Optimizing Trace Acetylene Removal from Acetylene/Ethylene Mixture in a Flexible Metal-Organic Framework by Crystal Downsizing.

Improving the gas separation performance of metal-organic frameworks (MOFs) by crystal downsizing is an important but often overlooked issue. Here, we report three different-sized flexible ZUL-520 MOFs (according to the crystal size from large to small, the three samples are, respectively, named ZUL-520-0, ZUL-520-1, and ZUL-520-2) with the same chemical structure for optimizing trace acetylene (C2H2) removal from acetylene/ethylene (C2H2/C2H4) mixture. The three differently sized activated ZUL-520 (denoted as ZUL-520a) exhibited almost identical C2H2 uptake of 4.8 mmol/g at 100 kPa, while the C2H2 uptake at 1 kPa increased with a downsizing crystal. The C2H2 uptake of activated ZUL-520-2 (denoted as ZUL-520-2a) at 1 kPa was ∼55% higher than that of activated ZUL-520-0 (denoted as ZUL-520-0a). The adsorption isotherms and adsorption kinetics validated that gas adsorptive separation is governed not only by adsorption thermodynamics but also by adsorption kinetics. In addition, all three different-sized ZUL-520a MOFs showed high C2H2/C2H4 selectivity. Grand canonical Monte Carlo (GCMC) simulations and dispersion-corrected density functional theory (DFT-D) computations illustrated a plausible mechanism of C2H2 adsorption in MOFs. Importantly, breakthrough experiments demonstrated that ZUL-520a can effectively separate the C2H2/C2H4 (1/99, v/v) mixture and the C2H4 productivity obtained by ZUL-520-2a was much higher than that by ZUL-520-0a. Our work may provide an easy but powerful strategy for upgrading the performance of gas adsorptive separation in MOFs.

Supramolecular Assembly of One-Dimensional Coordination Polymers for Efficient Separation of Xenon and Krypton.

Efficient separation and purification of xenon (Xe) from krypton (Kr) represent an industrially crucial but challenging process. While the adsorption-based separation of these atomic gases represents an energy-efficient process, achieving highly selective adsorbents remains a difficult task. Here, we demonstrate a supramolecular assembly of coordination polymers, termed as M(II)-dhbq (M = Mg, Mn, Co, and Zn; dhbq = 2,5-dihydroxy-1,4-benzoquinone), with high-density open metal sites (5.3 nm-3) and optimal pore size (5.5 Å), which are able to selectively capture Xe among other chemically inert gases including Kr, Ar, N2, and O2. Among M(II)-dhbq materials, Mn-dhbq exhibits the highest Xe uptake capacity of 3.1 mmol/g and a Xe/Kr selectivity of 11.2 at 298 K and 1.0 bar, outperforming many state-of-the-art adsorbents reported so far. Remarkably, the adsorption selectivity of Mn-dhbq for Xe/O2, Xe/N2, and Xe/Ar at ambient conditions reaches as high as 70.0, 139.3, and 64.0, respectively. Direct breakthrough experiments further confirm that all M(II)-dhbq materials can efficiently discriminate Xe atoms from other inert gases. It is revealed from the density functional theory calculations that the strong affinity between Xe and the coordination polymer is mainly attributed to the polarization by open metal sites.

Shell-like Xenon Nano-Traps within Angular Anion-Pillared Layered Porous Materials for Boosting Xe/Kr Separation.

Adsorptive separation of xenon (Xe) and krypton (Kr) is a promising technique but remains a daunting challenge since they are atomic gases without dipole or quadruple moments. Herein we report a strategy for fabricating angular anion-pillared materials featuring shell-like Xe nano-traps, which provide a cooperative effect conferred by the pore confinement and multiple specific interactions. The perfect permanent pore channel (4-5 Å) of Ni(4-DPDS)2 MO4 (M=Cr, Mo, W) can host Xe atoms efficiently even at ultra-low concentration (400 ppm Xe), showing the second-highest selectivity of 30.2 in Ni(4-DPDS)2 WO4 and excellent Xe adsorption capacity in Ni(4-DPDS)2 CrO4 (15.0 mmol kg-1 ). Crystallography studies and DFT-D calculations revealed the energy favorable binding sites and angular anions enable the synergism between optimal pore size and polar porosity for boosting Xe affinity. Dynamic breakthrough experiments demonstrated three MOFs as efficient adsorbents for Xe/Kr separation.

