Highly defective HKUST-1 with excellent stability and SO_(2) uptake: The hydrophobic armor effect of functionalized ionic liquids

Water stability is one of the most important factors restricting the practical application of metal organic frameworks (MOFs). In this work, wefabricate a highly defective HKUST-1 framework with a mixed valence of CuI/CuIIby mechanical ball milling method. This defective HKUST-1is embellished by functionalized ionic liquids as hydrophobic armor, making the hybrid HIL1@HKUST-1 exhibits outstanding water stability,remarkable SO_(2) adsorption (up to 5.71 mmol g^(-1)), and record-breaking selectivity (1070 for SO_(2)/CO_(2) and 31,515 for SO_(2)/N_(2)) at 25 ℃ and0.1 bar, even in wet conditions.

Carboxylic bacterial cellulose fiber-based hydrogel electrolyte with imidazole-type ionic liquid for dendrite-free zinc metal batteries

Aqueous zinc metal batteries are regarded as the most promising energy storage system due to their advantages of high safety,low cost,and high theoretical capacity.However,the growth of dendrites and the occurrence of side reactions hinder the development of zinc metal batteries.Despite previous attempts to design advanced hydrogel electrolytes,achieving high mechanical performance and ionic conductivity of hydrogel electrolytes has remained challenging.In this work,a hydrogel electrolyte with an ionic crosslinked network is prepared by carboxylic bacterial cellulose fiber and imidazole-type ionic liquid,following by a covalent network of polyacrylamide.The hydrogel electrolyte possesses a superior ionic conductivity of 43.76 mS cm^(−1),leading to a Zn^(2+)migration number of 0.45,and high mechanical performance with an elastic modulus of 3.48 GPa and an elongation at breaking of 38.36%.More importantly,under the anion-coordination effect of the carboxyl group in bacterial cellulose and[BF4]−in imidazole-type ionic liquid,the solvation sheath of hydrated Zn^(2+)ions and the nucleation overpotential of Zn plating are regulated.The results of cycled testing show that the growth of zinc dendrites is effectively inhibited and the generation of irreversible by-products is reduced.With the carboxylic bacterial cellulose-based hydrogel electrolyte,the Zn||Zn symmetric batteries offer good cyclability as well as Zn||Ti batteries.

Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20%(mass) Ni SO4aqueous solution at 130 ℃ and [Bmim]Cl at 150 ℃, the purity of a-chitin can be up to 96.5%(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.

Application of ionic liquids in hydrometallurgy of nonferrous metals

Ionic liquids as green solvents have shown important application in the extraction and separation of nonferrous metals.The new application perspective,the important fundamental and the applied studies of the extraction and separation of nonferrous metals in ionic liquids,including the dissolution and corrosion of metal and metal oxide,hydrometallurgy of chalcopyrite and metallic oxidized ore,and extraction and separation of metal ions,are introduced.

Ionic liquids for high performance lithium metal batteries

The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high ionic conductivity,non-flammability,and the properties of promoting the formation of stable SEI films.Deeply understanding the problems existing in lithium metal batteries and the role of ionic liquids in them is of great significance for improving the performance of lithium metal batteries.This article reviews the effects of the molecular structure of ionic liquids on ionic conductivity,Li^(+)ion transference number,electrochemical stability window,and lithium metal anode/electrolyte interface,as well as the application of ionic liquids in Li-high voltage cathode batteries,Li-O_(2) batteries and Li-S batteries.The molecular design,composition and polymerization will be the main strategies for the future development of ionic liquid-based electrolytes for high performance lithium metal battery.

Electron paramagnetic resonance studies of the chelate-based ionic liquid in different solvents

The electron paramagnetic resonance spectra of the chelate-based ionic liquid[C_(10)mim][Cu(F_6-acac)_3]in different solvents have been obtained at 120 K.It was found that the values of the^(63)Cu hyperfine coupling constants(A_(IL))of[C_(10)mim][Cu(F_6-acac)_3]in molecular solvents were from 116 to 180 Gauss.Moreover,the A_(IL)values in general ionic liquids are more complicated,and two sets of peaks can often be observed in their electron paramagnetic resonance spectra.Based on the Kamlet-Taft parameters,relative permittivity,the experimental results were discussed in terms of solvation effect and coordination of the solvents.

Deep Extractive Desulfurization of Gasoline with Ionic Liquids Based on Metal Halide

Ionic liquid [Et3NH]C1-FeCl3/CuCl was synthesized by mixing [Et3NH]Cl, anhydrous FeCl3 and anhydrous CuCl, and the desulfurization activity of this ionic liquid was tested. It exhibited remarkable ability in effective desulfurization of model gasoline （thiophene in n-octane） and fluid catalytic cracking （FCC） gasoline, and the sulfur removal of thiophene in model oil （V（IL）： V（oil）=0.08） could reach 93.9% in 50 min at 50 ℃. Low-sulfur （〈10 μg/g） FCC gasoline could be obtained after three extraction runs at an ionic liquid/oil volume ratio of 0.1, with the yield of FCC gasoline reaching 94.3%. The ionic liquid could be recycled 5 times with merely a slight decrease in activity.

