Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship

Luis A.  Gallego Villada; Päivi Mäki-Arvela; Narendra Kumar; Edwin A Alarcón; Zuzana Vajglova; Teija Tirri; Ilari Angervo; Robert Lassfolk; Mika Lastusaari; Dmitry Murzin

doi:10.1016/j.micromeso.2024.113098

Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship

Luis A. Gallego Villada^*
, Päivi Mäki-Arvela
, Narendra Kumar
, Edwin A Alarcón
, Zuzana Vajglova
, Teija Tirri
, Ilari Angervo
, Robert Lassfolk
, Mika Lastusaari
, Dmitry Murzin^*

^*Korresponderande författare för detta arbete

Forskningsoutput: Tidskriftsbidrag › Artikel › Vetenskaplig › Peer review

16 Citeringar (Scopus)

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Sammanfattning

Parent, hierarchical, and metal-modified hierarchical zeolite Y were investigated as heterogeneous catalysts in the R-(+)-limonene epoxidation, a catalytic route for synthesizing precursors of bio-polycarbonates, an alternative to isocyanate polyurethanes. The fresh catalysts underwent detailed characterization using XRD, N ₂ physisorption, TEM, SEM-EDX, pyridine-FTIR, NH ₃-TPD, CO ₂-TPD, UV–Vis-DRS, and solid-state NMR. Spent materials were investigated by TPO-MS and TGA, confirming low coke formation on the catalytic surface. The most active material was K–Sn-modified dealuminated zeolite Y, reflected in a high turnover frequency (TOF) of 96 h ⁻¹. This material exhibited the lowest Brønsted to Lewis acidity ratio (0.1), the highest mesoporosity fraction (43%), and the lowest total surface area (465 m ² g ⁻¹). Aprotic polar solvents with high polarity and medium donor capacity appeared suitable for limonene epoxidation. Limonene conversion of ca. 97% was reached at 70 °C, H ₂O ₂: limonene molar ratio = 7, and acetonitrile as a solvent, while selectivity to total monoepoxides exhibited values up to 96% under different reaction conditions. Hydration of internal epoxides to limonene diol was favored at high temperatures and high H ₂O ₂/limonene molar ratios. The efficiency of H ₂O ₂ reached maximum values of about 85% at low H ₂O ₂ amounts, while no significant influence was observed for temperature, catalyst amount, and the initial concentration of limonene. A plausible reaction mechanism was proposed for the R-(+)-limonene epoxidation with H ₂O ₂ based on the experimental findings.

Originalspråk	Amerikansk engelska
Artikelnummer	113098
Tidskrift	Microporous and Mesoporous Materials
Volym	372
Nummer	113098
DOI	https://doi.org/10.1016/j.micromeso.2024.113098
Status	Publicerad - 15 maj 2024
MoE-publikationstyp	A1 Tidskriftsartikel-refererad

Finansiering

The authors thank the Universidad de Antioquia for providing financial resources for this work through the project 2022–53000: “Transformation of monoterpenes through one-pot reactions over heterogeneous catalysts”, as part of the 2021–2022 Programmatic Call: Engineering and Technology. They also thank the Foundation for the Promotion of Research and Technology, project 2022–56550. Additionally, Luis A. Gallego-Villada is grateful to the Universidad de Antioquia for supporting his Ph.D. studies through the “Beca Doctoral Universidad de Antioquia” scholarship. The authors would like to express their gratitude to Dr. Julián Sánchez for his valuable advice on the reaction pathway. The authors thank the Universidad de Antioquia for providing financial resources for this work through the project 2022–53000 : “Transformation of monoterpenes through one-pot reactions over heterogeneous catalysts”, as part of the 2021–2022 Programmatic Call: Engineering and Technology. They also thank the Foundation for the Promotion of Research and Technology , project 2022–56550 . Additionally, Luis A. Gallego-Villada is grateful to the Universidad de Antioquia for supporting his Ph.D. studies through the “Beca Doctoral Universidad de Antioquia” scholarship.

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https://urn.fi/URN:NBN:fi-fe2024081264472

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Gallego Villada, L. A., Mäki-Arvela, P., Kumar, N., Alarcón, E. A., Vajglova, Z., Tirri, T., Angervo, I., Lassfolk, R., Lastusaari, M., & Murzin, D. (2024). Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship. Microporous and Mesoporous Materials, 372(113098), Artikel 113098. https://doi.org/10.1016/j.micromeso.2024.113098

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title = "Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship",

abstract = "Parent, hierarchical, and metal-modified hierarchical zeolite Y were investigated as heterogeneous catalysts in the R-(+)-limonene epoxidation, a catalytic route for synthesizing precursors of bio-polycarbonates, an alternative to isocyanate polyurethanes. The fresh catalysts underwent detailed characterization using XRD, N 2 physisorption, TEM, SEM-EDX, pyridine-FTIR, NH 3-TPD, CO 2-TPD, UV–Vis-DRS, and solid-state NMR. Spent materials were investigated by TPO-MS and TGA, confirming low coke formation on the catalytic surface. The most active material was K–Sn-modified dealuminated zeolite Y, reflected in a high turnover frequency (TOF) of 96 h −1. This material exhibited the lowest Br{\o}nsted to Lewis acidity ratio (0.1), the highest mesoporosity fraction (43\%), and the lowest total surface area (465 m 2 g −1). Aprotic polar solvents with high polarity and medium donor capacity appeared suitable for limonene epoxidation. Limonene conversion of ca. 97\% was reached at 70 °C, H 2O 2: limonene molar ratio = 7, and acetonitrile as a solvent, while selectivity to total monoepoxides exhibited values up to 96\% under different reaction conditions. Hydration of internal epoxides to limonene diol was favored at high temperatures and high H 2O 2/limonene molar ratios. The efficiency of H 2O 2 reached maximum values of about 85\% at low H 2O 2 amounts, while no significant influence was observed for temperature, catalyst amount, and the initial concentration of limonene. A plausible reaction mechanism was proposed for the R-(+)-limonene epoxidation with H 2O 2 based on the experimental findings.",