Microgeometry-independent equation for measuring infinite dilution activity coefficients using gas-liquid chromatography with static-wall-coated open-tubular columns.

Gas-liquid chromatography is an effective method to determine infinite dilution activity coefficients (γ∞). Wall-coated open-tubular (WCOT) column which offers more advantages over packed column should be a preferable column type; however, the small carrier gas flow rate and stationary phase amount in WCOT columns limit its application in the determination of γ∞. Mathematical strategy made some progress to avoid the quantification problem in the determination of γ∞ by static-wall-coated open-tubular (SWCOT) columns. However, the previously reported strategy was based on the assumption that SWCOT column was geometrically an ideal hollow cylinder, which indeed deviates from the reality. In this study, without that assumption, we derived a new microgeometry-independent equation by using the relationship between the hold-up volume (VM) and the volume of stationary phase (VL), and used it to measure the γ∞ of various organic solutes in two ionic liquids (ILs) 1­butyl­3-methylimidazolium dicyanamide and 1,3-dibutyronitrile-imidazolium bis((trifluoromethyl)sulfonyl)imide, both of which contain double cyano groups in the anion or cation. Phase loading study was adopted to eliminate the influence of interfacial adsorption to partition. The infinite dilution partial molar excess enthalpy, selectivity and capacity were directly calculated from the experimental γ∞ values, and the linear solvation energy relationship (LSER) model was used to characterize the specific properties of both ILs. This new established equation will promote the application of SWCOT columns in thermodynamic measurement and benefit the fast screening of novel solvents for chemical separation processes.

Engineering the Pore Size of Pillared-Layer Coordination Polymers Enables Highly Efficient Adsorption Separation of Acetylene from Ethylene.

The pore size of adsorbents plays a vital role in determining the overall separation performance of gas separation and purification by adsorption. In this work, the pore apertures of the coordination pillared layer (CPL) was systematically controlled by adjusting the length of pillared ligands. We used pyrazine, 4,4'-bipyridine, and 1,2-di(4-pyridyl)-ethylene with increased length to synthesize CPL-1 (L = pyrazine), CPL-2 (L = 4,4'-bipyridine), and CPL-5 [L = 1,2-di(4-pyridyl)-ethylene], respectively. The aperture size of these CPLs varies from 4 to 11 Å: CPL-1 (4 × 6 Å2), CPL-2 (9 × 6 Å2), and CPL-5 (11 × 6 Å2). Among the three frameworks, CPL-2 exhibits the highest C2H2 uptake at ambient conditions as it has moderate pore size and porosity. However, CPL-1 has the best separation performance in the breakthrough experiments with binary gas mixture of C2H2/C2H4, thanks to the optimal pore size nearly excluding C2H4, which is only observed in the state-of-the-art UTSA-300a so far. The DFT calculations were carried out to elucidate the specific adsorption sites for both acetylene and ethylene among these frameworks. The modeling results suggest that binding strength is highly related to aperture size and that CPL-1 shows the highest adsorption selectivity owing to the optimal pore size. This work demonstrates that engineering pore size enables us to fabricate the highly efficient metal-organic framework (MOF)-based adsorbents for specific gas separation on the basis of the isoreticular chemistry.

Highly efficient treatment of textile dyeing sludge by CO2 thermal plasma gasification.

