Poly(ionic liquid)-crosslinked graphene oxide/carbon nanotube membranes as efficient solar steam generators

Graphene oxide(GO)is regarded as a promising candidate to construct solar absorbers for addressing freshwater crisis,but the easy delamination of GO in water poses a critical challenge for practical solar desalination.Herein,we improve the stability of GO membranes by a self-crosslinking poly(ionic liquid)(PIL)in a mild condition,which crosslinks neighbouring GO nanosheets without blemishing the hydrophilic structure of GO.By further adding carbon nanotubes(CNTs),the sandwiched GO/CNT@PIL(GCP)membrane displays a good stability in pH=1 or 13 solution even for 270 days.The molecular dynamics simulation results indicate that the generation of water nanofluidics in nanochannels of GO nanosheets remarkably reduces the water evaporation enthalpy in GCP membrane,compared to bulk water.Consequently,the GCP membrane exhibits a high evaporation rate(1.87 kg m^(-2)h^(-1))and displays stable evaporation rates for 14 h under 1 kW m^(-2)irradiation.The GCP membrane additionally works very well when using different water sources(e.g.,dye-polluted water)or even strong acidic solution(pH=1)or basic solution(pH=13).More importantly,through bundling pluralities of GCP membrane,an efficient solar desalination device is developed to produce drinkable water from seawater.The average daily drinkable water amount in sunny day is 10.1 kg m^(-2),which meets with the daily drinkable water needs of five adults.The high evaporation rate,long-time durability and good scalability make the GCP membrane an outstanding candidate for practical solar seawater desalination.

Poly(Ionic Liquid) as an Anion Exchange Membrane for a 3.3 V Copper–Lithium Battery

Metal–metal battery bears great potential for next-generation large-scale energy storage system because of its simple manufacture process and low production cost.However,the cross-over of metal cations from the cathode to the anode causes a loss in capacity and influences battery stability.Herein,a coating of poly(ionic liquid)(PIL)with poly(diallyldimethylammonium bis(trifluoromethanesulfonyl)imide)(PDADMA^(+)TFSI^(−))on a commercial polypropylene(PP)separator serves as an anion exchange membrane for a 3.3 V copper–lithium battery.The PIL has a positively charged polymer backbone that can block the migration of copper ions,thus improving Coulombic efficiency,long-term cycling stability and inhibiting self-discharge of the battery.It can also facilitate the conduction of anions through the membrane and reduce polarization,especially for fast charging/discharging.Bruce-Vincent method gives the transport number in the electrolyte to be 0.25 and 0.04 for PP separator without and with PIL coating,respectively.This suggests that the PIL layer reduces the contribution of the internal current due to cation transport.The use of PIL as a coating layer for commercial PP separator is a cost-effective way to improve overall electrochemical performance of copper–lithium batteries.Compared to PP and polyacrylic acid(PAA)/PP separators,the PIL/PP membrane raises the Coulombic efficiency to 99%and decreases the average discharge voltage drop to about 0.09 V when the current density is increased from 0.1 to 1 mA cm^(−2).

Mesoporous poly(ionic liquid)s with dual active sites for highly efficient CO_(2)conversion

Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.

Wet-spun poly(ionic liquid)-graphene hybrid fibers for high performance all-solid-state flexible supercapacitors

It is crucial to develop flexible and wearable electronic devices that have attracted tremendous interest due to their merits on compactness,flexibility and high capacitive properties.Herein we report the continuously ordered macroscopic poly(ionic liquid)-graphene fibers by wet spinning method via liquid crystal assembly for supercapacitor application.The fabricated all-solid-state supercapacitors exhibited a high areal capacitance(268.2 mF cm 2)and volumetric capacitance(204.6 F cm 3)with an outstanding areal energy density(9.31μWh cm-2)and volumetric energy density(8.28 mWh cm-3).The fiber supercapacitors demonstrated exceptional cycle life for straight electrodes of about 10,000 cycles(94.2%capacitance retention)and flexibility at different angles(0°,45°,90°,180°)along with a good flexible cycling stability after 6000 cycles(92.7%capacitance retention).To date,such a novel poly(ionic liquid)-graphene fiber supercapacitors would be a new platform in real-time flexible electronics.

