Imidazolium group prompted alkaline anion-exchange membrane with high performance for efficient electrochemical CO_(2) conversion

Development of high-performance hydroxide-conductive membranes is a focus research subject owing to promising applications in electrochemical reduction of CO_(2)(eCO_(2)RR).However,few satisfactory membranes have been developed to maximize the performance of CO_(2) electrolyzers,despite its role as the core in regulating ion transport and preventing product crossover or fuel loss.Herein,we report the synthesis of alkaline anion-exchange membranes fabricated by poly(vinyl-alcohol)(PVA)and poly[(3-methyl-1-vinylimidazoliummethylsulfate)-co-(1-vinylpyrrolidone)](PQ44)for use in CO_(2) electrolysis.Owing to the unique imidazolium ring structure coupled with a three-dimensional semiinterpenetrating porous internal architecture,the PVA/PQ44-OH-membranes provide a high hydroxide conductivity(21.47 mS cm^(-1)),preferable mechanical property and thermal stability.In particular,the eCO_(2)RR used PVA/PQ44-OH^(-) as electrolyte membrane realized a charming Faradaic efficiency(88%)and partial current density(29 mA cm^(-2))at0.96 VRHE and,delivered the excellent durability over 20 h electrolysis in 0.5 mol L^(-1) KHCO_(3) electrolyte.Notably,it can even enable an ultrahigh current density beyond 100 mA cm^(-2) at^(-1).11 VRHE when the electrolyte was KOH instead,and produced the FEHCOOof 85%at a low potential of0.81 VRHE,superior to both commercial alkaline A201 and acidic Nafion117 membrane.

Synthesis and Surface Activity of Heterogemini Imidazolium Surfactants

A series of heterogemini imidazolium surfactants with two-methylene spacer groups （[Cm- 2-Cnim]Br2, m, n=8, 10, 12, 14, 16; m≠n） have been synthesized and characterized by 1H NMR and ESI-MS spectroscopy. The effects of various reaction parameters, including stoichiometry, reaction temperature and time, were investigated. In addition, the surface activity study about heterogemini imidazolium surfactants was carried out and the influences of dissymmetric degree on the surface properties were also discussed.

Synthesis of a kind of geminal imidazolium ionic liquid with long aliphatic chains

A novel geminal imidazolium ionic liquid with long hydrocarbon group, 1,4-bis （3-tetradecylimidazolium- 1-yl） butane bromide was synthesized and an efficient synthesized method was introduced detailedly. Its structure was determined by FT-IR, ^1H NMR and elemental analysis.

Benzoin Condensation in Imidazolium Based Room-temperature Ionic Liquids

Benzoin condensation promoted efficiently in three imidazolium based room tempera- ture ionic liquids [bmim]Br, [bmim]BF4 and [Bnmim]BF4 is reported for the first time. Benzoins were obtained in up to 91% yield within less than 30 min under mild conditions.

Unraveling Passivation Mechanism of Imidazolium-Based Ionic Liquids on Inorganic Perovskite to Achieve Near-Record-Efficiency CsPbI_(2)Br Solar Cells

The application of ionic liquids in perovskite has attracted wide-spread attention for its astounding performance improvement of perovskite solar cells(PSCs).However,the detailed mechanisms behind the improvement remain mysterious.Herein,a series of imidazolium-based ionic liquids(IILs)with different cations and anions is systematically investigated to elucidate the passivation mechanism of IILs on inorganic perovskites.It is found that IILs display the following advantages:(1)They form ionic bonds with Cs^(+)and Pb^(2+)cations on the surface and at the grain boundaries of perovskite films,which could effectively heal/reduce the Cs^(+)/I−vacancies and Pb-related defects;(2)They serve as a bridge between the perovskite and the hole-transport-layer for effective charge extraction and transfer;and(3)They increase the hydrophobicity of the perovskite surface to further improve the stability of the CsPbI_(2)Br PSCs.The combination of the above effects results in suppressed non-radiative recombination loss in CsPbI_(2)Br PSCs and an impressive power conversion efficiency of 17.02%.Additionally,the CsPbI_(2)Br PSCs with IILs surface modification exhibited improved ambient and light illumination stability.Our results provide guidance for an indepth understanding of the passivation mechanism of IILs in inorganic perovskites.