Textile dyeing sludge is complex hazardous material with increasing amount year by year, and the conventional treatment techniques are limited by many drawbacks such as water/soil contamination, incomplete degradation of hazardous organics or inefficient fixation of toxic heavy metals. This work reported the first example of thermal plasma gasification treatment of textile dyeing sludge in a homemade rotating arc plasma reactor, which not only significantly reduced the volume and eliminated the safety risk of textile dyeing sludge, but also produced valuable syngas that can be used for chemical industry. At a feed rate of 36 g/min and a CO2 flow rate of 0.43 Nm3/h (14.08 g/min), the carbon conversion efficiency of gasification was 99.9%; and the energy conversion efficiency could reach 71.8%; and the lower heating value of syngas-rich produced gas was 8.91 MJ/Nm3. At the same time, the volume reduction ratio of sludge was 41.19% and the fixing efficiency of the heavy metals in solid products reached above 99%. Toxicity characteristic leaching procedure confirmed the solid products were harmless in a wide environmental pH range. The proposed method exhibits its great potential of simultaneously realizing harmless, minimization and reclamation of textile dyeing sludge and even other hazardous solid waste.

Inverse Adsorption Separation of CO2/C2H2 Mixture in Cyclodextrin-Based Metal-Organic Frameworks.

The demand for CO2/C2H2 separation, especially the removal of CO2 impurity, continues to grow because of the high-purity C2H2 required for various industrial applications. The adsorption separation of C2H2 and CO2 via porous materials is gaining a considerable attention as it is more energy-efficient compared with cryogenic distillation. The ideal porous materials are those that preferentially adsorb CO2 over C2H2; however, very few adsorbents meet such requirement. Herein, two isostructural cyclodextrin-based CD-MOFs (CD-MOF-1 and CD-MOF-2) were demonstrated to have an inverse ability to selectively capture CO2 from C2H2 by single-component adsorption isotherms and dynamic breakthrough experiments. These two MOFs showed excellent adsorption capacity and benchmark selectivity (118.7) for CO2/C2H2 mixture at room temperature, enabling the pure C2H2 to be obtained in only one step. This work revealed that these materials were promising adsorbents for obtaining high-purity C2H2 via selectively capturing CO2 from C2H2.

Hybrid Deep Eutectic Solvents with Flexible Hydrogen-Bonded Supramolecular Networks for Highly Efficient Uptake of NH3.

Serious environmental concerns have led to a great demand for efficient uptake of NH3 by solvents. However, traditional aqueous absorbents have many shortcomings and efforts to use ionic liquids have met with limited success. A hybrid deep eutectic solvents (DESs) designed with a flexible hydrogen-bonded supramolecular network exhibits both exceptional NH3 uptake capacity and superior desorption-regeneration performance, along with superb NH3 /CO2 selectivity and environmental merit. Elucidated by molecular dynamic simulations and spectroscopic analysis, the abundant hydrogen-bonding sites in the hybrid DESs bind every atom of the NH3 molecule and enable strong physical reversible solvation, whereas the multiple interactions among the hybrid components create a flexible hydrogen-bonded supramolecular network and allow for solvent-unbreaking absorption to ensure the full participation of the solvent and process stability. A mass solubility of NH3 up to 0.13 g g-1 was achieved at 313 K and 101 kPa by the hybrid DES choline chloride/resorcinol/glycerol (1:3:5), which is higher than all reported ionic liquids and ordinary DESs. Moreover, the performance remained the same after ten absorption-desorption cycles and the DESs could be easily regenerated.

Enhanced self-assembly for the solubilization of cholesterol in molecular solvent/ionic liquid mixtures.

The development of new solvents combining greatly enhanced solubility for sparingly soluble compounds and good kinetic properties is challenging. In this study, we constructed a family of new molecular solvent/ionic liquid (IL) mixtures with amphiphilic, anionic functional long-chain carboxylate ionic liquids (LCC-ILs) as a key component for the solubilization of sparingly soluble compounds, using cholesterol as a model solute. Polarized optical microscopy (POM), wide angle X-ray diffraction (WAXD), Fourier-transform infrared (FTIR) spectra and 1H NMR showed that ordered mesoscopic structures, such as liquid crystals (LCs), were formed when cholesterol was dissolved in the mixtures, presenting a self-assembly induced dissolution mechanism driven by H-bond interaction and van der Waals forces in the mixtures. A synergistic effect between the molecular solvents and LCC-ILs was revealed, which contributed to enhanced solute-solvent self-assembly in dissolution over pure LCC-ILs and thus elevated solubility. Additionally, the effect of IL concentration, solvent type and anionic alkyl-chain length on self-assembly and solubility was investigated. These mixtures showed unparalleled solubilities for cholesterol, while maintaining a low viscosity. The quantitative solubilities (g g-1) of cholesterol were as high as 0.70, 0.84 and 0.82, respectively, at 25 °C in ethyl acetate/[P4444][C15H31COO] (50 wt%), n-heptane/[P4444][C15H31COO] (40 wt%) and ethyl acetate/[P4444][C17H35COO] (50 wt%) mixtures, which were the highest solubilities of cholesterol ever reported, six- to 980-fold higher than traditional molecular solvents and even one- to seven-fold higher compared to pure LCC-ILs. These results demonstrated the considerable potential of molecular solvent/LCC-ILs mixtures as promising solvents for solubilization and advanced separation processes.

