Sensitive voltammetric determination of xanthinol nicotinate at a carbon nanotubes-ionic liquid gel modified electrode

The electrochemistry of xanthinol nicotinate （Xan） was studied by cyclic voltammetry at a glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes （MWNTs） and room-temperature ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate （BMIMPF6）. The modified electrode exhibited good promotion to the electrochemical oxidation of Xan and an ultrasensitive electrochemical method was proposed for the determination of Xan. This method was successfully applied to the determination of Xan in Xan tablets. C 2009 XiaoYu Bao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Tuning the cross-linked structure of basic poly(ionic liquid)to develop an efficient catalyst for the conversion of vinyl carbonate to dimethyl carbonate

Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.

High Colloidal Stable Carbon Dots Armored Liquid Metal Nano-Droplets for Versatile 3D/4D Printing Through Digital Light Processing(DLP)

Liquid metal(LM)and liquid metal alloys(LMs)possess unique physicochemical features,which have become emerging and functionalized materials that are attractive applicants in various fields.Herein,uniform LM nanodroplets armored by carbon dots(LMD@CDs)were prepared and exhibited high colloidal stability in various solvents,as well as water.After optimization,LMD@CDs can be applied as functional additives for the 3D/4D printing of hydrogel and cross-linked resin through digital light processing(DLP).The light absorption of LMD@CDs not only improved the printing accuracy,but also led to the cross-linking density differential during the post-curing process.Base on the cross-linking density differential of soft hydrogel and photothermal performance of the LM,the 3D printed objects can exhibit stimulus responses to both water and laser irradiation.Additionally,the CDs shell and LM core of LMD@CDs provide the printed objects interesting photoluminescence and electric conductivity capabilities,respectively.We deduce this versatile 3D/4D printing system would provide a new platform for the preparation of multi-functional and stimuli-responsive advance materials.

Microwave-Assisted Confining Growth and Liquid Exfoliation of sp^(3)-Hybrid Carbon Nitride Nano/Micro-Crystals

As one promising carbon-based material,sp^(3)-hybrid carbon nitride has been predicted with various novel physicochemical properties.However,the synthesis of sp^(3)-hybrid carbon nitride is still limited by the nanaoscale,low crystallinity,complex source,and expensive instruments.Herein,we have presented a facile approach to the sp^(3)-hybrid carbon nitride nano/micro-crystals with microwave-assisted confining growth and liquid exfoliation.Actually,the carbon nitride nano/micro-crystals can spontaneously emerge and grow in the microwave-assisted polymerization of citric acid and urea,and the liquid exfoliation can break the bulk disorder polymer to retrieve the highly crystalline carbon nitride nano/micro-crystals.The obtained carbon nitride nano/micro-crystals present superior blue light absorption strength and surprising photoluminescence quantum yields of 57.96% in ethanol and 18.05%in solid state.The experimental characterizations and density functional theory calculations reveal that the interface-trapped localized exciton may contribute to the excellent intrinsic light emission capability of carbon nitride nano/micro-crystals and the interparticle staggered stacking will prevent the aggregation-caused-quenching partially.Finally,the carbon nitride nano/micro-crystals are demonstrated to be potentially useful as the phosphor medium in light-emitting-diode for interrupting blue light-induced eye damage.This work paves new light on the synthesis strategy of sp^(3)-hybrid carbon nitride materials and thus may push forward the development of multiple carbon nitride research.

Ionic liquids-SBA-15 hybrid catalysts for highly efficient and solvent-free synthesis of diphenyl carbonate

Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.

Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO_(2)to Propylene Carbonate

Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.

Enhancing CO_(2) transport with plasma-functionalized ionic liquid membranes

The ionic liquid(IL) 1-butyl-3-methylimidazolium tetrafluoroborate treated with radiofrequency plasma is proposed for functionalization and immobilization on polyethersulfone supports to form supported ionic liquid membranes for CO_(2) separation.The effects of treatment time and transmembrane pressure difference on CO_(2) permeance were evaluated.The best gas permeation performance was obtained with a treatment time of 10 min and the transmembrane pressure difference was 0.25 MPa.Characterization of the materials by Fourier transform infrared spectroscopy,x-ray photoelectron spectroscopy and nuclear magnetic resonance spectroscopy demonstrates that the IL is grafted with carboxyl groups and deprotonated through plasma treatment.A preliminary mechanism for the plasma treatment and facilitated transport of CO_(2)has been proposed on this basis.

