Nanosponge hierarchical micro-mesoporous MFI zeolites as a high-performance catalyst for the hydroamination of methyl acrylate with aniline

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F22%3A10453373" target="_blank" >RIV/00216208:11310/22:10453373 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=swM9k3lmhO" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=swM9k3lmhO</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.micromeso.2022.112087" target="_blank" >10.1016/j.micromeso.2022.112087</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Nanosponge hierarchical micro-mesoporous MFI zeolites as a high-performance catalyst for the hydroamination of methyl acrylate with aniline

Popis výsledku v původním jazyce

Zeolites catalyze the hydroamination of alkenes, alkynes and dienes, yielding valuable amines, enamines and imines with high efficiency and chemoselectivity (i.e., Markovnikov or anti-Markovnikov products) thanks to the architecture of their pore system and tunable acidity. However, their micropores may impose mass-transfer constraints on reaction rates. Nevertheless, the high external surface area of hierarchical micro-mesoporous zeolites should enable them to outperform conventional zeolites. To test our hypothesis, we compared the activity of hierarchical MFI zeolites of different crystal morphologies (i.e., nanosponge, nanosheet and microcrystalline desilicated samples) with that of conventional medium- (MFI) and large-pore (MOR and Beta) zeolites in the hydroamination of methyl acrylate with aniline. The results showed that nanosponge MFI had the highest activity (TOF = 32.9 h(-1)), reaching 57% yield of the anti-Markovnikov product N-[2-(methoxycarbonyl)ethyl] aniline. Furthermore, our kinetic study revealed a pseudo-second-order rate law with respect to aniline over the most active nanosponge MFI catalyst, with an apparent activation energy of 68.9 kJ/mol. The high external surface of this catalyst (371 m2/g) and its developed inter-crystalline mesopores (4.8 nm) suggest a kineticdriven hydroamination reaction. Therefore, hierarchical nanosponge aluminosilicate MFI zeolites stand out as promising heterogeneous catalysts of hydroamination reactions involving bulky substrates.

Název v anglickém jazyce

Nanosponge hierarchical micro-mesoporous MFI zeolites as a high-performance catalyst for the hydroamination of methyl acrylate with aniline

Popis výsledku anglicky

Zeolites catalyze the hydroamination of alkenes, alkynes and dienes, yielding valuable amines, enamines and imines with high efficiency and chemoselectivity (i.e., Markovnikov or anti-Markovnikov products) thanks to the architecture of their pore system and tunable acidity. However, their micropores may impose mass-transfer constraints on reaction rates. Nevertheless, the high external surface area of hierarchical micro-mesoporous zeolites should enable them to outperform conventional zeolites. To test our hypothesis, we compared the activity of hierarchical MFI zeolites of different crystal morphologies (i.e., nanosponge, nanosheet and microcrystalline desilicated samples) with that of conventional medium- (MFI) and large-pore (MOR and Beta) zeolites in the hydroamination of methyl acrylate with aniline. The results showed that nanosponge MFI had the highest activity (TOF = 32.9 h(-1)), reaching 57% yield of the anti-Markovnikov product N-[2-(methoxycarbonyl)ethyl] aniline. Furthermore, our kinetic study revealed a pseudo-second-order rate law with respect to aniline over the most active nanosponge MFI catalyst, with an apparent activation energy of 68.9 kJ/mol. The high external surface of this catalyst (371 m2/g) and its developed inter-crystalline mesopores (4.8 nm) suggest a kineticdriven hydroamination reaction. Therefore, hierarchical nanosponge aluminosilicate MFI zeolites stand out as promising heterogeneous catalysts of hydroamination reactions involving bulky substrates.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Microporous and Mesoporous Materials

ISSN

1387-1811

e-ISSN

1873-3093

Svazek periodika

341

Číslo periodika v rámci svazku

August

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

11

Strana od-do

112087

Kód UT WoS článku

000830080100002

EID výsledku v databázi Scopus

2-s2.0-85133589822