Incorporation of N-Methyl-d-glucamine Functionalized Oligomer into MIL-101(Cr) for Highly Efficient Removal of Boric Acid from Water.

Polymeric resins are practically important adsorbents in a wide variety of applications, but they generally suffer from low surface areas and limited functionalized adsorption sites owing to their closely compacted and tangled polymeric chains. A metal-organic framework (MOF)-polymer composite with enhanced adsorption capacity against the compacted polymeric resins was reported. The strategy to incorporate functionalized oligomer within the cavities of the MOF was demonstrated by the preparation of MIL-101(Cr) incorporated with N-methyl-d-glucamine-based organosiloxane polymer. The resulting MOF composite shows high efficiency for the removal of boric acid from water because of exceptionally high loading of functional groups responsible for the boron adsorption. This material offers promising perspectives for boron removal applications in seawater desalination.

Nonaqueous lyotropic ionic liquid crystals: preparation, characterization, and application in extraction.

A class of new ionic liquid (IL)-based nonaqueous lyotropic liquid crystals (LLCs) and the development of an efficient IL extraction process based on LC chemistry are reported. The nonaqueous LLCs feature extraordinarily high extraction capacity, excellent separation selectivity, easy recovery, and biocompatibility. This work also demonstrates that the introduction of self-assembled anisotropic nanostructures into an IL system is an efficient way to overcome the intrinsically strong polarity of ILs and enhances the molecular recognition ability of ILs. The distribution coefficients of IL-based LLCs for organic compounds with H-bond donors reached unprecedented values of 50-60 at very high feed concentrations (>100 mg mL(-1) ), which are 800-1000 times greater than those of common ILs as well as traditional organic and polymer extractants. The IL-based nonaqueous LLCs combining the unique properties of ILs and LCs open a new avenue for the development of high-performance extraction methods.

Immobilization of Ag(i) into a metal-organic framework with -SO3H sites for highly selective olefin-paraffin separation at room temperature.

Introduction of Ag(i) ions into a sulfonic acid functionalized MOF ((Cr)-MIL-101-SO3H) significantly enhances its interactions with olefin double bonds, leading to its much higher selectivities for the separation of C2H4-C2H6 and C3H6-C3H8 at room temperature over the original (Cr)-MIL-101-SO3H and other adsorbents at room temperature.

Preparation of porous cellulose 3,5-dimethylphenylcarbamate hybrid organosilica particles for chromatographic applications.

Organic-inorganic hybrids incorporating cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC)-functionalized silica particles can exhibit a high loading capacity with high loadings of the chiral selector. These materials offer considerable potential for use in preparative chiral separations. However, the preparation of these hybrid particles with high surface areas and controlled organic/inorganic ratios is challenging. We have found that by controlling the pH of sol-gel step and regulating the ratio of the inorganic precursor over CDMPC, unique functional hybrid particles could be prepared with optimum pore structure, novel interfacial features and excellent mechanical strength. The morphological features of these hybrid particles were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The organic content was determined by thermogravimetric analysis (TGA) and pore structure determined by Brunauer-Emmett-Teller (BET) analysis. These new hybrid particles exhibit excellent solvent durability, which is crucial for preparative chromatography. HPLC analysis of columns, packed with this material, confirmed solvent tolerance such as for chloroform, giving potential applications for large scale chromatographic separations.