Fixation of CO_2 by electrocatalytic reduction to synthesis of dimethyl carbonate in ionic liquid using effective silver-coated nanoporous copper composites

With high surface area,open porosity and high efficiency,a catalyst was prepared and firstly employed in electrocatalytic reduction of CO2 and electrosynthesis of dimethyl carbonate（DMC）.The electrochemical property for electrocatalytic reduction of CO2 in ionic liquid was studied by cyclic voltammogram（CV）.The effects of various reaction variables like temperature,working potential and cathode materials on the electrocatalytic performance were also investigated.80%yield of DMC was obtained under the optimal reaction conditions.

Glycerol carbonate synthesis from glycerol and dimethyl carbonate using guanidine ionic liquids

A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate. In this paper, a series of guanidine-based ionic liquids were synthesized to catalyze the transesterification of glycerol and dimethyl carbonate. The tunable basicity and the anion–cation cooperative effect were responsible for the obtained results. The [TMG][TFE] showed the best activity turnover frequency(TOF)of 1754.0 h^(-1), glycerol(GL) conversion of 91.8%, glycerol carbonate(GC) selectivity of 95.5%) at 80 °C with 0.1 mol% catalyst for 30 min. The reaction mechanism of the transesterification was also proposed.

Waste Activated Sludge Alkaline Fermentation Liquid as Carbon Source for Biological Nutrients Removal in Anaerobic Followed by Alternating Aerobic-Anoxic Sequencing Batch Reactors

Activated sludge process has been widely used to remove phosphorus and nitrogen from wastewater. However,the nitrogen and phosphorus removal is sometimes unsatisfactory due to the low influent COD.Another problem with the activated sludge process is that large amount of waste activated sludge is produced,which needs further treatment.In this study,the waste activated sludge alkaline fermentation liquid was used as the main carbon source for phosphorus and nitrogen removal under anaerobic followed by alternating aerobic-anoxic conditions,and the results were compared with those using acetic acid as the carbon source.The use of alkaline fermentation liquid not only affected the transformations of phosphorus,nitrogen,intracellular polyhydroxyalkanoates and glycogen, but also led to higher removal efficiencies for phosphorus and nitrogen compared with acetic acid.It was observed that ammonium was completely removed with either alkaline fermentation liquid or acetic acid as the carbon source. However,the former resulted in higher removal efficiencies for phosphorus(95%)and nitrogen(82%),while the latter showed lower ones(87%and 74%,respectively).The presence of a large amount of propionic acid in the alkaline fermentation liquid was one possible reason for its higher phosphorus removal efficiency.Exogenous instead of endogenous denitrification was the main pathway for nitrogen removal with the alkaline fermentation liquid as the carbon source,which was responsible for its higher nitrogen removal efficiency.It seems that the alkaline fermentation liquid can replace acetic acid as the carbon source for phosphorus and nitrogen removal in anaerobic fol- lowed by alternating aerobic-anoxic sequencing batch reactor.

An Efficient and Stable Ionic Liquid System for Synthesis of Ethylene Glycol via Hydrolysis of Ethylene Carbonate

An ionic liquid system of [Bmim]X/[Bmim]OH(X Cl,BF4,and PF6,) was developed for the hydroly-sis of ethylene carbonate to ethylene glycol. The important parameters,such as the variety of ionic liquids,molar ratio of [Bmim]X to [Bmim]OH,amount of ionic liquid,molar ratio of water to ethylene carbonate,reaction tem-perature,pressure and reaction time,were investigated systematically. Excellent yield(>93%) and high selectivity(99.5%) of ethylene glycol were achieved. Under the optimum reaction conditions,the ionic liquid system could be reused at least five times and the selectivity of ethylene glycol remained higher than 99.5%.