author = "\{Gallego Villada\}, \{Luis A.\} and P{\"a}ivi M{\"a}ki-Arvela and Narendra Kumar and Alarc{\'o}n, \{Edwin A\} and Zuzana Vajglova and Teija Tirri and Ilari Angervo and Robert Lassfolk and Mika Lastusaari and Dmitry Murzin",

year = "2024",

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doi = "10.1016/j.micromeso.2024.113098",

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Gallego Villada, LA , Mäki-Arvela, P , Kumar, N, Alarcón, EA, Vajglova, Z, Tirri, T, Angervo, I, Lassfolk, R, Lastusaari, M & Murzin, D 2024, 'Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship', Microporous and Mesoporous Materials, vol. 372, nr. 113098, 113098. https://doi.org/10.1016/j.micromeso.2024.113098

TY - JOUR

T1 - Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship

AU - Gallego Villada, Luis A.

AU - Mäki-Arvela, Päivi

AU - Kumar, Narendra

AU - Alarcón, Edwin A

AU - Vajglova, Zuzana

AU - Tirri, Teija

AU - Angervo, Ilari

AU - Lassfolk, Robert

AU - Lastusaari, Mika

AU - Murzin, Dmitry

PY - 2024/5/15

Y1 - 2024/5/15

N2 - Parent, hierarchical, and metal-modified hierarchical zeolite Y were investigated as heterogeneous catalysts in the R-(+)-limonene epoxidation, a catalytic route for synthesizing precursors of bio-polycarbonates, an alternative to isocyanate polyurethanes. The fresh catalysts underwent detailed characterization using XRD, N 2 physisorption, TEM, SEM-EDX, pyridine-FTIR, NH 3-TPD, CO 2-TPD, UV–Vis-DRS, and solid-state NMR. Spent materials were investigated by TPO-MS and TGA, confirming low coke formation on the catalytic surface. The most active material was K–Sn-modified dealuminated zeolite Y, reflected in a high turnover frequency (TOF) of 96 h −1. This material exhibited the lowest Brønsted to Lewis acidity ratio (0.1), the highest mesoporosity fraction (43%), and the lowest total surface area (465 m 2 g −1). Aprotic polar solvents with high polarity and medium donor capacity appeared suitable for limonene epoxidation. Limonene conversion of ca. 97% was reached at 70 °C, H 2O 2: limonene molar ratio = 7, and acetonitrile as a solvent, while selectivity to total monoepoxides exhibited values up to 96% under different reaction conditions. Hydration of internal epoxides to limonene diol was favored at high temperatures and high H 2O 2/limonene molar ratios. The efficiency of H 2O 2 reached maximum values of about 85% at low H 2O 2 amounts, while no significant influence was observed for temperature, catalyst amount, and the initial concentration of limonene. A plausible reaction mechanism was proposed for the R-(+)-limonene epoxidation with H 2O 2 based on the experimental findings.

AB - Parent, hierarchical, and metal-modified hierarchical zeolite Y were investigated as heterogeneous catalysts in the R-(+)-limonene epoxidation, a catalytic route for synthesizing precursors of bio-polycarbonates, an alternative to isocyanate polyurethanes. The fresh catalysts underwent detailed characterization using XRD, N 2 physisorption, TEM, SEM-EDX, pyridine-FTIR, NH 3-TPD, CO 2-TPD, UV–Vis-DRS, and solid-state NMR. Spent materials were investigated by TPO-MS and TGA, confirming low coke formation on the catalytic surface. The most active material was K–Sn-modified dealuminated zeolite Y, reflected in a high turnover frequency (TOF) of 96 h −1. This material exhibited the lowest Brønsted to Lewis acidity ratio (0.1), the highest mesoporosity fraction (43%), and the lowest total surface area (465 m 2 g −1). Aprotic polar solvents with high polarity and medium donor capacity appeared suitable for limonene epoxidation. Limonene conversion of ca. 97% was reached at 70 °C, H 2O 2: limonene molar ratio = 7, and acetonitrile as a solvent, while selectivity to total monoepoxides exhibited values up to 96% under different reaction conditions. Hydration of internal epoxides to limonene diol was favored at high temperatures and high H 2O 2/limonene molar ratios. The efficiency of H 2O 2 reached maximum values of about 85% at low H 2O 2 amounts, while no significant influence was observed for temperature, catalyst amount, and the initial concentration of limonene. A plausible reaction mechanism was proposed for the R-(+)-limonene epoxidation with H 2O 2 based on the experimental findings.

U2 - 10.1016/j.micromeso.2024.113098

DO - 10.1016/j.micromeso.2024.113098

M3 - Artikel

SN - 1387-1811

VL - 372

JO - Microporous and Mesoporous Materials

JF - Microporous and Mesoporous Materials

IS - 113098

M1 - 113098

ER -

Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship

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