CO₂Absorption Performance of “Dry Matter” Prepared with Amino Acid-Based Ionic Liquids

Dry Matter (DM) is a powdery substance which is composed of micro droplets and surrounding hydrophobic silica nanoparticles. Because of the much larger surface area than that of the corresponding bulk liquid, DM, which contains amino-functionalized ionic liquids (ILs), is a promising CO2 absorption material provided with quick absorption speed. In the present study, we successfully prepared powdery DMs by utilizing aqueous solutions of amino acid-based ILs (tetraethylammonium glycine [N2222][Gly], and tetraethylammonium alanine [N2222][Ala]). Although a DM with lysine-based IL (N2222) [Lys]) was also prepared, only a soufflé-like material was obtained. We measured CO2 absorption performance for the DMs to find that the mass-base absorption ability (mass-base A.A.) (CO2 mol/DM kg) and the mol-base one (CO2 mol/IL mol) of [N2222][Lys] were ca. two times of [N2222][Gly] and [N2222][Ala], while the absorption speed of the former was inferior to the latter two, i.e., ca.15 min vs. 5 min for 90% absorption. In order to improve the mass-base A.A. of [N2222][Gly], we used 10% of aqueous poly(allylamine) (PAlAm) solution instead of water. The resultant mass-base A.A. proved to be significantly larger (1.9) than either of those of the respective single component systems (1.1 and 0.75 for the bulk IL and aq. PAlAm, respectively), and comparable to the A.A. (1.6 - 2.5) of 20% - 30% monoethanolamine solution which is commonly used in industrial application.

An ultrasonic-ionic liquid process for the efficient acid catalyzed hydrolysis of feather keratin

A novel efficient method for hydrolyzing feather keratin using an ultrasonic-ionic liquid coupling process has been developed, with reaction conditions optimized using response surface analysis of data obtained from single factor optimization studies. Ultrasonic irradiation(225 W power) of feathers in 8.4 mol·L^(-1) hydrochloric acid containing 1-butyl-3-methylimidazolium chloride as a cosolvent at 80 °C for 1.4 h, followed by heating at 110 °C for 8.3 h, resulted in hydrolysis of their keratin component in an excellent 83.1% yield. Compared with previous methods, this new method employs reduced amounts of hydrochloric acid, shorter reaction time, and affords amino acid hydrolysis products in higher yield.

Alkylation of Isobutane and Isobutene in Acidic Polyether Ionic Liquids

The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.

Preparation of lactic acid from glucose in ionic liquid solvent system

A new reaction system was designed to economically convert glucose to lactic acid environment-friendly. Hydrophobic ionic liquids were chosen as solvent that can promote the decomposition reaction of glucose, and the catalytic performance of the solid bases was evaluated. Both the reaction temperature and time can affect the yield of lactic acid. A high yield （97%） of lactic acid was achieved under the optimal reaction condition. The IH NMR spectra and HPLC-MS were used to identify the formation of the lactic acid and variations of ionic liquid. It is found that ionic-liquids have a unique solvent effect for glucose and bases. Water can be used as solvent to extract calcium lactate. This shows a great potential of hydrophobic ionic liquids in the solid bases catalyzed reaction that is limited by the weak solubility of solid bases in organic and water solution.

Supported ionic liquid sorbents for CO_2 capture from simulated flue-gas

Supported ionic liquid(IL) sorbents for CO_2 capture were prepared by impregnating tetramethylammonium glycinate([N1111][Gly]) into four types of porous materials in this study. The CO_2 adsorption behavior was investigated in a thermogravimetric analyzer(TGA). Among them, poly(methyl methacrylate)(PMMA)-[N1111][Gly]exhibits the best CO_2 adsorption properties in terms of adsorption capacity and rate. The CO_2 adsorption capacity reaches up to 2.14 mmol·g-1 sorbent at 35 °C. The fast CO_2 adsorption rate of PMMA-[N1111][Gly] allows 60 min of adsorption equilibrium time at 35 °C and much shorter time of 4 min is achieved at 75 °C. Further, Avrami's fractional-order kinetic model was used and fitted well with the experiment data, which shows good consistency between experimental results and theoretical model. In addition, PMMA-[N1111][Gly] remained excellent durability in the continuous adsorption–desorption cycling test. Therefore, this stable PMMA-[N1111][Gly] sorbent has great potential to be used for fast CO_2 adsorption from flue-gas.