AgBF_4/[emim][BF_4] supported ionic liquid membrane for carbon monoxide/nitrogen separation

In this paper,AgBF_4/[emim][BF_4] supported ionic liquid membranes(SILMs) were prepared successfully for CO/N_2 separation using nitrogen pressure immobilization procedures.The incorporation of AgBF_4 could decrease membrane weight loss,improve the pressure-resistant ability,and keep the critical pressure(0.45 MPa) of the SILMs.The high viscosity and undissolved Ag BF_4 solids in membrane liquid would disturb gas molecular transport through membrane and give rise to the gas transport resistance.Therefore,the gas permeability decreased remarkably with increasing AgBF_4 carrier content in the membrane.When the molar ratio of AgBF_4 to [emim][BF_4] increased from 0:1 to 0.3:1,the CO/N_2 selectivity of the SILMs showed a great increase from ～1 to ～9 at 20 °C and 0.4 MPa,suggesting that AgBF_4 was an effective carrier for CO facilitated transport.The permeabilities of N_2 and CO increased at higher transmembrane pressure,indicating that molecular transport would dominate the transport process at high pressure.The temperature-dependent gas permeability followed the Arrhenius equation.Moreover,the differences between the activation energies of CO and N_2 became larger after introducing AgBF_4,resulting in more obvious decrease in the CO/N_2 selectivity at higher operating temperature.

Molecular Dynamics Simulation for the Binary Mixtures of High Pressure Carbon Dioxide and Ionic Liquids

Molecular dynamics simulation with an all-atom force field has been carded out on the two binary sys- tems of [bmim][PF6]-CO2 and [bmim][NO3]-CO2 to study the transport properties, volume expansion and micro- structures. It was found that addition of CO2 in the liquid phase can greatly decrease the viscosity of ionic liquids （ILs） and increase their diffusion coefficient obviously. Furthermore, the volume expansion of ionic liquids was found to increase with the increase of the mole fraction of CO2 in the liquid phase but less than 35% for the two simulated systems, which had a significant difference with CO2 expanded organic solvents. The main reason was that there were some void spaces inter and intra the molecules of ionic liquids. Finally, site to site radial distribution functions and corresponding number integrals were investigated and it was found that the change of microstructures of ILs bv addition CO2 had a great influence on the orooerties of ILs.

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.

Pulsed laser ablation in liquid of sp-carbon chains:Status and recent advances

This review provides a discussion of the current state of research on sp-carbon chains synthesized by pulsed laser ablation in liquid.In recent years,pulsed laser ablation in liquid(PLAL)has been widely employed for polyynes synthesis thanks to its flexibility with varying laser parameters,solvents,and targets.This allows the control of sp-carbon chains properties as yield,length,termination and stability.Although many reviews related to PLAL have been published,a comprehensive work reporting the current status and advances related to the synthesis of sp-carbon chains by PLAL is still missing.Here we first review the principle of PLAL and the mechanisms of formation of sp-carbon chains.Then we discuss the role of laser fluence(i.e.energy density),solvent,and target for sp-carbon chains synthesis.Lastly,we report the progress related to the prolonged stability of sp-carbon chains by PLAL encapsulated in polymeric matrices.This review will be a helpful guide for researchers interested in synthesizing sp-carbon chains by PLAL.

Nanoconfinement effect of nanoporous carbon electrodes for ionic liquid-based aluminum metal anode

Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deliver higher energies,compared to current lithium ion batteries.However,the mechanism of charge delivery in the newly developed,ionic liquid-based electrolytic system for RABs differs from that in conventional organic electrolytes.Thus,targeted research efforts are required to address the large overpotentials and cycling decay encountered in the ionic liquid-based electrolytic system.In this study,a nanoporous carbon(NPC)electrode with well-developed nanopores is used to develop a high-performance aluminum anode.The negatively charged nanopores can provide quenched dynamics of electrolyte molecules in the aluminum deposition process,resulting in an increased collision rate.The fast chemical equilibrium of anionic species induced by the facilitated anionic collisions leads to more favorable reduction reactions that form aluminum metals.The nanoconfinement effect causes separated nucleation and growth of aluminum nanoparticles in the multiple confined nanopores,leading to higher coulombic efficiencies and more stable cycling performance compared with macroporous carbon black and 2D stainless steel electrodes.