One of the distinctive properties of ionic liquids over molecular solvents and inorganic salts: enhanced basicity stemming from the electrostatic environment and "free" microstructure.

The basicity of ionic liquids (ILs) underlies many important IL-based processes including the dissolution and conversion of cellulose, the capture of CO2, and metal catalysis. In this work, we have disclosed the nature of the basicity of ILs, i.e., the difference between the basicity of IL and the basicity of the molecular solvent and inorganic salt, through a quantitative electrostatic and electronic analysis of the molecular surface for the first time. The results reveal one of the distinctive properties of ILs (enhanced basicity over molecular solvents and inorganic salts with the same basic site) stemming from their special electrostatic environment and microstructure. The enhancement is significant, from either the electrostatic aspect or the covalent aspect of basicity. The peculiar electrostatic environment of ILs leads to stronger basicity than similar molecular solvents, and the relatively freer microstructure of ILs contributes to the enhancement of basicity over their inorganic analogues. These results are highly instructive for better understanding the unique value of ILs and designing novel ILs to improve the efficiency of basicity-related processes.

Enhancing the basicity of ionic liquids by tuning the cation-anion interaction strength and via the anion-tethered strategy.

Ionic liquids (ILs) with relatively strong basicity often show impressive performance in chemical processes, so it is important to enhance the basicity of ILs by molecular design. Here, we proposed two effective ways to enhance the basicity of ILs: by weakening the cation-anion interaction strength and by employing the anion-tethered strategy. Notably, two quantum-chemical parameters, the most negative surface electrostatic potential and the lowest surface average local ionization energy, were adopted as powerful tools to demonstrate the electrostatic and covalent aspects of basicity, respectively, at the microscopic level. It was shown that, for the ILs with the same anion (acetate or trifluoroacetate), the basicity of the ILs could be enhanced when the cation-anion interaction strength was weakened. For the acetate anion-based ILs, the hydrogen-bonding basicity scale (ß) increased by 29% when the cation changed from 1-butyl-3-methylimidazolium ([Bmim]) to tetrabutylphosphonium ([P4444]), achieving one of the highest reported ß values for ILs. Moreover, it was also demonstrated that, when an amine group was tethered to the anion of the IL, its basicity was stronger than when it was tethered to the cation. These results are highly instructive for designing ILs with strong basicity and for improving the efficiency of IL-based processes, such as CO2 capture, SO2 and acetylene absorption, dissolution of cellulose, extraction of bioactive compounds, and so on.

Separation of long chain fatty acids with different number of unsaturated bonds by fractional extraction: experimental and COSMO-RS study.

Long chain unsaturated fatty acids (LCUFAs) are important food components and dietary supplements due to their beneficial health effects. The key process to produce high-purity LCUFAs is to separate long chain fatty acids (LCFAs) with different degrees of unsaturation and chain lengths. This process faces great challenge because of similar physico-chemical properties of fatty acids concerned. In this work, fractional extraction is proposed to separate LCFAs, using eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), conjugated linoleic acids (CLAs), oleic acid (OA) and stearic acid (SA) as model LCFAs. COSMO-RS calculations were performed for fast extractant screening and exploring the potential separation mechanism. Satisfactory distribution coefficients and high selectivities were obtained in extraction equilibrium experiments. Simulation and experimental validation of fractional extraction were performed, and high purity and high yield of CLAs were obtained. EPA and DHA could be separated thoroughly from OA, though they could not be separated each other.

Synthesis and characterization of cellulose 3,5-dimethylphenylcarbamate silica hybrid spheres for enantioseparation of chiral ß-blockers.