A novel ligand-free palladium catalytic system with SO_3H-functional ionic liquids as cocatalyst for amidocarbonylation reaction

Effects of Lewis acid BF3·OEt2, and BrCnsted acids TsOH, CF3COOH, H3PO4, and HCIO4 as cocatalyst respectively on the ligand-free palladium-catalyzed amidocarbonylation were investigated. SO3H-functional ionic liquids 1-methyl-3-（4-sulfonic acid）butylimidazolium hydrosulfate [MIm（CH2）4803H][HSO4] and 1-methyl-3-（4-sulfonic acid）butylimidazolium triflate [MIm（CH2）4SO3H][OTf] were firstly employed as cocatalysts instead of these Lewis acid and Brφnsted acids. By using a ligand-free and weak corrosive catalyst in situ prepared form PdBr2, LiBr.H2O, and [MIm（CH2）4SO3H][OTf], the arnidocarbo- nylation of benzaldehyde, acetamide, and CO could proceed smoothly and afford N-acetyl-α-phenylglycine with yield of 58% in [C6mim]PF6 medium.

The direct electrochemistry of glucose oxidase based on the synergic effect of amino acid ionic liquid and carbon nanotubes

Amino acid ionic liquids(AAILs) have attracted much attention due to their special chemical and physical properties,especially their outstanding biocompatibility and truly green aspect.In this work,a novel electrochemical biosensing platform based on AAILs/carbon nanotubes(CNTs) composite was fabricated.AAILs were used as a novel solvent for glucose oxidase(GOD) and the GOD-AAILs/CNTs/GC electrode was conveniently prepared by immersing the carbon nanotubes(CNTs) modified glassy carbon(GC) electrode into AAILs containing GOD.The direct electrochemistry of GOD on the GOD-AAILs/CNTs/GC electrode has been investigated and a pair of reversible peaks was obtained by cyclic voltammetry.The immobilized glucose oxidase could retain bioactivity and catalyze the reduction of dissolved oxygen.Due to the synergic effect of AAILs and CNTs,the GOD-AAILs/CNTs/GC electrode shows excellent electrocatalytic activity towards glucose with a linear range from 0.05 to 0.8 mM and a detection limit of 5.5 μM(S/N = 3).Furthermore,the biosensor exhibits good stability and ability to exclude the interference of commonly coexisting uric and ascorbic acid.Therefore,AAILs/CNTs composite can be a good candidate biocompatible material for the direct electrochemistry of the redox-active enzyme and the construction of third-generation enzyme sensors.

Baeyer-Villiger Oxidation of Cyclic Ketones Catalyzed by Amino Acid Ionic Liquids

A series of amino-acid-based ionic liquids was synthesized via one-step protonation of the corresponding L-amiiio acid by utilizing an array of proton sources.The catalytic activity of the amino-acid-based ionic liquids for the Baeyer-Villiger oxidation of cyclic ketones was investigated using cyclopentanone as a model cycloketone.Theproline-based ionic liquid[ProH]CF3SO3 was shown to exliibit thebest catalytic activity.The reaction condition was optimized to give the following reagent ratio of h(cyclopentanone):n(catalyst):w(H2O2)=1:0.06:4,60℃and 6 h.Under the optimum conditions,the conversion of cyclopentanone was 96.57%and the selectivity forδ-valerolactone was 73.01%.The catalytic activity was shown to be constant after 4 cycles.A simple treatment was allowed for the recover and the reuse of[ProH]CF3S03.The successful utilization of[ProH]CF3SO3 to catalyze a host of cyclic ketones via Baeyer-Villiger oxidation clearly demonstrated the capacity of[ProH]CF3S03 to tolerate variation in the substrate.