Quantum chemical aided molecular design of ionic liquids as green electrolytes for electrodeposition of active metals

Quantum chemical calculation was used to estimate the reduction potentials of 25 organic cations and the oxidation potentials of 11 anions.This information was used to select promising cations and anions for the preparation of ionic liquids as green electrolytes for electrodeposition of active metals.The reasonable linear correlations between the lowest unoccupied molecular orbital(LUMO)energies and the reduction potentials of cations,and the linear relationships between the oxidation potentials and the highest occupied molecular orbital(HOMO)energies of anions were obtained.The orders of electrochemical stability for cations and anions being obtained agree well with the experimental measurements.The suitable ionic liquids with sufficiently wide electrochemical windows for electrodeposition of active metals are suggested to be[Emim]NTf2,[Bmim]NTf2,[Bmim]BF4, [Bmim]PF6,[Bmim]CTf3,[Emim]BF4,[Emim]PF6,[Emim]CTf3..

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.

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.

Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid

Direct conversion of cellulose into 5-hydroxymethylfurfural(HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride(Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone(FHMK),and furfural(FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives(HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF(35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeCl3/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF(39.9%) with total yield(63.8%) of furans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals(5~20 min).

Metal organic framework‐ionic liquid hybrid catalysts for the selective electrochemical reduction of CO_(2) to CH4

The electrochemical reduction of CO_(2) towards hydrocarbons is a promising technology that can utilize CO_(2) and prevent its atmospheric accumulation while simultaneously storing renewable en‐ergy.However,current CO_(2) electrolyzers remain impractical on a large scale due to the low current densities and faradaic efficiencies(FE)on various electrocatalysts.In this study,hybrid HKUST‐1 metal‐organic framework‒fluorinated imidazolium‐based room temperature ionic liquid(RTIL)electrocatalysts are designed to selectively reduce CO_(2) to CH_(4).An impressive FE of 65.5%towards CH_(4) at-1.13 V is achieved for the HKUST‐1/[BMIM][PF_(6)]hybrid,with a stable FE greater than 50%maintained for at least 9 h in an H‐cell.The observed improvements are attributed to the increased local CO_(2) concentration and the improved CO_(2)‐to‐CH_(4) thermodynamics in the presence of the RTIL molecules adsorbed on the HKUST‐1‐derived Cu clusters.These findings offer a novel approach of immobilizing RTIL co‐catalysts within porous frameworks for CO_(2) electroreduction applications.

New Ionic Liquids with Buffering and Chelating Abilities for Enzyme Engineering

Ionic liquids (ILs) with buffering and chelating abilities were designed and synthesized on the basis of ethylenediaminetetraacetic acid (EDTA) for the development of buffered enzymatic IL systems and for enzymatic reaction in heavy metal containing aqueous system. Transesterification activity of Candida antarctica lipase B dissolved in the hydroxyl-functionalized IL was buffer dependent. High activity and outstanding stability was obtained with the buffered enzymatic IL systems for the transesterification. In heavy metal containing aqueous system, EDTA IL buffers as Hg2+ chelators protected horseradish peroxidase (HRP) against Hg2+-induced denaturation and precipitation. Higher pH favored the protection, while at lower pH the protection diminished. We can conclude that the new ILs possess both buffering and chelating abilities.

Ionic Interactions in Molecular and Liquid States ofPolyvalent Metal Halides

Progress in the development of phenomenological models for the microscoplc interactions in the halides of polyvalent metals is reviewed, with main attention to neutral and ionized molecular states and to the melts of these materials. The following physical problems are discussed: (1)bond bending in the molecules of the alkaline-earth halides, (2) binding of molecular dimers and halogen transfer reactions relevant to the melts of trivalent metal halides, (3) stability of molecular ions in liquid mixtures of polyvalent metal halides and alkali halides, and (4) stabilityof molecular ions and reduced-valence states in molten cryolite under addition of sodium metal.

Recent progress in ionic liquid-based electrolytes for nonaqueous and aqueous metal batteries

Nonaqueous Li metal batteries(LMBs)and aqueous Zn metal batteries(ZMBs)are promising next-generation secondary batteries owing to their high energy density.Selecting an appropriate electrolyte is critical for addressing the safety issues nonaqueous and aqueous metal batteries can encounter.Ionic liquids(ILs)have been widely used in secondary metal batteries because they are non-flammable,present good thermal stability,and have wide electrochemical windows.This review highlights the research progress on IL-based electrolytes for stable Li/Zn metal anodes.We focus particularly on these electrolytes'electrochemistry and functionalities at the electrolyte/anode interface for inhibiting dendrite growth,preventing side reactions,and enhancing electrochemical performance.It is expected that this review will shed some light on the development of ILs for nextgeneration metal batteries.