Two Coordination Novel Polymers Based on a Flexible Ligand N,N'-diacetic Acid Imidazolium

{[Cu_3（cis-DAM）_4（OH）_2]·12H_2O}_n 1 and [Ag_3（trans-DAM）_2（NO_3）]_n 2 with a flexible ligand N,NA-diacetic acid imidazolium（HDAM） were synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic I222 space group with a = 12.033（2）,b = 12.498（3）,c = 14.963（3） A,V = 2250.4（8） A^3,Z = 8,C_7H_（13.5）N_2O_（7.5）Cu_（0.75）,M_r = 293.35,D_c = 1.732 g·cm^-3,F（000） = 1210,GOF = 1.087,the final R（I 〉 2σ（I）） = 0.0521 and w R（all data） = 0.1386. Compound 2 crystallizes in the monoclinic C2/c space group with a = 21.601（4）,b = 8.321（2）,c = 13.589（3） A,β = 126.95（3）°,V = 1951.9（7） A^3,Z = 8,C_7H_7N_（2.5）O_（5.5）Ag_（1.5）,M_r = 375.96,D_c = 2.559 g·cm^-3,F（000） = 1448,GOF = 1.017,R（I 〉 2σ（I）） = 0.0222 and w R（all data） = 0.0633. Compound 1 displays a novel 2D layer,consisting of a couple of left-helical chains with a pitch of 12.498（3） A formed by μ_3-cis-DAM~– ligands and Cu（1） ions,which are stabilized by hydrogen bonding interactions to give a 3D supramolecular framework. As for 2,Ag（1） ions are doubly bridged by trans-DAM~– and NO_3~– to form [Ag（1）_2O_4] chains,which are further connected by Ag（2） and trans-DAM~– to build a 3D framework. Additionally,thermogravimetric analyses,FT-IR spectroscopy,UV-visible spectroscopy,and the fluorescent properties were discussed.

Structure of Co-crystals Formation from Imidazolium and Aromatic Ligands

In this study, two new co-crystals based on rigid imidazolium ligand （2,2＇-（（1,1’- biphenyl）-4,4＇-diyl）bis（2H-imidazo[1,5-a]pyridine-4-ium） hexafluorophosphate （L）） and 4,4＇- bipyridine （Bpy） and benzene （Ben）, formulated as L（Bpy）0.5 （co-crystal 1） and L（Ben） （co-crystal 2）, were obtained. Crystal data for 1： Pī space group with α = 10.921（4）, b = 16.998（6）, c = 17.666（6） A, α = 95.720（7）, β = 104.272（7）, γ = 93.340（6）°, V = 3150.5（19） A^3 and Z = 2; and crystal data for 2： monoclinic C2/m space group with α = 25.90（2）, b = 9.631（9）, c = 6.371（6） A, β = 95.26（2）°, V = 1583（2） A3 and Z = 2. Co-crystal 1 was dependent on hydrogen bonds and π···π stacking, while only hydrogen bonds are present in 2. Two new co-crystals were characterized by IR, NMR spectra, thermogravimetric and ultraviolet absorption analyses.

Dual-ionic imidazolium salts to promote synthesis of cyclic carbonates at atmospheric pressure

Novel dual-ionic imidazolium salts are shown to display excellent catalytic activity for cycloaddition of carbon dioxide and epoxides under room temperature and atmospheric pressure(0.1 MPa)without any solvent and co-catalyst leading to 96.1%product yield.It can be reused five times to keep the product yield over 90%.These intriguing results are attributed to a new reaction mechanism,which is supported by theoretical calculations along with the measurements of ^(13)C NMR spectrum and Fourier transform infrared spectroscopy(FT-IR).The excellent catalytic activity can be traced to a CO_(2)-philic group along with an electrophilic hydrogen atom.Our work shows that incorporation of CO_(2)-philic group is an feasible pathway to develop the new efficient ionic liquids.

