A generalizable strategy based on the rule of“like dissolves like”to construct porous liquids with low viscosity for CO_(2)capture

Porous liquids(PLs),an emerging porous material with permanent cavities,have attracted extensive attention in recent years.However,the current construction methods are complicated and resulting PLs possess high viscosity values,which cannot meet the requirements of practical industrial applications.Herein,we demonstrate a generalizable and simple strategy to prepare type III PLs with low viscosity based on the rule of“like dissolves like”.Specifically,the monoglycidyl ether terminated polydimethylsiloxane(denoted by E-PDMS)is attached to the surface of Universitetet i Oslo(UiO)-66-NH_(2)via covalent linkage,constructing the pore generator(UiO-66-NH_(2)-E-PDMS,denoted by P-UiO-66).Then,P-UiO-66 is dispersed into different types and amounts of sterically hindered solvents(PDMS400 or PDMS6000),obtaining a series of type III PLs(denoted by P-UiO-66-PLs)with permanent cavities and low viscosities.The gas sorption-desorption test shows that P-UiO-66-PLs have an enormous potential for CO_(2)/N_(2) selective separation.Besides,the porosity of P-UiO-66-PLs and the CO_(2)sorption mechanism are demonstrated by molecular simulation.Furthermore,the generality of the synthesis strategy is confirmed by the successful construction of PLs using two other amino-metal-organic frameworks(MOFs)(MIL-53(Al)-NH_(2)and MIL-88B(Fe)-NH_(2)).Importantly,it’s worth noting that the strategy based on the rule of“like dissolves like”sheds light on the preparation of other types of PLs for task-specific applications.

Underlying solvent-based factors that influence permanent porosity in porous liquids

Porous liquids(PLs)offer the potential to combine the ready handling and mature industry status of liquid absorbents,with the high permanent porosity of metal organic frameworks.To be functional,these nanocomposites need to satisfy a number of performance parameters,such as stability and viscosity of the porogen-solvent combination,avoiding solvent penetration into metal organic framework(MOF)pores,suitable capacities,and kinetics for gas sorption.In this work,we systematically investigate the component materials to elucidate the parametric space where stable photoluminescence(PL)can be generated.In this situation,deeper conclusions were able to be drawn with regard to the influence of hydrophobicity/philicity on the properties of the resulting nanocomposites.Zeolitic imidazolate frameworks(ZIFs)were combined with a range of solvents varying in steric bulk,to deliver CO_(2)sorption capacities as high as 4.2 mmol·g^(-1)at 10 bar.These findings may have broader implications for future investigations of this tantalising field of nanocomposites.

Advanced Materials for NH_(3)Capture:Interaction Sites and Transport Pathways

Ammonia(NH3)is a carbon-free,hydrogen-rich chemical related to global food safety,clean energy,and environmental protection.As an essential technology for meeting the requirements raised by such issues,NH3 capture has been intensively explored by researchers in both fundamental and applied fields.The four typical methods used are(1)solvent absorption by ionic liquids and their derivatives,(2)adsorption by porous solids,(3)abadsorption by porous liquids,and(4)membrane separation.Rooted in the development of advanced materials for NH3 capture,we conducted a coherent review of the design of different materials,mainly in the past 5 years,their interactions with NH3 molecules and construction of transport pathways,as well as the structure–property relationship,with specific examples discussed.Finally,the challenges in current research and future worthwhile directions for NH3 capture materials are proposed.

Design of dual-functional protic porous ionic liquids for boosting selective extractive desulfurization

Porous ionic liquids have demonstrated excellent performance in the field of separation,attributed to their high specific surface area and efficient mass transfer.Herein,task-specific protic porous ionic liquids(PPILs)were prepared by employing a novel one-step coupling neutralization reaction strategy for extractive desulfurization.The single-extraction efficiency of PPILs reached 75.0%for dibenzothiophene.Moreover,adding aromatic hydrocarbon interferents resulted in a slight decrease in the extraction efficiency of PPILs(from 45.2%to 37.3%,37.9%,and 33.5%),indicating the excellent extraction selectivity of PPILs.The experimental measurements and density functional theory calculations reveal that the surface channels of porous structures can selectively capture dibenzothiophene by the stronger electrophilicity(Eint(HS surface channel/DBT)=-39.8 kcal mol^(-1)),and the multiple extraction sites of ion pairs can effectively enrich and transport dibenzothiophene from the oil phase into PPILs throughπ...π,C-H...πand hydrogen bonds interactions.Furthermore,this straightforward synthetic strategy can be employed in preparing porous liquids,offering new possibilities for synthesizing PPILs with tailored functionalities.