The effect of temperature on ionic liquid modified Fe-N-C catalysts for alkaline oxygen reduction reaction

Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies operated at room temperature it remains unclear whether the IL-associated boosting effect can be maintained at elevated temperature, which is of high relevance for practical applications in low temperature fuel cells. Herein, Fe-N-C catalysts were modified by introducing small amounts of hydrophobic ionic liquid, resulting in boosted electrocatalytic activity towards the alkaline oxygen reduction reaction at room temperature. It is demonstrated that the boosting effect can be maintained and even strengthened when increasing the electrolyte temperature up to 70℃. These findings show for the first time that the incorporation of ionic liquid is a suited method to obtain advanced noble metal-free electrocatalysts that can be applied at operating temperature condition.

Electronic Properties of Nanopore Edges of Ferromagnetic Graphene Nanomeshes at High Carrier Densities under Ionic-Liquid Gating

Graphene edges with a zigzag-type atomic structure can theoretically produce spontaneous spin polarization despite being a critical-metal-free material. We have demonstrated this in graphene nanomeshes (GNMs) with honeycomb-like arrays of low-defect hexagonal nanopores by observing room-temperature ferromagnetism and spin-based phenomena arising from the zigzag-pore edges. Here, we apply extremely high electric fields to the ferromagnetic (FM) GNMs using an ionic-liquid gate. A large on/off-ratio for hole current is observed for even small applied ionic-liquid gate voltages (Vig). Observations of the magnetoresistance behavior reveal high carrier densities of ~1013 cm-2 at large Vig values. We find a maximum conductance peak in the high -Vig region and its separation into two peaks upon applying a side-gate (in-plane external) voltage (Vex). It is discussed that localized edge-π band with excess-density electrons induced by Vig and its spin splitting for majority and minority of spins by Vex (half-metallicity model) lead to these phenomena. The results must realize critical-element-free novel spintronic devices.

添加剂在离子液体电沉积金属及合金中的应用

近年来,基于离子液体电沉积制备金属和合金镀层已被广泛应用于多个研究领域,其电沉积过程可以克服传统水溶液体系电化学窗口窄、易受析氢副反应干扰等缺陷;相较于高温熔盐体系,离子液体可在温和条件下电沉积制备活泼金属及其合金.离子液体具有较高的黏度,导致离子迁移速率低,电沉积过程中易产生浓差极化,从而影响沉积产物的品质和性能.通过向离子液体电沉积体系中引入添加剂可以改变活性物种的电化学还原电位,进而影响晶粒的电化学结晶过程,显著改善沉积层的微观结构和性能.本文归纳总结了添加剂对离子液体中电沉积活泼金属、过渡金属和贵金属及其合金等方面的研究进展,系统分析了当前添加剂在离子液体电沉积金属及合金过程中的作用机理、效用和局限性,并展望了未来离子液体电沉积添加剂的重点研究方向.

离子液体辅助合成纳米金属氧化物的研究进展

离子液体的物理化学特性和氢键作用能够辅助纳米金属氧化物的定向生长,具有传统溶剂所不具备的优点,在纳米金属氧化物材料合成方面受到重视。综述了离子液体辅助合成TiO_(2),ZnO,γ-Al_(2)O_(3),ZrO_(2)四种纳米金属氧化物的最新研究进展,重点结合离子液体阴阳离子的影响及诱导机制进行讨论。最后总结了离子液体辅助合成纳米金属氧化物可能面临的挑战和未来的研究方向。

MOFs基多孔液体的合成及其气体吸附分离的应用

多孔液体(PLs)是一种兼具多孔固体材料与流动液体材料两者优点的新型材料,自2007年PLs的概念首次被提出以来,已经受到了广泛关注。目前,基于不同多孔客体(如多孔有机笼、金属有机多面体、共价有机框架、多孔碳、沸石、空心硅、金属有机框架等)的PLs陆续被报道,作为多孔客体,其中金属有机框架(MOFs)由于其比表面积大、可调的孔隙结构、良好的热稳定性及化学稳定性等优点,成为制备PLs优异的先进多孔客体,但目前鲜有基于MOFs的PLs的专门综述。以UiO-66、ZIF基PLs为代表归纳了MOFs基PLs的合成进展,并总结了其在气体吸附分离领域的应用,最后,对MOFs基PLs的未来发展进行了展望。