Fabrication of poly(vinylidene fluoride) membrane via thermally induced phase separation using ionic liquid as green diluent

Ionic liquid(IL),1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6)as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF)membranes via thermally induced phase separation(TIPS).Phase diagram of PVDF/[BMIM]PF6 was measured.The effects of polymer concentration and quenching temperature on the morphologies,properties,and performances of the PVDF membranes were investigated.When the polymer concentration was 15 wt%,the pure water flux of the fabricated membrane was up to nearly 2000 L·m-2·h-1,along with adequate mechanical strength.With the increasing of PVDF concentration and quenching temperature,mean pore size and water permeability of the membrane decreased.SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6)presented spherulite structure.And the PVDF membranes were represented asβphase by XRD and FTIR characterization.It provides a new way to prepare PVDF membranes with piezoelectric properties.

Swelling acidic poly(ionic liquid)s as efficient catalysts for the esterification of cyclohexene and formic acid

Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sulfuric acid.The swelling ability of acidic PILs was greatly affected by cross-linker content and chain length of 3-alkyl-substituents on imidazolium.Cross-linked network structures could be observed from the cryogenic scanning electron microscopy(cryo-SEM)images of the swollen acidic PILs in formic acid.Acidic PILs with network structures in swollen state exhibited excellent activities in the esterification of cyclohexene and formic acid,and the catalytic activities were in positive correlation with their swelling abilities.Acidic PIL with 3-octyl-substituent and 2.5 mol%DVB(PIL-C8-2.5DVB-HSO4)had the highest swelling ability in formic acid and exhibited comparable catalytic activities with homogeneous catalysts such as sulfuric acid and p-toluenesulfonic acid.

Polymeric ionic liquids(PILs)with high acid density:Tunable catalytic performance for biodiesel production

A series of polymeric ionic liquids(PILs)used as effective heterogeneous catalysts for biodiesel production via esterification of free fatty acids(FFAs)were effectively prepared by the reaction of poly(ethylene imine)(PEI)polymers with different molecular weight and 1,3-propanesultone,followed by the further acidification with differential effective acids,i.e.H2SO4,CF3SO3H,CH3SO3H or p-toluenesulfonic acid(p-TSA).Ultrahigh acidity and catalytic performance were achieved and could be fine-tuned by simply adjusting the molecular weight of PEI and by further treatment of acids.Specifically,under the optimal conditions(i.e.reaction temperature was 70℃,reaction time was 2.0 h,catalyst dosage was 3.15%(mass),and alcohol/acid molar ratio was 14:1)acquired through the Box-BEHNKEN response surface methodology,a high oleic acid conversion of 98.42%could be obtained over the optimal PIL,PEI(70000)-PS-p-TSA.Additionally,our PILs also showed high generality for esterification of other FFAs,with general high conversion over 90%noted in each case even under much milder reaction conditions compared to other conventional catalysts.

Pyrolyzing soft template-containing poly(ionic liquid)into hierarchical N-doped porous carbon for electroreduction of carbon dioxide

Heteroatom-doped carbon materials have demonstrated great potential in the electrochemical reduction reaction of CO_(2)(CO_(2)RR)due to their versatile structure and function.However,rational structure control remains one challenge.In this work,we reported a unique carbon precursor of soft template-containing porous poly(ionic liquid)(PIL)that was directly synthesized via free-radical self-polymerization of ionic liquid monomer in a soft template route.Variation of the carbonization temperature in a direct pyrolysis process without any additive yielded a series of carbon materials with facile adjustable textural properties and N species.Significantly,the integration of soft-template in the PIL precursor led to the formation of hierarchical porous carbon material with a higher surface area and larger pore size than that from the template-free precursor.In CO_(2)RR to CO,the champion catalyst gave a Faraday efficiency of 83.0%and a current density of 1.79 mA·cm^(-2)at-0.9 V vs.reversible hydrogen electrode(vs.RHE).The abundant graphite N species and hierarchical pore structure,especially the unique hierarchical small-/ultramicropores were revealed to enable better CO_(2)RR performance.

NMR signal separation of ionic liquids by poly( sodium-p-styrenesulfonate)-assisted chromatographic NMR spectroscopy--Dedicated to Professor Xiuwen Han on the occasion of her 80th birthday

Diffusion-ordered nuclear magnetic resonance spectroscopy(DOSY),dubbed chromato-graphic NMR spectroscopy,can be used to simultaneously distinguish and identify the structures of components in a mixture according to their different diffusion coefficients.In order to improve the resolution of DOSY on the diffusion dimension,a lot of matrices have been developed to expand the application of this technique in mixture analysis.However,there is no matrix to detect the mixture of ionic liquids(ILs).Herein,we introduced a new matrix,poly(sodium-p-styrenesulfonate)(PSSNa),which can be used to fully separate the signals of a mixture of different ILs.The mixture of three imidazolium ILs of 1-butyl-3-methylimidazolium bromide,1-allyl-3-vinylimidazolium bromide and 1-arboxymethy-3-methylimidazolium chloride could be fully distinguished by virtue of their different interactions with PSSNa.We also investigated the influences of PSSNa amount,IL con-centration and solution pH value on the signal resolution of mixtures.This work provides a scientific reference for the analysis of the other IL analytes.

