {362},
   year = {2023}
}

TY  - JOUR
ID  - 2310124
AU  - Macháč, Petr - Stýskalík, Aleš - Moravec, Zdeněk - Pinkas, Jiří
PY  - 2023
TI  - Non-hydrolytic sol-gel synthesis of zirconium phosphonates with controlled mesoporosity
JF  - Microporous and Mesoporous Materials
VL  - 362
IS  - December
SP  - 1-10
EP  - 1-10
PB  - Elsevier
SN  - 13871811
KW  - Zirconium phosphonates
KW  - Non-hydrolytic
KW  - Sol-gel
KW  - Silylamine elimination
KW  - Mesoporous
KW  - Hybrid
KW  - Xerogel
KW  - Surface area
KW  - Catalysis
KW  - Epoxide opening
UR  - https://doi.org/10.1016/j.micromeso.2023.112787
N2  - We disclose the preparation of high-surface-area mesoporous zirconium phosphonates by the non-hydrolytic sol-gel reactions (NHSG) of Zr(NEt2)4 with trimethylsilylated phosphonates RP(O)(OSiMe3)2 (R = Me, tBu, Ph, OSiMe3), and bis-phosphonates (Me3SiO)2(O)P–X–P(O)(OSiMe3)2 (X = CH2, C6H4, CH2(C6H4)CH2, and CH2(C6H4)2CH2) in dry toluene under ambient pressure. Zirconium phosphonate xerogels are prepared by condensation reaction with the elimination of silylamine Me3SiNEt2. This irreversible reaction provides the amorphous xerogels and drives the formation of the porous structure. The influence of organic moieties bonded to phosphorus atoms on porosity was examined in this study. The final surface area of dried xerogels reached 720 m2 g−1 without any extra templating agent. Xerogels were characterized by 13C, 29Si, and 31P solid-state NMR to define atomic homogeneity and evidence the presence of organic phosphonate substituents and residual amido and trimethylsilyl groups. The amount of residual reactive groups was determined by gravimetric measurements and the thermal analysis (TG-DSC) method. These groups may be applied in post-synthetic surface modification, such as controlling the hydrophobic/hydrophilic properties. The catalytic properties of NHSG-prepared xerogels were tested on a model reaction of aminolysis of styrene oxide in a batch mode employing relatively bulky molecules. Products were identified and quantified by the 1H NMR spectroscopy. Catalyst performance parameters, such as selectivity, conversion, turnover frequency, and others, were exceeded compared to benchmark microporous layered zirconium phosphonate catalysts.
ER  -

MACHÁČ, Petr, Aleš STÝSKALÍK, Zdeněk MORAVEC and Jiří PINKAS. Non-hydrolytic sol-gel synthesis of zirconium phosphonates with controlled mesoporosity. \textit{Microporous and Mesoporous Materials}. Elsevier, 2023, vol.~362, December, p.~1-10. ISSN~1387-1811. Available from: https://dx.doi.org/10.1016/j.micromeso.2023.112787.

Detailed Information on Publication Record