Ionic Liquid 1-Vinyl-3-dodecylimidazole Bromide Embedded Hybrid Monolithic Column and Its Versatile Post-modification with Amino Acids

The amino acids post-modified ionic liquids-based hybrid monolithic columns were successfully developed.For the first step,using 1-vinyl-3-dodecylimidazole bromide(VDI·Br)and polyhedral oligomeric silsesquioxane methacryl substituted(POSS-MA)as monomer and crosslinking agent,the monolithic POSS-VDI matrix material was polymerized in 100μm capillary.The prepared POSS-VDI column is of ion-exchange/reverse-phase mixed-mode retention characteristics.The column e fficiency reached 137,000 N/m for thioureas.The POSS-VDI column has also been successfully applied to recognize and analyze the eff ective components of Traditional Chinese Medicines Fangji and the Root of Kudzu Vine.Furthermore,based on its good chromatographic performances,in the second step,amino acids L-Proline(L-Pro),Glycine(Gly)or DLPhenylalanine(DL-Phe)were further exploited as the anion exchangers to post-modify the POSS-VDI column.The new POSS-VDI-Pro,POSS-VDI-Gly and POSS-VDI-Phe columns exhibited diff erent separation selectivity for the complex egg white protein sample.The present work provides a good route to fabricate versatile amino acids and ionic liquids modified monolithic columns with good separation selectivity.

Bronsted-Lewis双酸性离子液体催化合成乙酸正丁酯

以3-氨基-1-丙磺酸、氯化锌、盐酸为原料制备了一系列Bronsted-Lewis双酸性离子液体。离子液体中磺酸基提供Bronsted酸性,阴离子提供Lewis酸性。采用FTIR、1HNMR、13CNMR、元素分析对合成的离子液体进行了结构表征;对离子液体的Bronsted酸性、Lewis酸性、腐蚀性进行了测定。使用该离子液体催化合成了乙酸正丁酯并利用响应曲面法考察了最佳反应条件。结果表明,在反应温度103℃,催化剂[NH3C3H6SO3H]Cl/0.75ZnCl2(0.75代表3-氨基-1-丙磺酸盐酸盐与氯化锌物质的量比为1.00∶0.75)用量为正丁醇质量的10.03%,n(乙酸)∶n(正丁醇)=1.00∶1.22,反应时间4.92 h,带水剂环己烷用量为正丁醇质量的20%条件下,乙酸正丁酯收率可达97.28%。[NH3C3H6SO3H]Cl/0.75Zn Cl2重复使用5次后,催化剂活性没有明显降低。

氨基酸离子液体在能量存储和生物质资源化中的研究进展

氨基酸作为蛋白质的基本组分,由于分子结构中同时含酸性和碱性基团(羧基和氨基),可以方便地设计以氨基酸为阴离子或阳离子的氨基酸离子液体。氨基酸离子液体具有溶解性强、低熔点和热稳定性高等优势,可以作为碳前驱体、溶剂、催化剂和吸附剂等应用到储能、生物质资源化以及碳中和等领域。本文概述了近7年氨基酸离子液体在超级电容器电极材料、生物质提取及催化转化和二氧化碳分离捕集方面的研究工作,重点综述了以氨基酸离子液体为前驱体在超级电容器碳电极材料方面的研究进展,并展望了氨基酸离子液体的应用及发展前景。

Tribological evaluation of environmentally friendly ionic liquids derived from renewable biomaterials

