Influence of active-site proximity in zeolites on Brønsted acid-catalyzed reactions at the microscopic and mesoscopic levels

Teng Li; Sang Ho Chung; Stefan Nastase; Adrian Galilea; Yan Wang; Ildar Mukhambetov; Moussa Zaarour; Juan Carlos Navarro de Miguel; Jurjen Cazemier; Abhay Dokania; Liliana Panarone; Jorge Gascon; Luigi Cavallo; Javier Ruiz-Martínez

doi:10.1016/j.checat.2023.100540

Influence of active-site proximity in zeolites on Brønsted acid-catalyzed reactions at the microscopic and mesoscopic levels

Teng Li, Sang Ho Chung, Stefan Nastase, Adrian Galilea, Yan Wang, Ildar Mukhambetov, Moussa Zaarour, Juan Carlos Navarro de Miguel, Jurjen Cazemier, Abhay Dokania, Liliana Panarone, Jorge Gascon, Luigi Cavallo, Javier Ruiz-Martínez^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

Zeolites are the catalytic workhorses of various relevant reactions, primarily because of their acidic properties. However, there have been few studies on unraveling the influence of Al distribution on acid-catalyzed reactions at the mesoscopic and microscopic levels. Taking the methanol-to-aromatics (MTA) process as a paradigm, we compared the catalytic performance of two H-ZSM-5 zeolites with comparable properties, except for Al distribution, i.e., intraparticle distribution and Al proximity at the nanoscale. Our results demonstrate that Al enrichment at positions closer to the external surface results in more paired acid sites that exhibit enhanced activity than the isolated ones. Moreover, such Al organization accelerates progression of cascade reactions to yield aromatics and alleviate their diffusion out. Exploiting this Al-zoning feature, we further fabricated hollow zeolites by desilication. Combining the optimized active sites with the improved diffusion and void-confinement properties of hollow crystals results in the highest capacity to produce aromatics.

Original language	English (US)
Article number	100540
Journal	Chem Catalysis
Volume	3
Issue number	6
DOIs	https://doi.org/10.1016/j.checat.2023.100540
State	Published - Jun 15 2023

Bibliographical note

Funding Information:
This work was supported by a baseline grant ( BAS/1/1402-01-01 ) and Competitive Research Grant ( URF/1/4391-01-01 ) from King Abdullah University of Science and Technology ( KAUST ). The authors gratefully thank Dr. Selvedin Telalovic for support in characterization and Dr. Youssef Saih for support in PID tests. We thank Ella Maru Studio for the scientific illustration of the graphical abstract.

Publisher Copyright:
© 2023 The Author(s)

Keywords

Al zoning
aluminum distribution
hollow zeolite
isolated acid sites
methanol to aromatics
paired acid sites
SDG9: Industry innovation and infrastructure
zeolite

ASJC Scopus subject areas

Chemistry (miscellaneous)
Physical and Theoretical Chemistry
Organic Chemistry

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10.1016/j.checat.2023.100540

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Li, T., Chung, S. H., Nastase, S., Galilea, A., Wang, Y., Mukhambetov, I., Zaarour, M., Navarro de Miguel, J. C., Cazemier, J., Dokania, A., Panarone, L., Gascon, J., Cavallo, L., & Ruiz-Martínez, J. (2023). Influence of active-site proximity in zeolites on Brønsted acid-catalyzed reactions at the microscopic and mesoscopic levels. Chem Catalysis, 3(6), Article 100540. https://doi.org/10.1016/j.checat.2023.100540

@article{56008eb7ea2848159ada92a376116d5b,

title = "Influence of active-site proximity in zeolites on Br{\o}nsted acid-catalyzed reactions at the microscopic and mesoscopic levels",

abstract = "Zeolites are the catalytic workhorses of various relevant reactions, primarily because of their acidic properties. However, there have been few studies on unraveling the influence of Al distribution on acid-catalyzed reactions at the mesoscopic and microscopic levels. Taking the methanol-to-aromatics (MTA) process as a paradigm, we compared the catalytic performance of two H-ZSM-5 zeolites with comparable properties, except for Al distribution, i.e., intraparticle distribution and Al proximity at the nanoscale. Our results demonstrate that Al enrichment at positions closer to the external surface results in more paired acid sites that exhibit enhanced activity than the isolated ones. Moreover, such Al organization accelerates progression of cascade reactions to yield aromatics and alleviate their diffusion out. Exploiting this Al-zoning feature, we further fabricated hollow zeolites by desilication. Combining the optimized active sites with the improved diffusion and void-confinement properties of hollow crystals results in the highest capacity to produce aromatics.",

keywords = "Al zoning, aluminum distribution, hollow zeolite, isolated acid sites, methanol to aromatics, paired acid sites, SDG9: Industry innovation and infrastructure, zeolite",

author = "Teng Li and Chung, {Sang Ho} and Stefan Nastase and Adrian Galilea and Yan Wang and Ildar Mukhambetov and Moussa Zaarour and {Navarro de Miguel}, {Juan Carlos} and Jurjen Cazemier and Abhay Dokania and Liliana Panarone and Jorge Gascon and Luigi Cavallo and Javier Ruiz-Mart{\'i}nez",

