Theoretical study on the mechanism of oxidative–extractive desulfurization in imidazolium-based ionic liquid

Yuan, Penghui; Zhang, T. T.; Cai, Aofei; Cui, Chunsheng; Liu, He‐Yang; Bao, Xiao Jun

doi:10.1039/c6ra16731d

Cited by 5 publications

(3 citation statements)

References 42 publications

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“…ILs can possibly decrease the energy barrier associated with the oxidation of Th and thus are highly useful compared to the usual solvents like acetonitrile. 219 The multiple roles of ILs in desulfurization can be better understood from earlier reviews. 220 Oxidants leaving no unwanted side-products are more preferable for the catalytic ODS.…”

Section: Solvent and Oxidantmentioning

confidence: 99%

A comprehensive review on oxidative desulfurization catalysts targeting clean energy and environment

et al. 2020

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Section: Solvent and Oxidantmentioning

confidence: 99%

A comprehensive review on oxidative desulfurization catalysts targeting clean energy and environment

et al. 2020

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“…Computational simulations have been utilized extensively to aid in the discovery of high-performance IL/DES-based extractants for sulfur removal. , Multiple theoretical methods have been applied to investigate interactions between IL/DESs and sulfur compounds, predict the properties of IL/DESs-sulfur mixtures, and assist in the design and screening of different IL/DESs for extraction desulfurization. For example, computational methods that include the conductor-like screening model for realistic solvents (COSMO-RS), − quantum mechanics, , molecular dynamics (MD), , and Monte Carlo (MC) have provided significant insights into the desulfurization process. In this work, MD simulations have been performed to elucidate the intermolecular interactions responsible for the efficient extraction of the TS, DBT, and MDBT sulfur compounds (Scheme ) using five different imidazolium-based ILs and two unique DESs.…”

Section: Introductionmentioning

confidence: 99%

Uncovering the Critical Factors that Enable Extractive Desulfurization of Fuels in Ionic Liquids and Deep Eutectic Solvents from Simulations

Yue

Acevedo

2023

J. Phys. Chem. B

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Environmental regulatory agencies have implemented stringent restrictions on the permissible levels of sulfur compounds in fuel to reduce harmful emissions and improve air quality. Problematically, traditional desulfurization methods have shown low effectiveness in the removal of refractory sulfur compounds, e.g., thiophene (TS), dibenzothiophene (DBT), and 4-methyldibenzothiophene (MDBT). In this work, molecular dynamics (MD) simulations and free energy perturbation (FEP) have been applied to investigate the use of ionic liquids (ILs) and deep eutectic solvents (DESs) as efficient TS/DBT/MDBT extractants. For the IL simulations, the selected cation was 1-butyl-3methylimidazolium [BMIM] and the anions included chloride [Cl], thiocyanate [SCN], tetrafluoroborate [BF 4 ], hexafluorophosphate [PF 6 ], and bis-(trifluoromethylsulfonyl)amide [NTf 2 ]. The DESs were composed of choline chloride with ethylene glycol (CCEtg) or with glycerol (CCGly). Calculation of excess chemical potentials predicted the ILs to be more promising extractants with energies lower by 1−3 kcal/mol compared to DESs. Increasing IL anion size was positively correlated to enhanced solvation of S-compounds, which was influenced by energetically dominant solute−anion interactions and favorable solute-[BMIM] π−π stacking. For the DESs, the solvent components offered a range of synergistic, yet comparatively weaker, electrostatic interactions that included hydrogen bonding and cation−π interactions. An in-depth analysis of the structure of IL and DES systems is presented, along with a discussion of the critical factors behind experimental trends of S-compound extraction efficiency.

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“…With the increasing pursuit of greener and more sustainable chemistry in recent years, the significant contribution of ionic liquids (ILs) to organic synthesis by improving the reaction environment and reaction rate has become indispensable. − ILs not only exhibit an outstanding performance as an extractive agent or solvent , but also play an important role in creating mild reaction conditions by dramatically decreasing the reaction energy barrier such as in cycloaddition, − desulfurization, − and esterification , reactions.…”

Section: Introductionmentioning

confidence: 99%

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

Yan

Huo

et al. 2022

ACS Sustainable Chem. Eng.

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By density functional theory (DFT), we report a detailed mechanistic study on the synthesis of methylacrolein (MAL) by a mild Mannich reaction of formaldehyde (FA) and propionaldehyde (PA) catalyzed by sec-amine short-chain aliphatic acid ionic liquids (ILs). ILs exhibit excellent catalytic activity and create mild reaction conditions (45 °C) by dramatically decreasing the reaction energy barrier (24.43 kcal mol −1 ) in the decomposition step of Mannich bases (MBs) comapred to without ILs. Three key intermediates observed by DFT calcutations were identified by electron spray ionization mass spectrometry (ESI-MS) analysis. We systematically investigated the catalytic effect of ILs with different sec-amines (HNR 2 , R = CH 3 , C 2 H 5 , etc.) on the activation energy and different short-chain aliphatic acids (RCOOH, R= H, CH 3 et al.) on the decomposition step of MBs. This work is intended to provide a thorough explanation of the synthesis mechanism of the mild Mannich reaction of MAL catalyzed by ILs from the theoretical aspect, which may give a favorable guidance for the practical application.

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Theoretical study on the mechanism of oxidative–extractive desulfurization in imidazolium-based ionic liquid

Abstract: The oxidation of TH to SP by H2O2 with the assistance of IL experiences two steps via two transition states.

Cited by 5 publications

References 42 publications

A comprehensive review on oxidative desulfurization catalysts targeting clean energy and environment

A comprehensive review on oxidative desulfurization catalysts targeting clean energy and environment

Uncovering the Critical Factors that Enable Extractive Desulfurization of Fuels in Ionic Liquids and Deep Eutectic Solvents from Simulations

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

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