Unlike most of the conventional ionic liquids(ILs) derived from non-renewable resources, five environmentally friendly ILs([Ch][AA] ILs) derived from amino acids(AAs) and choline(Ch) were synthesized using biomaterials by a simple, green route: acid–base reaction of Ch and AAs. The thermal and corrosion properties, as well as viscosity, of the prepared ILs were examined. The results revealed that the anion structure of ILs plays a dominant role in their thermal and viscosity behavior. These ILs exhibited less corrosion toward copper, related to their halogen-, sulfur-, and phosphorus-free characteristics. The tribological behavior of the synthesized ILs was examined using a Schwingungs Reibung und Verschleiss tester, and the results indicated that these ILs exhibit good friction-reducing and anti-wear properties as lubricants for steel/steel contact. Results from energy-dispersive spectroscopy and X-ray photoelectron spectroscopy indicated that the good tribological properties of [Ch][AA] ILs are related to the formation of a physically adsorbed film on the metal surface during friction.

生物柴油制备技术的研究进展

生物柴油不仅燃烧性能与石油柴油相当,且具有环境友好、资源可再生的优点,是替代石油柴油的理想燃料之一。综述了热裂解法和酯交换法(包括化学催化法、酶催化法和超临界法)制备生物柴油的最新研究进展,并探讨了各种制备方法的优缺点和应用前景。为降低生物柴油成本,应采用廉价原料(如废油脂)。对于酸值高的废油脂,宜采用固体酸和离子液体等环境友好催化剂。

氨基酸离子液体对壳聚糖溶解性能的影响

合成了一系列氨基酸类离子液体,从中筛选出对溶解壳聚糖具有良好性能的离子液体——甘氨酸盐酸盐离子液体。在常温常压下考察了该离子液体1%～10%水溶液对壳聚糖的溶解能力,溶解壳聚糖能力最大能达到6.32%(质量分数,下同)。对离子液体重复使用5次后,溶解能力没有明显下降。采用X射线衍射(XRD)和红外光谱(FT-IR)对再生的壳聚糖进行表征,结果表明,壳聚糖在溶解过程中没有发生衍生化。甘氨酸盐酸盐离子液体水溶液是壳聚糖的良溶剂。

氨基酸离子液体润滑剂的结构与摩擦学行为的关系

利用酸碱中和法合成了一系列季铵盐和季膦盐氨基酸离子液体(AAILs)润滑剂,以合成润滑油聚α-烯烃(PAO10)和传统含氟离子液体1-丁基-3-甲基咪唑双三氟甲烷磺酰亚胺盐(L-F104)作为参照样,评价了粘温性能、热稳定性以及作为不同摩擦副润滑剂的润滑性能,探索了阴、阳离子结构对其物理化学性质和摩擦学性能的影响规律。结果表明:季膦盐氨基酸离子液体的粘温性能和热稳定性明显优于季铵盐氨基酸离子液体;这些离子液体中,阴离子上硫元素的引入可显著提高其粘温性能,而芳环的引入却使其粘温性能明显下降。结构对其摩擦学性能的影响规律与摩擦副种类有关:当钢/钢、钢/铜摩擦副作为润滑剂时,在常温或高温条件下,均具有优异的减摩抗磨性能;当钢/铝摩擦副作为润滑剂时,只有含芳基的季铵盐氨基酸离子液体具有优于PAO 10和L-F104减摩抗磨性能。

氨基酸离子液体-MDEA混合水溶液的CO2吸收性能

为改善N-甲基二乙醇胺(MDEA)水溶液对CO2气体的吸收性能,选择了四甲基铵甘氨酸([N1111][Gly])、四乙基铵甘氨酸([N2222][Gly])、四甲基铵赖氨酸([N1111][Lys])、四乙基铵赖氨酸([N2222][Lys])4种功能性离子液体作为活化剂与其复配组成新型CO2吸收剂。用恒定容积法考察了总质量分数为30%的混合溶液吸收CO2的性能,分析了离子液体在水溶液中与MDEA通过质子传递相互促进吸收CO2的机理。实验结果显示离子液体能够显著提高MDEA水溶液吸收CO2的速率,且吸收速率随着添加量的增加而提高。在本文所用的几种混合吸收剂中,阴离子为赖氨酸的离子液体混合吸收剂具有较高的吸收负荷;而[N1111][Gly]-MDEA混合溶液对CO2的初期吸收速率最快,同时[N1111][Gly]-MDEA混合吸收剂的再生效率高于其他离子液体混合吸收剂,达到98%。