Differentiation of Chemisorption and Physisorption of Carbon Dioxide on Imidazolium-type Poly(ionic liquid)Brushes

Amine-functionalized imidazolium-based poly(ionic liquid)brushes on mesoporous silica were synthesized via"grafting through"technique and were applied as model sorbents to understand physisorption and chemisorption of carbon dioxide molecules.The experimental results reveal that the total adsorption capacity of model sorbents derived from temperature programmed desorption(TPD)approach reaches 1.72 mmol·g^-1 that is much higher than the sum of adsorption capacity of bare mesoporous silica and free polymers at 25℃under carbon dioxide partial pressure of 0.2 bar.The proposed physical adsorption and chemical adsorption of carbon dioxide molecules in TPD response curves were validated by volumetric desorption measurement.It is also observed that physical adsorption is completely reversible and chemical adsorption is irreversible.The results demonstrate that the temperature programmed desorption technique is an effective approach to differentiate chemisorption and physisorption of gaseous species on solid sorbents,which is beneficial for understanding of adsorption mechanism and materials design.

New methacrylic imidazolium poly (ionic liquid) gel with super swelling capacity for oil-in-water emulsions

A new polymeric ionic liquid gel was prepared with 1-[(2-methacryloyloxy)ethyl]-3-methylimidazolium bromide(MEMImBr) via radiation-induced polymerization and cross-linking at room temperature.The resultant PMEMImBr gel exhibits high strength and flexibility as well as special swelling behavior in oil-in-water(O/W)emulsions.The swelling behavior of PMEMImBr gel in emulsions is similar to that in water except that the swelling rate in emulsions is slightly smaller than that in water.The organic solvents with higher polarity in the emulsions contribute to the swelling of PMEMImBr gels,and the O/W proportion of emulsion in the swollen gel equals approximately that of original emulsion when the concentration of organic solvent is lower than 0.2 g/g.

Ionic liquids/deep eutectic solvents for CO_(2) capture:Reviewing and evaluating

The CO_(2)solubilities(including CO_(2)Henry’s constant)in physical-and chemical-based ILs/DESs and the COSMO-RS models describing these properties were comprehensively collected and summarized.The summarized results indicate that chemical-based ILs/DESs are superior to physical-based ILs/DESs for CO_(2)capture,especially those ILs have functionalized cation and anion,and superbase DESs;some of the superbase DESs have higher CO_(2)solubilities than those of ILs;the best physical-and chemical-based ILs,as well as physical-and chemicalbased DESs are[BMIM][BF4](4.20 mol kg^(-1)),[DETAH][Im](11.91 mol kg^(-1)),[L-Arg]-Gly 1:6(4.92 mol kg^(-1))and TBD-EG 1:4(12.90 mol kg^(-1)),respectively.Besides the original COSMO-RS mainly providing qualitative predictions,six corrected COSMO-RS models have been proposed to improve the prediction performance based on the experimental data,but only one model is with universal parameters.The newly determined experimental results were further used to verify the perditions of original and corrected COSMO-RS models.The comparison indicates that the original COSMO-RS qualitatively predicts CO_(2)solubility for some but not all ILs/DESs,while the quantitative prediction is incapable at all.The original COSMO-RS is capable to predict CO_(2)Henry’s constant qualitatively for both physical-based ILs and DESs,and quantitative prediction is only available for DESs.For the corrected COSMO-RS models,only the model with universal parameters provides quantitative predictions for CO_(2)solubility in physical-based DESs,while other corrected models always show large deviations(>83%)compared with the experimental CO_(2)Henry’s constants.