Ab Initio Calculation of Room Temperature Ionic Liquid 1-Ethyl-3-Methyl-Imidazolium Chlorocuprate (Ⅰ)

The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^＋（1-ethyl-3-methyl-imidazolium^＋）, CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM＋^-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2- pairs. Full optimization and frequency analyses of EMIM^＋, CuCl2^-, Cu2Cl3^-, CuC13^-, eight initial EMIM^＋-CuCl2^-, six EMIM^＋-Cu2Cl3^-, and four EMIM^＋-CuCl3^2- geometries have been carried out using Gaussian-94 soft-package at 6-31＋G（d,p） basis set level for hydrogen, carbon, nitrogen, chlorine atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy of EMIM^＋-CuCl2^-, EMIM＋-Cu2Cl3^-, EMIM^＋-CuCl3^2-, single EMIM^＋, CuCl2^-, Cu2Cl3^-, and CuCl3^2- have been comparatively studied. The calculated results showed that EMIM^＋-CuCl2^- pair conformer of lowest energy was five ring parallel to Cl-Cu-Cl with 3.2A distance, EMIM^＋-CuCl3^2- pair conformer of lowest energy was five ring parallel to CuCl3^2-plane with 3.4A distance, and the optimized EMIM^＋-Cu2Cl3^- pair conformer of lowest energy was five ring perpendicular to Cl-Cu-Cl-Cu-Cl plane with 3.0A distance between the terminal Cl atoms and the 5-ring of EMIM^＋. The cohesion between cations and anions is brought about by C-H. C1 hydrogen bonds that are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency. The assigned frequencies were in agreement with the experimental report. The low energy of interaction because of the bulkyasymmetry of EMIM＋ and the charge dispersion of cation and anion leads to the low melting point of the ionic liquids, EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2-. The interaction energy of EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2- is 309.0 kJ/mol, 316.8 kJ/mol, and 320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions was also investigated by single point energy scan.

Syntheses and Crystal Structures of Two Coordination Polymers Based on a Flexible Ligand N,N'-Diacetic Acid Imidazolium

Two coordination compounds with a flexible ligand N,N？-diacetic acid imidazolium（HDAM）,{[Co（trans-DAM）（bipy）（H2O）2]（OH）·4H2O}n 1 and {[Cd（trans-DAM）（bipy）（H2O）]（NO3）？2H2O}n 2（bipy = 4,4＇-bipyridine）,were prepared and characterized by single-crystal X-ray diffraction.Compound 1 crystallizes in monoclinic,space group P2/n with a = 7.589（6）,b = 11.444（2）,c = 12.894（3）（A°）,β = 90.99（3）°,V = 1119.8（4）（A°）^3,Z = 4,C8.5H14N2O5.5Co0.5,Mr = 261.68,Dc = 1.552 g/cm^3,F（000） = 546,μ = 0.832 mm^-1,the final R = 0.0657 and wR = 0.1958.Compound 2 crystallizes in the monoclinic C2 space group with a = 17.479（4）,b = 11.689（2）,c = 11.670（2）,β = 117.13（3）°,V = 2121.9（7）3,Z = 4,C17H21N5O10Cd,Mr = 567.79,Dc = 1.777 g/cm^3,F（000） = 1144,μ = 1.096 mm^-1,the final R = 0.0233 and wR = 0.0638.In 1,the Co（II） ions are linked by μ2-trans-DAM-and bipy ligands to build a 2D（4,4） rectangular grid layer,exhibiting a 4-connected sql net.As for 2,μ3-trans-DAM-and bipy bridge Cd（II） ions form a 2D double-layer,consisting of a couple of（4,4） grid layers,which can be viewed as a（3,4）-connected network.In both compounds,the 2D structures are stabilized by hydrogen bonding interactions to give 3D supramolecular frameworks.Additionally,FT-IR spectroscopy,UV-Visible spectroscopy,and the fluorescent properties are discussed.

A Novel 2D Architecture from Bismuth and Flexible Ligand N,N'-Diacetic Acid Imidazolium Chloride

A new compound {[Bi（trans-DAM）（cis-DAM）（H2O）]NO3·H2O}n 1 derived from bismuth and the flexible ligand N,N＇-diacetic acid imidazolium chloride （H2DAMCl） was obtained by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic P21/c space group with a = 9.2298（18）, b = 13.339（3）, c = 17.090（3） , β = 105.38（2）°, V = 2028.7（7）A^3, Z = 4, C14H18N5O13Bi, Mr = 673.31, Dc = 2.204 g/cm^3, F（000） = 1296, μ = 8.772 mm-1, the final R = 0.0472 and wR = 0.1441 for 4129 observed reflections （I 〉 2σ（I））. In 1, the carboxylic groups from DAM- ligands adopt a cheating mode to link bismuth ions to form a 2D sheet network. These sheets are further connected by hydrogen bonding interactions to give an interesting 3D supramolecular framework. 2D correlation analysis of IR of 1 with thermal and magnetic perturbation was introduced to ascertain the characteristic adsorption of the groups overlapped in the 1D IR spectrum. Additionally, compound 1 exhibits fluorescent emission at room temperature.