结直肠癌、基质和正常结肠黏膜显微解剖区域N-糖组的显著多样性

Aberrant glycosylation is considered to be a hallmark of colorectal cancer(CRC),as demonstrated by various studies.While the N-glycosylation of cell lines and serum has been widely examined,the analysis of cancer-associated N-glycans from tissues has been hampered by the heterogeneity of tumors and the complexity of N-glycan structures.To overcome these obstacles,we present a study using laser capture microdissection that makes it possible to largely deconvolute distinct N-glycomic signatures originating from different regions of heterogeneous tissues including cancerous,stromal,and healthy mucosa cells.N-glycan alditols were analyzed by means of porous graphitized carbon liquid chromatographyelectrospray ionization tandem mass spectrometry,enabling the differentiation and structural characterization of isomeric species.In total,116 N-glycans were identified that showed profound differences in expression among cancer,stroma,and normal mucosa.In comparison with healthy mucosa,the cancer cells showed an increase in a2-6 sialylation and monoantennary N-glycans,as well as a decrease in bisected N-glycans.Moreover,specific sialylated and(sialyl-)LewisA/X antigen-carrying N-glycans were exclusively expressed in cancers.In comparison with cancer,the stroma showed lower levels of oligomannosidic and monoantennary N-glycans,LewisA/X epitopes,and sulfation,as well as increased expression of(core-)fucosylation and a2-3 sialylation.Our study reveals the distinct N-glycomic profiles of different cell types in CRC and control tissues,proving the necessity of their separate analysis for the discovery of cancer-associated glycans.

Porous solid inspired hyper-crosslinked polymer liquids with highly efficient regeneration for gas purification

Separation media that combine the desired material properties within a single material for a given process remain an ongoing challenge for the gas separations in industry.Process integration of porous solid adsorbents is difficult due to their limited volumetric capacity,whereas issues of volatility and high regeneration temperatures exist for liquid amines and physical solvents.Herein,we report a family of polymer liquids inspired by hyper-crosslinked polymers(HCPs),a class of highly swellable network polymers.Compared with a chemically similar porous solid,the HCP-liquids demonstrate good volumetric capacity and improved selectivity of carbon dioxide over methane.Uptake appears to be enhanced by intramolecular swelling of the HCP-liquids at elevated pressures,while guests are strongly rejected from the HCP-liquids at slightly elevated temperatures,leading to highly efficient regeneration.Heat of adsorption and specific heat capacity of the HCP-liquids are also low,further suggesting favourable process thermodynamics.Additionally being easily prepared at scale,the presented HCP-liquids represent a promising step towards a material with the requisite properties to replace conventional scrubbing solvents to drastically reduce the footprint and energy needs of gas separations.

FTIR investigation of the interfacial properties and mechanisms of CO_(2) sorption in porous ionic liquids

Porous liquids,which are liquids with permanent porosity,have received significant attention as a new class of materials with the potential for far-reaching impacts in a variety of applications including gas separation.In this work,in situ Fourier transform infrared spectroscopy measurements were conducted to investigate the mechanism of carbon dioxide absorption in a porous ionic liquid consisting of ZIF-8 combined with 8,80-(3,6-dioxaoctane-1,8-diyl)bis(1,8-diazabicyclo[5.4.0]undec-7-en-8-ium)bis(trifluoromethanesulfonyl)imide([DBU-PEG][(Tf_(2)N)_(2)]).While the vibrational modes of the pure ionic liquid remain relatively unchanged,the incorporation of carbon dioxide leads to slight structural fluctuations in the ZIF-8 framework whether it is pure solid or as integrated into the porous ionic liquid.The analysis of the vibrational modes of the porous ionic liquid suggests that the interaction of the CO_(2) occurs more strongly with the ring structure of the ZIF-8 framework.The splitting of the asymmetric stretch of the CO_(2) into multiple peaks upon sorption indicate the presence of multiple environments,which could be a combination of free and physisorbed CO_(2) or simply multiple binding sites within the porous ionic liquid.A better understanding of gas sorption mechanisms in this unique material could lead to new porous ionic liquids with enhanced separations properties.

Selective electroreduction of carbon dioxide to formic acid on electrodeposited SnO_2@N-doped porous carbon catalysts

Electrocatalytic reduction of CO_2 is a promising route for energy storage and utilization. Herein we synthesized SnO_2 nanosheets and supported them on N-doped porous carbon (N-PC) by electrodeposition for the first time. The SnO_2 and N-PC in the SnO_2@N-PC composites had exellent synergistic effect for electrocatalytic reduction of CO_2 to HCOOH. The Faradaic efficiency of HCOOH could be as high as 94.1% with a current density of 28.4 mA cm-2 in ionic liquid-MeCN system. The reaction mechanism was proposed on the basis of some control experiments. This work opens a new way to prepare composite electrode for electrochemical reduction of CO_2.

Synthesis of porous aromatic framework with Friedel–Crafts alkylation reaction for CO_2 separation

A novel porous aromatic framework, PAF-8, derived from tetraphenylsilane as basic building unit, was successfully synthesized via Friedel-Crafts alkylation reaction. This PAF material had high thermal stability as well as high surface area （785 m^2 g^-1） calculated from the Brunauer-Emmett-Teller （BET） model. Meanwhile, PAF-8 possessed high performances in gas sorption and especially for CO2 separation.