Liquid Crystalline Polymers XIII Main Chain Thermotropic Copoly (Arylidene-Ether)s Containing 4-Teriary Butyl-Cyclohexanone Moiety Linked with Polymethylene Spacers

A new homologous series of thermotropic liquid crystalline copoly(arylidene-ether)s based on 4-teriary butyl cyclohexanone moiety were synthesized by solution polycondensation of 4,4’-diformyl-α,ω-diphenoxyalkanes, Ia-d or 4,4’- diformyl-2,2’-dimethoxy-α,ω-diphenoxyalkanes IIa-d with the 4-teriary butyl-cyclohexanone III and cyclopentanone. A model compound IV was synthesized from the monomer III with benzaldehyde and characterized by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range 0.22 - 0.92 dI/g. All the copoly(arylidene-ether)s were insoluble in common organic solvents but dissolved completely in concentrated H2SO4 and formic acid. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by DSC and optical polarizing microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermogravimetric analyses of those polymers were evaluated by TGA and DSC measurements and correlated to their structural units. X-Ray analysis showed that copolymers having some degree of crystallinity in the region 2q = 5° -60°. In addition, the morphological properties of selected examples were tested by Scanning electron microscopy.

A NEW STRATEGY FOR THE DESIGN OF LIQUID CRYSTALLINE POLYMERS WITH FLEXIBLE AND APOLAR BUILDING BLOCKS

The synthesis and characterization of a new series of liquid crystalline polymers, poly(dicycloalkylvinylterephthalate)s, are reported. The basic building blocks of these polymers are not mesogenic by themselves. However,very stable mesophases can be generated by self-assembly of the polymer molecules. This approach suggests a novel designstrategy of liquid crystalline polymers with flexible and apolar building blocks.

Immobilization of Functionalized Ionic Liquid on Sol-Gel Derived Silica for Efficient Removal of H_2S

An innovative approach to H2 S capture has been developed using several metal-based ionic liquids([Bmim]Cl·CuCl_2, [Bmim]Cl·FeCl_3, [Bmim]Cl·ZnCl_2, [Bmim]Br·CuCl_2, and [Bmim]Br·FeCl_3) immobilized on the sol-gel derived silica, which is superior to purely viscous ionic liquid with a crucial limit of high temperature, low mass transfer rate,and mass loss. The adsorbents were characterized by the Fourier transform infrared spectrometer, transmission electron microscope, N_2 adsorption/desorption, X-ray photoelectron spectroscopy, and thermal analysis techniques. The effects of the metal and halogen in IL, the loading amount of IL, and the adsorption temperature were studied by dynamic adsorption experiments at a gas flow rate of 100 mL/min. The H2 S adsorption results have showed that the optimal adsorbent and adsorption temperature are 5% [Bmim]Cl·CuCl_2/silica gel and 20—50 ℃, respectively. H_2 S can be captured and oxidized to elemental sulfur, and [Bmim]Cl·CuCl_2/silica gel can be readily regenerated by air. The excellent efficiency of H2 S removal may be attributed to the formation of nano-scaled and high-concentration [Bmim]Cl·CuCl_2 confined in silica gel, indicating that the immobilization of [Bmim]Cl·CuCl_2 on the sol-gel derived silica can be used for H2 S removal promisingly.

SYNTHESIS AND CHARACTERIZATION OF THERMOTROPIC LIQUID CRYSTALLINE POLY(ESTER-IMIDE)S

A new series of thermotropic liquid crystalline poly(ester- imide)s were synthesized via a solution polycondensation process.The polymers were also characterized by IR,DSC,polarizing microscopy and WAXD measurements.

Poly(amide-6-b-ethylene oxide)/[Bmim][Tf2N] blend membranes for carbon dioxide separation

Poly（amide-6-b-ethylene oxide）（Pebax1657）/1-butyl-3-methylimidazo-lium bis[trifluoromethyl）sulfonyl]-imide（[Bmim][Tf2N]） blend membranes with different [Bmim][Tf2N] contents were prepared via solution casting and solvent evaporation method. The permeation properties of the blend membranes for CO2, N2,CH4 and H2 were studied, and the physical properties were characterized by differential scanning calorimeter（DSC） and X-ray diffraction（XRD）. Results showed that [Bmim][Tf2N] was dispersed as amorphous phase in the blend membranes, which caused the decrease of Tg（PE） and crystallinity（PA）. With the addition of [Bmim][Tf2N], the CO2 permeability increased and reached up to approximately 286 Barrer at 40 wt%[Bmim][Tf2N], which was nearly double that of pristine Pebax1657 membrane. The increase of CO2 permeability may be attributed to high intrinsic permeability of [Bmim][Tf2N], the increase of fractional free of volume（FFV） and plasticization effect. However, the CO2 permeability reduced firstly when the [Bmim][Tf2N]content was below 10 wt%, which may be due to that the small ions of [Bmim][Tf2N] in the gap of polymer chain inhibited the flexibility of polymer chain; the interaction between Pebax1657 and [Bmim][Tf2N]decreased the content of EO units available for CO2 transport and led to a more compact structure. For Pebax1657/[Bmim][Tf2N] blend membranes, the permeabilities of N2, H2 and CH4decreased with the increase of feed pressure due to the hydrostatic pressure effect, while CO2 permeability increased with the increase of feed pressure for that the CO2-induced plasticization effect was stronger than hydrostatic pressure effect.

