Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and
DFT-Calculated 27Al NMR Parameters

J 2024

Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters

KEJÍK, Martin; Jiri BRUS; Lukas JEREMIAS; Lucie ŠIMONÍKOVÁ; Zdeněk MORAVEC et. al.

Základní údaje

Originální název

Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters

Autoři

KEJÍK, Martin (203 Česká republika, domácí); Jiri BRUS; Lukas JEREMIAS; Lucie ŠIMONÍKOVÁ (203 Česká republika, domácí); Zdeněk MORAVEC (203 Česká republika, domácí); Libor KOBERA; Aleš STÝSKALÍK (203 Česká republika, domácí); Craig E. BARNES a Jiří PINKAS (203 Česká republika, garant, domácí)

Vydání

Inorganic Chemistry, American Chemical Society, 2024, 0020-1669

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 4.300 v roce 2023

Kód RIV

RIV/00216224:14310/24:00135477

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1021/acs.inorgchem.3c04035

UT WoS

001158206500001

EID Scopus

2-s2.0-85184001568

Klíčová slova anglicky

Aromatic compounds; Condensation; Ligands; Materials; Nuclear magnetic resonance spectroscopy

Štítky

CF NMR, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 27. 3. 2025 08:03, Mgr. Marie Novosadová Šípková, DiS.

Anotace

V originále

Porous aluminosilicates are functional materials of paramount importance as Lewis acid catalysts in the synthetic industry, yet the participating aluminum species remain poorly studied. Herein, a series of model aluminosilicate networks containing [L–AlO3] (L = THF, Et3N, pyridine, triethylphosphine oxide (TEPO)) and [AlO4]− centers were prepared through nonhydrolytic sol–gel condensation reactions of the spherosilicate building block (Me3Sn)8Si8O20 with L–AlX3 (X = Cl, Me, Et) and [Me4N] [AlCl4] compounds in THF or toluene. The substoichiometric dosage of the Al precursors ensured complete condensation and uniform incorporation, with the bulky spherosilicate forcing a separation between neighboring aluminum centers. The materials were characterized by 1H, 13C, 27Al, 29Si, and 31P MAS NMR and FTIR spectroscopies, ICP-OES, gravimetry, and N2 adsorption porosimetry. The resulting aluminum centers were resolved by 27Al TQ/MAS NMR techniques and assigned based on their spectroscopic parameters obtained by peak fitting (δiso, CQ, η) and their correspondence to the values calculated on model structures by DFT methods. A clear correlation between the decrease in the symmetry of the Al centers and the increase of the observed CQ was established with values spanning from 4.4 MHz for distorted [AlO4]− to 15.1 MHz for [THF–AlO3]. Products containing exclusively [TEPO–AlO3] or [AlO4]− centers could be obtained (single-site materials). For L = THF, Et3N, and pyridine, the [AlO4]− centers were formed together with the expected [L–AlO3] species, and a viable mechanism for the unexpected emergence of [AlO4]− was proposed.

Návaznosti

EH22_008/0004572, projekt VaV

Název: Kvantové materiály pro aplikace v udržitelných technologiích

GJ20-03636Y, projekt VaV

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

Investor: Grantová agentura ČR, Nové katalyzátory pro přípravu 1,3-butadienu z ethanolu

MUNI/A/1575/2023, interní kód MU

Název: Metody chemické a fyzikálně-chemické analýzy pro studium přírodních a syntetických materiálů.

Investor: Masarykova univerzita, Metody chemické a fyzikálně-chemické analýzy pro studium přírodních a syntetických materiálů.

90242, velká výzkumná infrastruktura

Název: CIISB III

90254, velká výzkumná infrastruktura

Název: e-INFRA CZ II

Citovat

KEJÍK, Martin; Jiri BRUS; Lukas JEREMIAS; Lucie ŠIMONÍKOVÁ; Zdeněk MORAVEC; Libor KOBERA; Aleš STÝSKALÍK; Craig E. BARNES a Jiří PINKAS. Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters. Inorganic Chemistry. American Chemical Society, 2024, roč. 63, č. 5, s. 2679-2694. ISSN 0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.3c04035.

@article{2371497,
   author = {Kejík, Martin and Brus, Jiri and Jeremias, Lukas and Šimoníková, Lucie and Moravec, Zdeněk and Kobera, Libor and Stýskalík, Aleš and Barnes, Craig E. and Pinkas, Jiří},
   article_number = {5},
   doi = {http://dx.doi.org/10.1021/acs.inorgchem.3c04035},
   keywords = {Aromatic compounds; Condensation; Ligands; Materials; Nuclear magnetic resonance spectroscopy},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters},
   url = {https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04035},
   volume = {63},
   year = {2024}
}

TY  - JOUR
ID  - 2371497
AU  - Kejík, Martin - Brus, Jiri - Jeremias, Lukas - Šimoníková, Lucie - Moravec, Zdeněk - Kobera, Libor - Stýskalík, Aleš - Barnes, Craig E. - Pinkas, Jiří
PY  - 2024
TI  - Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters
JF  - Inorganic Chemistry
VL  - 63
IS  - 5
SP  - 2679-2694
EP  - 2679-2694
PB  - American Chemical Society
SN  - 00201669
KW  - Aromatic compounds
KW  - Condensation
KW  - Ligands
KW  - Materials
KW  - Nuclear magnetic resonance spectroscopy
UR  - https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04035
N2  - Porous aluminosilicates are functional materials of paramount importance as Lewis acid catalysts in the synthetic industry, yet the participating aluminum species remain poorly studied. Herein, a series of model aluminosilicate networks containing [L–AlO3] (L = THF, Et3N, pyridine, triethylphosphine oxide (TEPO)) and [AlO4]− centers were prepared through nonhydrolytic sol–gel condensation reactions of the spherosilicate building block (Me3Sn)8Si8O20 with L–AlX3 (X = Cl, Me, Et) and [Me4N] [AlCl4] compounds in THF or toluene. The substoichiometric dosage of the Al precursors ensured complete condensation and uniform incorporation, with the bulky spherosilicate forcing a separation between neighboring aluminum centers. The materials were characterized by 1H, 13C, 27Al, 29Si, and 31P MAS NMR and FTIR spectroscopies, ICP-OES, gravimetry, and N2 adsorption porosimetry. The resulting aluminum centers were resolved by 27Al TQ/MAS NMR techniques and assigned based on their spectroscopic parameters obtained by peak fitting (δiso, CQ, η) and their correspondence to the values calculated on model structures by DFT methods. A clear correlation between the decrease in the symmetry of the Al centers and the increase of the observed CQ was established with values spanning from 4.4 MHz for distorted [AlO4]− to 15.1 MHz for [THF–AlO3]. Products containing exclusively [TEPO–AlO3] or [AlO4]− centers could be obtained (single-site materials). For L = THF, Et3N, and pyridine, the [AlO4]− centers were formed together with the expected [L–AlO3] species, and a viable mechanism for the unexpected emergence of [AlO4]− was proposed.
ER  -

KEJÍK, Martin; Jiri BRUS; Lukas JEREMIAS; Lucie ŠIMONÍKOVÁ; Zdeněk MORAVEC; Libor KOBERA; Aleš STÝSKALÍK; Craig E. BARNES a Jiří PINKAS. Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters. \textit{Inorganic Chemistry}. American Chemical Society, 2024, roč.~63, č.~5, s.~2679-2694. ISSN~0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.3c04035.

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