A cellulose derivative-based chiral stationary phase (CSP) is considered one of the most widely applied CSPs due to its powerful enantioseparation ability. The high loading capacity and mechanical strength of CSPs are crucial for their application in preparative chromatography, such as a simulated moving bed. Compared to traditional cellulose-based CSPs that have been adsorbed onto chromatographic supports, organic-inorganic hybrid CSPs exhibit a potentially higher loading capacity and mechanical strength by increasing the density of chiral recognition groups. A hybrid cellulose 3,5-dimethylphenylcarbamate chiral stationary phase (organic/inorganic: 70/30, w/w) was prepared via a sol-gel method and characterized with several analytical techniques, including Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and (29)Si cross polarization/magic angle spinning nuclear magnetic resonance ((29)Si CP/MAS NMR). In addition, the as-synthesized hybrid chiral silica spheres were treated with an end-capping process to mask the residual silica hydroxyl groups. Compared to a commercial Chiralpak IB column, better separation of ß-blocker drugs, including pindolol (selectivity of 5.55), metoprolol (2.30), propranolol (1.96), bisoprolol (1.74) and atenolol (1.46), on the end-capped CSP was achieved using liquid chromatography, which suggests that the packing material synthesized in this work has sufficient chiral discriminating ability for the effective separation of ß-blocker drugs.

Salt-enhanced removal of 2-ethyl-1-hexanol from aqueous solutions by adsorption on activated carbon.

2-Ethyl-1-hexanol has extensive industrial applications in solvent extraction, however, in view of its potential pollution to environment, the removal and recovery of 2-ethyl-1-hexanol is considered an essential step toward its sustainable use in the future. In this work, we report the removal of 2-ethyl-1-hexanol from aqueous solutions containing salts in high concentrations by adsorption on a coal-based activated carbon. Adsorption thermodynamics showed that the experimental isotherms were conformed well to the Langmuir equation. Also it was found that inorganic salts, i.e. MgCl2 and CaCl2 in high concentration significantly enhanced the adsorption capacity from 223 mg/g in the deionized water to 277 mg/g in a saline water. This phenomenon of adsorption enhancement could be ascribed to the salt-out effect. Kinetic analysis indicated that adsorption kinetics follows the pseudo-second-order equation and the adsorption rate constants increase with the salt concentration. The dynamic breakthrough volume and adsorbed amount of 2-ethyl-1-hexanol were significantly elevated when the salt is present in the water. The dynamic saturated adsorption amount increased from 218.3mg/g in the deionized water to 309.5mg/g in a salt lake brine. The Tomas model was well applied to predict the breakthrough curves and determine the characteristics parameters of the adsorption column.

Enantiomeric separation of citalopram base by supercritical fluid chromatography.

The chiral separation of citalopram base by supercritical fluid chromatography on a semipreparative Chiralpak AD column was studied with the use of three alcohol-type modifiers (methanol, ethanol, and 2-propanol) with different volume percentages (5, 10, and 15%). The best separation was achieved when 10% 2-propanol was used in the presence of 0.1% diethylamine as additive. Under these conditions, the resolution reached 2.15 and the selectivity was 1.388. In addition, other parameters that affected the retention and separation properties, i.e. temperature, pressure, and density, were studied in detail. At the same pressure, a decrease in the temperature improved the enantioselectivity as the experimental temperature range was below the isoelution temperature. However, the temperature dependence of the retention factor was complicated. As a rule, the retention factor decreased when the temperature increased at the same density. A satisfactory regression of the logarithm of the retention factor versus density and temperature was obtained using a simplified lattice-fluid model. Surprisingly, the relationship between the Henry constant and density can be accurately correlated by using the same quadratic equation.

Feasibility of ionic liquids as extractants for selective separation of vitamin D3 and tachysterol3 by solvent extraction.

A selective separation of vitamin D3 and tachysterol3 by solvent extraction with 7 organic solvents and 11 ionic liquids (ILs) has been reported. Among organic solvents sulfolane showed optimal extraction performance, giving only a selectivity of 1.44 for tachysterol3 over vitamin D3. ILs with unsaturated bonds demonstrated high selectivity probably due to their different π-π interactions with the two compounds. A pyrrolidinium-based ionic liquid, for example, [BMPr][NTf2], provided the highest selectivity up to 1.77. Acceptable selectivity and distribution coefficients were observed by a combination of organic solvents and ILs as extracting agents. In this work, the effects of concentrations, anions, cations, and substituent of ILs were investigated, which may provide a rational strategy for the design of novel ILs for extractive separation of structural analogues. The purification and recovery of vitamin D33 via continuous multistage extractions were simulated, indicating that IL-based liquid-liquid extraction might be superior to traditional organic solvents in practical production.