Unveiling the mechanisms of carboxylic acid esterification on acid zeolites for biomass-to-energy: A review of the catalytic process through experimental and computational studies

Gomes, Glaucio José; Zalazar, María Fernanda; Padilha, Janine Carvalho; Costa, Michelle Budke; Bazzi, Claudio Leones; Arroyo, Pedro Augusto

doi:10.1016/j.chemosphere.2023.140879

Cited by 5 publications

(3 citation statements)

References 194 publications

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“…A previous kinetic study suggested that the esterification mechanism proceeds through a surface AA/ethanol coadsorbed complex, where adsorption of both reactants should be involved in the rate-determining reaction step . Subsequent studies combining Thermogravimetric analysis coupled with Fourier Transform Infrared (TG-FTIR) spectroscopy, Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, and density functional theory (DFT) showed that the adsorption of the carboxylic acid on the BAS in a single step is crucial to determine the reaction mechanism on tridimensional zeolites. , A comprehensive review was recently published, which reinforces the need for an in-depth study of acid adsorption in order to gain a better understanding of the mechanism involved in this reaction . Furthermore, a molecular-level understanding of the interactions between the reactants and the catalyst surface is critical for a rational catalyst design.…”

Section: Introductionmentioning

confidence: 99%

“…22,23 A comprehensive review was recently published, which reinforces the need for an in-depth study of acid adsorption in order to gain a better understanding of the mechanism involved in this reaction. 19 Furthermore, a molecular-level understanding of the interactions between the reactants and the catalyst surface is critical for a rational catalyst design. In summary, a comprehensive understanding of the adsorption modes of adsorbates within zeolites and their interactions with the catalytic site is essential for unraveling the underlying mechanisms of these processes and exploring the potential applications of zeolites.…”

Section: Introductionmentioning

confidence: 99%

“…Current research focuses on the uses of solid Bro̷nsted acid catalysts for the esterification of carboxylic acids, with the aim of exploring different reaction mechanisms. − Heterogeneous acid catalysis on zeolites takes place at the solid−gas or solid−liquid phase interface. This involves a variety of acidic sites and restricted empty spaces within the zeolite framework.…”

Section: Introductionmentioning

confidence: 99%

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Comparative Study of Adsorbed Complexes inside Pores and Cavities of Acid Zeolites with Different Topology: Experimental and Theoretical Insights into Confinement Effects

Romero Ojeda,

Gomes,

Bittencourt

et al. 2024

J. Phys. Chem. C

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The distinctive topology of pores and cavities of zeolites plays a key role in several applications including catalysis, adsorption, and ion exchange, where confinement effects are significant and can affect the selectivity, stability, and reactivity of catalytic processes. In this study, the effect of confinement on the adsorption of acetic acid on zeolites H-ZSM-5, H-Beta, H-Y, and H-MOR was evaluated by means of thermogravimetric analysis coupled with Fourier Transform Infrared (TG-FTIR) spectroscopy and density functional calculations, including electron density analysis by quantum theory of atoms in molecules. The catalysts were characterized using X-ray powder diffraction (XRD), attenuated total reflection (ATR), and Fourier transform infrared (FTIR) spectroscopy of adsorbed Pyridine (FTIR-Py). TG-FTIR for the first mass loss process, adsorption energy calculations, and electron density results show that the strength of the adsorption of acetic acid between the different acidic zeolites decreases in the order of H-MOR > H-ZSM-5 > H-Beta > H−Y. Adsorption of acetic acid within H-ZSM-5 and H-MOR allows to maximize the interactions with the zeolite framework and thus the confinement, resulting in an additional stabilization in the adsorption process. In contrast, for H-Beta and H−Y zeolites, the confinement effect on the acetic acid molecule is small, and the adsorption energy is mostly related to the interactions at the active site (BAS and basic site).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Comparative Study of Adsorbed Complexes inside Pores and Cavities of Acid Zeolites with Different Topology: Experimental and Theoretical Insights into Confinement Effects

Romero Ojeda,

Gomes,

Bittencourt

et al. 2024

J. Phys. Chem. C

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Porous Materials for the Heterogeneously Catalyzed Synthesis of High Value‐Added Products: Latest Trends and Future Prospects

Sanoja‐López,

Luque

2024

Chemistry An Asian Journal

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Heterogeneous catalysis currently stands as a foundational area in materials synthesis and applied chemistry. In this context, emphasizing the significance of heterogeneous catalysis in expediting chemical reactions and controlling the formation of desired products using porous materials represents an intriguing approach in the current technological landscape. This work delves into the synthesis and design of a variety of porous materials, encompassing microporous, mesoporous and macroporous materials (e.g. carbonaceous materials, metal oxides, MOFs, zeolites and functionalized analogues), alongside their properties and characteristics pivotal in heterogeneous catalysis. among others, and their subsequent modification, underscoring the significance of tailoring porous materials for specific catalytic applications.

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Revealing the Mechanism of Ketonization of Acetic Acid on HBEA Zeolite via Metadynamics Simulations

Liu,

Zhao,

Liu

et al. 2024

ChemCatChem

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Ketonization of biomass‐derived carboxylic acids offers a promising approach to remove oxygen and upgrade into valuable chemicals. However, the mechanism on Brønsted acid site (BAS) confined in micropores of zeolite remains elusive, due to the difficulty to observe the reaction intermediates experimentally and to locate the transition state via static density functional theory (DFT) calculations. Herein, ketonization of acetic acid on HBEA at 673 K was studied by metadynamics simulations based on DFT. The first reaction step was the concerted protonation and dehydroxylation of acetic acid, resulting in an electrophilic acylium cation and H2O (ΔG‡ = 1.53 eV). The subsequent likely steps, including C‐C coupling through the nucleophilic attack of acetic acid (path I), ketene (path II), and 1,1‐dihydroxyethene and (path III) toward acylium cation were tracked and compared. The high barriers for formation of more nucleophilic intermediates of ketene and 1,1‐dihydroxyethene made the overall path II and III less favorable than the direct coupling between acetic acid and acylium cation (path I, ΔG‡ = 2.15 eV). These results indicate that acylium cation is a key intermediate, and the C‐C coupling between acetic acid and acylium cation via nucleophilic attach is the most favorable path on BAS confined in zeolite.

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Unveiling the mechanisms of carboxylic acid esterification on acid zeolites for biomass-to-energy: A review of the catalytic process through experimental and computational studies

Cited by 5 publications

References 194 publications

Comparative Study of Adsorbed Complexes inside Pores and Cavities of Acid Zeolites with Different Topology: Experimental and Theoretical Insights into Confinement Effects

Comparative Study of Adsorbed Complexes inside Pores and Cavities of Acid Zeolites with Different Topology: Experimental and Theoretical Insights into Confinement Effects

Porous Materials for the Heterogeneously Catalyzed Synthesis of High Value‐Added Products: Latest Trends and Future Prospects

Revealing the Mechanism of Ketonization of Acetic Acid on HBEA Zeolite via Metadynamics Simulations

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