Functional Poly(ionic liquid)Porous Membranes:From Fabrications to Advanced Applications

Polyelectrolyte porous membranes(PPMs)belong to the most interesting classes of materials,because the synergy of tunable pore sizes and charge nature of polyelectrolyte endow them with wide-ranging practical applications.However,owing to the water solu-bility and ionic nature of the polyelectrolytes,traditional polyelectrolytes are difficult to use in scalable preparation of high-quality PPMs through the well-developed industrial methods.Poly(ionic liquid)s(PIL)are a subclass of functional polyelectrolytes bearing ionic liquid groups in their repeating unites,inheriting the advantages of ionic liquids(ILs)and macromolecular architecture features.In recent years,along with rapid development of PIL materials chemistry,considerable and significant developments involving the novel preparation methods,and structure-property-function relationships of PPMs have been made.In this review,we highlight the latest discovery and proceedings of PPMs,particularly the advancements in how to tailor structures and properties of PPMs by ra-tional structure design of PILs.The formation mechanisms of various PPMs were also discussed in detail from the viewpoint of PILs molecular structures.A future perspective of the challenges and promising potential of PPMs is cast on the basis of these achieve-ments.We expect that these analyses and deductions will be useful for the design of useful PPMs and serve as a source of inspira-tion for the design of future multifunctional PPMs.

Block Copolymer Solid Electrolytes Based on Comb-Like Poly(ethylene glycol)Plasticized Poly(ionic liquid)s for Lithium-Ion Batteries

Electrolytes based on poly(ionic liquid)s(PILs)have attracted great attention in the fields of next-generation solid lithium-ion batteries.However,the low ionic conductivity prevents their practical applications.Herein,we report novel solid electrolytes based on block copolymers composed of PILs and comb-like poly(ethylene glycol)(PEG),which were synthesized via ring-opening metathesis polymerization of 3-(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1-butyl-1H-imidazol-3-ium bis((trifluoromethyl)sulfonyl)amide and poly(ethylene glycol monomethyl ether)bicyclo[2.2.1]hept-5-ene-2-carboxylate.Comb-like PEG acts as plasticizers in block copolymers dominated by PILs to promote the mobility of PILs segments.Effects of the copolymer composition and length of the comb-like PEG chain on ionic conductivity were investigated.The optimized electrolyte delivers the highest ionic conductivity of 1.5×10^(–5)S·cm^(–1)at 30℃,and robust electrochemical stability up to 4.6 V.A solid-state Li/LiFePO4 cell using the optimized electrolyte demonstrates good cycle performance at 0.2 C with high capacity retention of 92%after 70 cycles at 50℃.

Dual-Resistance of Ion Migration and Moisture Erosion via Hydrolytic Crosslinking of Siloxane Functionalized Poly(Ionic Liquids)for Efficient and Stable Perovskite Solar Cells

The inevitable ion migration that occurs within ionic polycrystalline perovskite film results in inferior longterm stability of perovskite solar cells(PVSCs)that cannot meet the commercial requirements.Here,a novel poly(ionic liquid)named poly-1-vinyl-3-propyltrimethoxysilane imidazolium chloride(PImIL-SiO)is first introduced into perovskite to strengthen grain boundaries(GBs)and construct dual-functional barriers against internal ion migration and external moisture erosion for fabricating highly efficient and stable PVSCs.PImIL-SiO-containing imidazoliumcations and pendant siloxane groups contribute to passivation of bulk defects and anchoring of GBs,which effectively hinders ion migration channels,thus reducing perovskite film phase separation and device hysteresis.Furthermore,the intrinsically hydrophobic PImIL-SiO automatically forms a secondary protective barrier to endow the perovskite film with ultrahigh moisture corrosion resistance through the hydrolyzation reaction of siloxane with the permeated moisture.Consequently,the PImIL-SiO-modified PVSCs achieve a champion power conversion efficiency(PCE)of 22.46%,accompaniedby excellent thermal andhumidity stabilities where the non-encapsulated devices retain 87%of the initial PCE after aging at 85℃for 250 h and>85%of the initial PCE over 1100 h in air with a relative humidity of 50–70%.