氨基酸离子液体清洁催化合成阿司匹林

以氨基酸为原料采用一步法合成了3种氨基酸离子液体,将其代替浓H2SO4用于催化乙酸酐和水杨酸的乙酰化反应,清洁合成阿司匹林。考察了离子液体种类及用量、原料配比、反应温度、时间等因素对合成阿司匹林的影响。结果表明,该离子液体对于合成阿司匹林具有良好的催化效果,在水杨酸20mmol、乙酸酐40mmol、谷氨酸硫酸盐离子液体([Glu]HSO4)2mmol、反应温度70℃、反应时间30min的条件下,阿司匹林分离产率可达84.8%。增大投料量,产率还会进一步升高,并且离子液体可重复使用。

氨基酸离子液体应用研究进展

氨基酸离子液体是一类新型的功能化离子液体,除了具有常规离子液体的低蒸汽压、低熔点、宽液程、溶解性好和稳定性高等性质外,还具有很强的氢键网络结构、稳定的手性中心、双配位基团、生物兼容性和可生物降解等许多独特的性质。本文综述了近年来氨基酸离子液体在溶解生物质、气体吸收、手性分离、催化等方面的应用研究进展。

氨基酸离子液体作为不同摩擦副润滑剂的性能研究

设计合成了三种具有不同官能团结构的氨基酸类离子液体,采用SRV-Ⅳ微动摩擦磨损试验机考察了其作为Si_3N_4/Si_3N_4和钢/钢摩擦副润滑剂的摩擦学性能,并与丙三醇进行对比,采用扫描电镜和X射线光电子能谱仪分析磨斑形貌和表面元素的化学状态.结果表明:三种氨基酸类离子液体均能适用于两种摩擦副的润滑,并具有良好的减摩抗磨性能.羟基和羧基官能团的存在不仅有效增强了离子液体在基底上的物理吸附作用,同时还促使其与摩擦副发生摩擦化学反应.比较三种离子液体的摩擦学性能发现,同时含有两个羧基的谷氨酸四丁基磷盐离子液体的减磨性能优于其他两种只含一个羟基或羧基基团的离子液体.

微/纳米ZnO绒球的制备及其在自然光下催化降解有机染料性能（英文）

以谷氨酸氟硼酸(GluBF4)离子液体水溶液为反应介质,以物质的量比为1:6的二水合醋酸锌[Zn(Ac)2 2H2O]和氢氧化钠为原料,室温下制备前驱体,再微波辅助加热制备了纳米氧化锌粉体,获得了纳米结构微米尺寸纳米Zn O绒球.利用场发射扫描电镜(FESEM)、X射线衍射(XRD)、比表面(BET)、能量色散谱(EDS)等对产物进行了表征.所得产物为六方晶系纤锌矿结构,粉体粒径20.4 nm,绒球比表面积为28.3 m2g–1,产物纯度较高,收率95.3%.同时探讨了纳米Zn O绒球生成的可能机理.该纳米材料在日光下显示较高的光催化活性和稳定性.分别配制浓度为10 mg L–1的100 m L甲基橙(MO)和甲基紫(MV)水溶液,30 mg纳米氧化锌为光催化降解催化剂,太阳光激发下5 h脱色率分别达到74.3%和96.9%;溶液总有机碳(TOC)含量随光降解的进行缓慢下降;光催化剂重复利用5次,催化剂形貌不变、颜色不变,质量基本未发生变化.