Recovery of carbon monoxide from flue gases by reactive absorption in ionic liquid imidazolium chlorocuprate(I): Mass transfer coefficients

Recovery of carbon monoxide from flue gases by selective absorption of carbon monoxide in an imidazolium chlorocuprate（l） ionic liquid is considered in this work as an alternative to the use of molecular volatile solvents such as aromatic hydrocarbons. The present work evaluates the CO mass transfer rates from the gas phase to the ionic liquid solutions in the absence of chemical reaction. To that end, carbon dioxide was employed as an inert model gas and absorption experiments were performed to assess the influence of different process variables in a batch reactor with fiat gas-liquid interface. The experimental mass transfer coefficients showed significant var- iation with temperature, （3.4-10.9） × 10^-7 m·s^-1 between 293 and 313 K; stirring speed, （10.2- 33.1）× 10^-7 m.s 1 between 100 and 300 r·min^-1; and concentration of copper（1）, （6.6-10.2） × 10^-7 m·s^-1 between 0.25 and 2 mol· L^- 1. In addition, the mass transfer coefficients were eventually found to follow a poten- tial proportionality of the type kL ∝μ^-0.5 and the dimensionless correlation that makes the estimation of the mass transfer coefficients possible in the studied range of process variables was obtained： Sh=10^-2.64 Re^1.07 , Sc^0.75,These results constitute the first step in the kinetic analysis of the reaction between CO and imidazolium chlorocuprate（I） ionic liquid that determines the design of the separation units.

Probing the intrinsic catalytic activity of carbon nanotubes for the metal-free oxidation of aromatic thiophene compounds in ionic liquids

A metal-free catalytic system combining oxidized carbon nanotubes (oCNTs) and ionic liquids (ILs) is presented for the oxidation of aromatic thiophene compounds with H2O2 as an oxidant. The oCNTs exhibit impressively high activity and stability in the system, which show an even better performance than those of some reported metal catalysts. The ILs are proved to have indispensable influence on the enhanced catalytic performance of the oCNTs. Detailed characterization by TG-MS and XPS demonstrates that the carbonyl groups are the active sites for the oxidation process, which is further supported by the deactivation and the model catalysts experiments. The quantitative analysis of different oxygen groups in oCNTs could be achieved by an isothermal temperature programmed TG-MS method. The concentration of carbonyl groups is 1.46 mmol per 1 g oCNTs and the tuiriover frequency of oCNTs could also be obtained (10.7 h^-1 in the presence of OmimPF6). H2O2 decomposition experiments combined with the EPR results reveal that the presence of OmimPF6 can avoid the intermediate HO· to form O2 and then improve the catalytic performance of oCNTs for the oxidation of dibenzothiophene.

On the liquid-phase technology of carbon fiber/aluminum matrix composites

The main problems with the liquid-phase technology of carbon fiber/aluminum matrix composites include poor wetting of the fiber with liquid aluminum and formation of aluminum carbide on the fibers’surface.This paper aims to solve these problems.The theoretical and experimental dependence of porosity on the applied pressure were determined.The possibility of obtaining a carbon fiber/aluminum matrix composite wire with a strength value of about 1500 MPa was shown.The correlation among the strength of the carbon fiber reinforced aluminum matrix composite,the fracture surface,and the degradation of the carbon fiber surface was discussed.

Analysis of the Carbon Nano-Structures Formation in Liquid Arcing

Graphite electrodes were used for the direct current （DC） arc discharge in water. And high-resolution transmission electron microscopy （HRTEM） was used to investigate the products. Based on the experimental phenomena and nano-structure products, arc plasma characteristics in water were analyzed theoretically. Two growth regions and relevant growth modes were proposed to interpret the formation mechanisms of nano-structures by arc discharge in water. Furthermore, liquid nitrogen and cross magnetic field was applied to change the arcing state respectively, and new carbon nano-structures were obtained. Their formation mechanisms were also analyzed correspondingly.