Theoretical insights into CO2/N2 selectivity of the porous ionic liquids constructed by ion-dipole interactions

Yin, Jie; Zhang, Jinrui; Wang, Chao; Lv, Naixia; Jiang, Wei; Liu, Hui; Li, Hongping; Zhu, Wenshuai; Ji, Hongbing

doi:10.1016/j.molliq.2021.117676

Cited by 27 publications

(12 citation statements)

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“…Electrostatic potential analysis is an effective method to determine the interaction sites among molecules. , As depicted in Figure , the surface of Br and O was rich in electrons and could interact with electron-deficient H atoms through hydrogen bonds. Based on the plots in Figure c,d, four representative conformations were selected for optimization (Figure S1).…”

Section: Results and Discussionmentioning

confidence: 99%

Rational Design of Caprolactam-Based Deep Eutectic Solvents for Extractive Desulfurization of Diesel Fuel and Mechanism Study

Yin

Luo

et al. 2022

ACS Sustainable Chem. Eng.

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Deep eutectic solvents (DESs) are considered novel alternatives compared to organic solvents and ionic liquids. However, the low extractive efficiency of fuel oil has limited its wide application in desulfurization of diesel fuel. In this work, a series of caprolactam-based DESs were prepared using caprolactam as a hydrogen bond donor (HBD) and tetrabutylammonium halides as hydrogen bond acceptors (HBAs). By screening different halide anions and molar ratios of HBD and HBA, the DES tetrabutylammonium bromide/caprolactam (TBAB/CPL = 1:2) showed the highest desulfurization efficiency with the Nernst partition coefficient of 5.04, which was much higher than those of most metal-free DESs and ILs. The desulfurization efficiency could reach as high as 96.6% after a two-stage extraction. Finally, the extraction mechanism was investigated systematically using 1H nuclear magnetic resonance and Fourier transform infrared spectroscopies. Then, a density functional theory study suggested that hydrogen bonding and C–H···π interaction between DES and dibenzothiophene accounted for the higher desulfurization efficiency, enabling DES to effectively remove dibenzothiophene from the model fuels.

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Section: Results and Discussionmentioning

confidence: 99%

Rational Design of Caprolactam-Based Deep Eutectic Solvents for Extractive Desulfurization of Diesel Fuel and Mechanism Study

Yin

Luo

et al. 2022

ACS Sustainable Chem. Eng.

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“…The electrostatic potential analysis is an effective tool to predict the interaction sites [39]. The electrostatic potential is one of the important physical properties of molecules that defines the work carried out to move a unit positive charge from infinity to a point in space around the molecule [40]. As many atoms constitute a molecule, the molecular charge distribution is no longer uniform but has positive and negative potential regions due to the difference in electronegativity of individual atoms [41].…”

Section: Speciesmentioning

confidence: 99%

Ag Atom Anchored on Defective Hexagonal Boron Nitride Nanosheets As Single Atom Adsorbents for Enhanced Adsorptive Desulfurization via S-Ag Bonds

et al. 2022

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Single atom adsorbents (SAAs) are a novel class of materials that have great potential in various fields, especially in the field of adsorptive desulfurization. However, it is still challenging to gain a fundamental understanding of the complicated behaviors on SAAs for adsorbing thiophenic compounds, such as 1-Benzothiophene (BT), Dibenzothiophene (DBT), and 4,6-Dimethyldibenzothiophene (4,6-DMDBT). Herein, we investigated the mechanisms of adsorptive desulfurization over a single Ag atom supported on defective hexagonal boron nitride nanosheets via density functional theory calculations. The Ag atom can be anchored onto three typical sites on the pristine h-BN, including the monoatomic defect vacancy (B-vacancy and N-vacancy) and the boron-nitrogen diatomic defect vacancy (B-N-divacancy). These three Ag-doped hexagonal boron nitride nanosheets all exhibit enhanced adsorption capacity for thiophenic compounds primarily by the S-Ag bond with π-π interaction maintaining. Furthermore, from the perspective of interaction energy, all three SAAs show a high selectivity to 4,6-DMDBT with the strong interaction energy (−33.9 kcal mol−1, −29.1 kcal mol−1, and −39.2 kcal mol−1, respectively). Notably, a little charge transfer demonstrated that the dominant driving force of such S-Ag bond is electrostatic interaction rather than coordination effect. These findings may shed light on the principles for modeling and designing high-performance and selective SAAs for adsorptive desulfurization.

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“…Therefore, computational methods such as DFT and classical MD simulations provide the atomic scale resolution necessary to identify different binding sites and their relatively stability in PL systems. For example, six unique binding sites were identified via DFT simulations of CO 2 binding in a POC + crown-ether Type 2 PL, including inside the pore, on the surface of the porous host, in the pore widow, along the vertex of the POC, between the POC and the solvent, and between two solvent molecules Figure includes snapshots of these representative CO 2 binding sites.…”

Section: Gas Adsorption Propertiesmentioning

confidence: 99%

“…Optimized configurations for 18-C-6 PL adsorbing CO 2 lies (a) between the crown and the cage, (b) at the widow, (c) inside the cage, and (d) outside the cation. Reproduced with permission from ref (2021, Elsevier).…”

Section: Gas Adsorption Propertiesmentioning

confidence: 99%

“…Creation and design of a PL with the highly tuned gas capture properties requires fundamental and mechanistic understanding of gas adsorption, binding, and selectivity that can be transformed through the application of computational methods. Significant work has already been initiated on the use of computational methods for analysis of PLs, including DFT ,,,, and classical MD simulations ,,,, for identification of binding sites and energies. A challenge here is the ability to model increasingly complex PL compositions with sufficient fidelity to identify the mechanisms of gas capture.…”

Section: Future Needs and Research Directionsmentioning

confidence: 99%

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Porous Liquids: Computational Design for Targeted Gas Adsorption

Rimsza

Nenoff

2022

ACS Appl. Mater. Interfaces

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In this Perspective, we present the unique gas adsorption capabilities of porous liquids (PLs) and the value of complex computational methods in the design of PL compositions. Traditionally, liquids only contain transient pore space between molecules that limit long-term gas capture. However, PLs are stable fluids that that contain permanent porosity due to the combination of a rigid porous host structure and a solvent. PLs exhibit remarkable adsorption and separation properties, including increased solubility and selectivity. The unique gas adsorption properties of PLs are based on their structure, which exhibits multiple gas binding sites in the pore and on the cage surface, varying binding mechanisms including hydrogen-bonding and π–π interactions, and selective diffusion in the solvent. Tunable PL compositions will require fundamental investigations of competitive gas binding mechanisms, thermal effects on binding site stability, and the role of nanoconfinement on gas and solvent diffusion that can be accelerated through molecular modeling. With these new insights PLs promise to be an exceptional material class with tunable properties for targeted gas adsorption.

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Theoretical insights into CO2/N2 selectivity of the porous ionic liquids constructed by ion-dipole interactions

Cited by 27 publications

References 50 publications

Rational Design of Caprolactam-Based Deep Eutectic Solvents for Extractive Desulfurization of Diesel Fuel and Mechanism Study

Rational Design of Caprolactam-Based Deep Eutectic Solvents for Extractive Desulfurization of Diesel Fuel and Mechanism Study

Ag Atom Anchored on Defective Hexagonal Boron Nitride Nanosheets As Single Atom Adsorbents for Enhanced Adsorptive Desulfurization via S-Ag Bonds

Porous Liquids: Computational Design for Targeted Gas Adsorption

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