Electrochemical extraction of lead from urea-1-ethyl-3-methylimidazolium fluoride system containing PbO at 353 K

To electrochemically extract Pb from PbO at room temperature, a new electrolyte, urea-1-ethyl-3-methylimidazolium fluoride(urea-[EMIM]F), was synthesized to dissolve PbO. Afterwards, the electrochemical behavior of Pb in this electrolyte was studied. The density, viscosity and conductivity of this electrolyte were investigated before electroextraction. The electrochemical behavior of Pb in the urea-[EMIM]F system was recorded via cyclic voltammograms, chronoamperometry and potentiostatic electrolysis. The results illustrate that Pb can be electrochemically extracted from PbO in this system at room temperature and that Pb reduction involves a quasireversible process and follows a one-step and two-electron transfer process. The reduction of Pb proceeds with a three-dimensional(3 D) progressive model. With an increase in temperature, the onset potentials for Pb reduction shift anodically. The diffusion coefficient of Pb(II) is determined to be 6.88×10-10 cm2/s at 353 K. Additionally, spherical Pb particles are obtained after electrodeposition in the urea-[EMIM]F system via potentiostatic electrolysis.

A New Type of Biomimetic Model: Design, Synthesis andCharacteriration of Imidazolium Bis-Estrogen

Two imidazolium bis-estrogens as a new type of biomimetic model, which possesspotential multiple biomimetic functions, were srnthesized in gcod yields by three steps fromestrogen. All new compounds were characterized by MS, 1HNMR and elemental analysis.

DFT Studies on the Isomerization of Butene Double Bond Catalyzed by 1-Butyl-3-methyl-imidazolium in Ionic Liquid

The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.

Strong dual-state emission of unsymmetrical and symmetrical thiazolothiazole-bridged imidazolium salts

A novel thiazolothiazole-bridged imidazole derivative(1) was found to exhibit blue fluorescence in gaseous state or in methanol and yellow fluorescence in solid state. The N-alkylation of imidazole subunit(s) in 1 using n-propyl iodide generated unsymmetrically or symmetrically alkylated thiazolothiazolebridged imidazolium salts with good water solubility and remarkably strong emission in solution. Furthermore, the replacement of iodide counter-anion by triflate or bis(trifluoromethane sulfonyl)imide achieved remarkably strong emission in solid state and in solution as well as good water solubility. The strong fluorescence of dicationic salts with triflate and NTf_(2)^(-)counter-anions in solid state can be ascribed to their twisted and rigid structures induced by interionic C-H···F hydrogen bonding.

四种烷基咪唑磷酸酯离子液体的热力学性质

针对烷基咪唑磷酸酯离子液体的热物性数据较少的问题,本文在常压下测定了1-乙基-3-甲基咪唑磷酸二氢盐([EMIM][DHP])、1-乙基-3-甲基咪唑磷酸二甲酯盐([EMIM][DMP])、1-乙基-3-甲基咪唑磷酸二乙酯盐([EMIM][DEP])、1-丁基-3-甲基咪唑磷酸二丁酯盐([BMIM][DBP])四种烷基咪唑磷酸酯离子液体的密度、黏度(293.15~353.15K)和电导率(293.15~343.15K),并且测定了四种离子液体的热稳定性。结果表明,离子液体的密度、黏度随温度的升高而减小,而电导率随温度的升高而增大。采用自然对数方程关联四种离子液体的密度,根据实验值计算到了离子液体体积性质;采用VFT方程关联离子液体黏度和电导率,其中密度与电导率的实验值与模型相关系数R2达到0.9999,黏度相关系数R2达到0.99999,实验测定的数据与模型一致;四种离子液体的热稳定性相近,分解温度均在271.9~278.6℃范围内;瓦尔登规则分析表明,四种烷基咪唑磷酸酯离子液体符合Walden规则,而[EMIM][DMP]和[EMIM][DEP]被归类为“good ionic liquids”。

