The Effects of Functional Groups and Missing Linkers on the Adsorption Capacity of Aromatic Hydrocarbons in UiO-66 Thin Films

The adsorption of benzene, toluene, ethylbenzene, and xylene isomers, also known as BTEX, from the gas phase into porous thin films of the metal–organic framework UiO-66-X, where X = H, NH2, and NO2, was measured to quantify adsorption capacity. The thin films were grown by a vapor-conversion method onto Au-coated quartz microbalance crystals. The MOF thin films were characterized by IR and Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The thin films were activated by heating under high vacuum and exposed to each gas to calculate the Henry’s constant. The results demonstrate that the functional groups in the organic linker and missing-linkers both play important roles in the adsorption capacity. Several trends can be observed in the data. First, all the compounds in the BTEX family have lower Henry’s constants in the UiO-66-H films compared to the UiO-66-NH2 and UiO-66-NO2 films, which can largely be attributed to the absence of a functional group on the linker. Second, at 25 °C, the Henry’s constants for all the BTEX compounds in UiO-66-NO2 films are larger than UiO-66-NH2 films. Third, the role of missing linkers is addressed by comparing the measured adsorption capacity to ideal pore filling. The results show that the UiO-66-H films are the most defect-free and the UiO-66-NO2 films have the most missing linker defects.

Ionic Liquids/Deep Eutectic Solvents-Based Hybrid Solvents for CO2 Capture

The CO2 solubilities (including CO2 Henry’s constants) and viscosities in ionic liquids (ILs)/deep eutectic solvents (DESs)-based hybrid solvents were comprehensively collected and summarized. The literature survey results of CO2 solubility illustrated that the addition of hybrid solvents to ILs/DESs can significantly enhance the CO2 solubility, and some of the ILs-based hybrid solvents are super to DESs-based hybrid solvents. The best hybrid solvents of IL–H2O, IL–organic, IL–amine, DES–H2O, and DES–organic are [DMAPAH][Formate] (2.5:1) + H2O (20 wt %) (4.61 mol/kg, 298 K, 0.1 MPa), [P4444][Pro] + PEG400 (70 wt %) (1.61 mol/kg, 333.15 K, 1.68 MPa), [DMAPAH][Formate] (2.0:1) + MEA (30 wt %) (6.24 mol/kg, 298 K, 0.1 MPa), [TEMA][Cl]-GLY-H2O 1:2:0.11 (0.66 mol/kg, 298 K, 1.74 MPa), and [Ch][Cl]-MEA 1:2 + DBN 1:1 (5.11 mol/kg, 298 K, 0.1 MPa), respectively. All of these best candidates show higher CO2 solubility than their used pure ILs or DESs, evidencing that IL/DES-based hybrid solvents are remarkable for CO2 capture. For the summarized viscosity results, the presence of hybrid solvents in ILs and DESs can decrease their viscosities. The lowest viscosities acquired in this work for IL–H2O, IL–amine, DES–H2O, and DES–organic hybrid solvents are [DEA][Bu] + H2O (98.78 mol%) (0.59 mPa·s, 343.15 K), [BMIM][BF4] + DETA (94.9 mol%) (2.68 mPa·s, 333.15 K), [L-Arg]-GLY 1:6 + H2O (60 wt %) (2.7 mPa·s, 353.15 K), and [MTPP][Br]-LEV-Ac 1:3:0.03 (16.16 mPa·s, 333.15 K) at 0.1 MPa, respectively.

Mathematical description of ethylamine sorption from air by fibrous cation exchangers under conditions of limited sorbate permeability

A mathematical model for description of the sorption capacity of ion exchangers on alkaline compounds protonizable in aqueous solutions (exemplified by ammonia, mono-, diand triethylamine) was proposed. The Henry’s constants for these substances were experimentally determined. The model accounts for the concentration and acid-base properties of the sorbate, relative air humidity, acid-base properties and exchange capacity of the ion exchanger, as well as spatial availability of functional groups for interaction under conditions of limited permeability of polymeric ion exchanger. The applicability of the model is illustrated by processing the experimental results on the sorption of ammonia and ethylamines by fibrous carboxylic and sulfonic cation exchangers. Good agreement between the calculated and experimental data is observed.

Distribution of ammonia, mono-, di- and triethylamine in the water solution–gas phase system.

The equilibrium distribution of ammonia, ethylamine, diethylamine and triethylamine between their aqueous solutions and the gas phase at 25 ± 0.1 °C have been investigated under equilibrium conditions. Based on the results obtained (using the equations of Henry’s law and the ionization constant), Henry’s constants for these substances have been calculated with the consideration of their interaction with water. It was established that Henry’s law is valid, at least, in the range of amine concentrations in the air 0–200 mg/m3.