note = "Funding Information: This work was supported by a baseline grant ( BAS/1/1402-01-01 ) and Competitive Research Grant ( URF/1/4391-01-01 ) from King Abdullah University of Science and Technology ( KAUST ). The authors gratefully thank Dr. Selvedin Telalovic for support in characterization and Dr. Youssef Saih for support in PID tests. We thank Ella Maru Studio for the scientific illustration of the graphical abstract. Publisher Copyright: {\textcopyright} 2023 The Author(s)",

year = "2023",

month = jun,

day = "15",

doi = "10.1016/j.checat.2023.100540",

language = "English (US)",

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Li, T , Chung, SH , Nastase, S, Galilea, A, Wang, Y , Mukhambetov, I , Zaarour, M , Navarro de Miguel, JC , Cazemier, J, Dokania, A, Panarone, L, Gascon, J , Cavallo, L & Ruiz-Martínez, J 2023, 'Influence of active-site proximity in zeolites on Brønsted acid-catalyzed reactions at the microscopic and mesoscopic levels', Chem Catalysis, vol. 3, no. 6, 100540. https://doi.org/10.1016/j.checat.2023.100540

TY - JOUR

T1 - Influence of active-site proximity in zeolites on Brønsted acid-catalyzed reactions at the microscopic and mesoscopic levels

AU - Li, Teng

AU - Chung, Sang Ho

AU - Nastase, Stefan

AU - Galilea, Adrian

AU - Wang, Yan

AU - Mukhambetov, Ildar

AU - Zaarour, Moussa

AU - Navarro de Miguel, Juan Carlos

AU - Cazemier, Jurjen

AU - Dokania, Abhay

AU - Panarone, Liliana

AU - Gascon, Jorge

AU - Cavallo, Luigi

AU - Ruiz-Martínez, Javier

N1 - Funding Information: This work was supported by a baseline grant ( BAS/1/1402-01-01 ) and Competitive Research Grant ( URF/1/4391-01-01 ) from King Abdullah University of Science and Technology ( KAUST ). The authors gratefully thank Dr. Selvedin Telalovic for support in characterization and Dr. Youssef Saih for support in PID tests. We thank Ella Maru Studio for the scientific illustration of the graphical abstract. Publisher Copyright: © 2023 The Author(s)

PY - 2023/6/15

Y1 - 2023/6/15

N2 - Zeolites are the catalytic workhorses of various relevant reactions, primarily because of their acidic properties. However, there have been few studies on unraveling the influence of Al distribution on acid-catalyzed reactions at the mesoscopic and microscopic levels. Taking the methanol-to-aromatics (MTA) process as a paradigm, we compared the catalytic performance of two H-ZSM-5 zeolites with comparable properties, except for Al distribution, i.e., intraparticle distribution and Al proximity at the nanoscale. Our results demonstrate that Al enrichment at positions closer to the external surface results in more paired acid sites that exhibit enhanced activity than the isolated ones. Moreover, such Al organization accelerates progression of cascade reactions to yield aromatics and alleviate their diffusion out. Exploiting this Al-zoning feature, we further fabricated hollow zeolites by desilication. Combining the optimized active sites with the improved diffusion and void-confinement properties of hollow crystals results in the highest capacity to produce aromatics.

AB - Zeolites are the catalytic workhorses of various relevant reactions, primarily because of their acidic properties. However, there have been few studies on unraveling the influence of Al distribution on acid-catalyzed reactions at the mesoscopic and microscopic levels. Taking the methanol-to-aromatics (MTA) process as a paradigm, we compared the catalytic performance of two H-ZSM-5 zeolites with comparable properties, except for Al distribution, i.e., intraparticle distribution and Al proximity at the nanoscale. Our results demonstrate that Al enrichment at positions closer to the external surface results in more paired acid sites that exhibit enhanced activity than the isolated ones. Moreover, such Al organization accelerates progression of cascade reactions to yield aromatics and alleviate their diffusion out. Exploiting this Al-zoning feature, we further fabricated hollow zeolites by desilication. Combining the optimized active sites with the improved diffusion and void-confinement properties of hollow crystals results in the highest capacity to produce aromatics.

KW - Al zoning

KW - aluminum distribution

KW - hollow zeolite

KW - isolated acid sites

KW - methanol to aromatics

KW - paired acid sites

KW - SDG9: Industry innovation and infrastructure

KW - zeolite

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U2 - 10.1016/j.checat.2023.100540

DO - 10.1016/j.checat.2023.100540

M3 - Article

AN - SCOPUS:85150928273

SN - 2667-1107

VL - 3

JO - Chem Catalysis

JF - Chem Catalysis

IS - 6

M1 - 100540

ER -

Influence of active-site proximity in zeolites on Brønsted acid-catalyzed reactions at the microscopic and mesoscopic levels

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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