咪唑鎓盐基材料电催化二氧化碳还原研究进展

随着化石能源的使用日益增加,大气中CO_(2)的浓度不断上升,给环境带来了挑战。通过催化将CO_(2)转化为高附加值化学品为解决这些问题提供了一个机会,并为燃料合成开辟了一条新的途径,最终有助于减少CO_(2)排放并实现碳中和。在众多的方法中,利用可再生清洁能源进行CO_(2)电还原反应(CO_(2)RR)以其反应条件温和、反应进度可控、环境友好以及可以产生大量的附加值产品而受到重视。在此背景下,咪唑鎓基材料及其衍生物已成为CO_(2)RR的有潜力的候选材料。这些材料对CO_(2)有很强的亲和力,并且在CO_(2)RR系统中作为电解质和电催化剂都有应用。所以它们的主要优点之一是能够在催化体系中富集CO_(2),有效地抑制析氢副反应(HER),并提高CO_(2)RR产物的选择性。了解电催化条件下咪唑鎓基离子液体(Im-ILs)与CO_(2)分子之间的相互作用机制对于从分子角度深入了解为什么添加Im-ILs可以改善CO_(2)RR性能至关重要。此外在非均相电催化剂中,Im-ILs作为表面修饰基团和捕集剂,可以显著改变催化剂的表面环境和疏水性,从而促进CO_(2)RR。值得注意的是,Lehn型和金属卟啉分子催化剂中的咪唑鎓基团已被发现对这些催化剂在CO_(2)RR中的性能有影响。N-杂环卡宾(NHC)基电催化剂作为咪唑鎓与CO_(2)相互作用的活性形式之一,表现出优异的CO_(2)RR性能。将NHC基电催化剂引入多孔多相催化剂和分子催化剂中,可以稳定金属纳米颗粒,提高捕获CO_(2)的能力,从而提高CO_(2)RR活性。总之,在CO_(2)RR中使用咪唑鎓基材料对于推进CO_(2)转化,实现可持续、有效合成高附加值化学品具有巨大的前景。

2,4,5-三碘基咪唑在微通道式反应器中的硝化反应

采用微通道式反应技术,以2,4,5-三碘基咪唑(2,4,5-TII)为原料,分别在20%、50%、65%、98%不同质量分数的硝酸中进行硝化反应,合成2,4,5-三硝基咪唑的咪唑盐(2,4,5-TNI咪唑盐);采用傅里叶变换红外光谱(FT-IR)、核磁共振光谱(NMR)、元素分析(EA)和熔点测定法等表征了产物结构。结果表明,采用微通道式硝化反应技术时,由2,4,5-TII制备2,4,5-TNI咪唑盐最优工艺条件为:2,4,5-TII与98%硝酸摩尔比为1∶20、在微通道式反应器停留时间6min、反应液温度70~72℃,得率为21.8%。微通道式反应工艺与常规釜式反应工艺相比,具有反应时间短、硝化试剂用量降低、反应温度略有降低、得率略有提高的优点,但也无法完全避免氧化副反应的发生。

One-pot synthesis of various xanthene derivatives using ionic liquid1,3-disulfonic acid imidazolium hydrogen sulfate as an efficient and reusable catalyst under solvent-free conditions

In this study, 1,3-disulfonic acid imidazolium hydrogen sulfate （DSIMHS） is used as an efficient and reusable ionic liquid for the green, mild, and efficient synthesis of xanthenes under solvent-free conditions. Simple and easy work-up, low cost, green process, short reaction times and excellent yields of the products are the advantages of this procedure. Further, the catalyst can be recycled and reused at least for four times without a noticeably decrease in its catalytic activity.

Porous nitrogen/halogen dual-doped nanocarbons derived from imidazolium functionalized cationic metal-organic frameworks for highly efficient oxygen reduction reaction

Heteroatom-doped carbon materials as alternative catalysts for oxygen reduction reaction(ORR)have drawn increasing attention due to their tunable chemical and electronic structures for achieving high activity and stability. However, there still remains a great challenge to fabricate porous heteroatoms dual-doped carbons with uniformly doping in a facile and controllable way. Herein,imidazole/imidazolium-functionalized metal-organic frameworks(MOFs) are employed as precursors and templates to achieve porous nitrogen and halogen dual-doped nanocarbons. Among these carbon materials, the as-prepared nitrogen/bromine dual-doped catalyst BrNC-800 exhibits the best ORR performance with a positive half-wave potential at 0.80 V(vs. RHE) in 0.1 mol L-1 KOH, which is comparable to the benchmark commercial 20 wt% Pt/C catalyst. BrNC-800 shows excellent long term stability and methanol tolerance.This work provides a facile approach to fabricate highly efficient heteroatoms dual-doped carbon catalysts for energy conversion.