离子液体在生物质利用方面的应用

能源和环境危机日益严重,生物质作为唯一可再生的碳源,其开发利用备受关注.同时离子液体因其不挥发、较好的稳定性和可重复利用等优点,可作为新型绿色溶剂.近年来,离子液体和生物质利用的研究交叉渗透,研究者们完成了一系列离子液体在生物质利用方面的应用研究.本文主要从生物基离子液体和离子液体作为生物质利用的介质两方面对该研究进行...     

果糖在酸性离子液体中脱水制备5-羟甲基糠醛

制备了多种离子液体,并将其作为催化剂和溶剂催化果糖脱水制备5-羟甲基糠醛（HMF）。 制备的酸性离子液体包括磺酸基功能化酸性离子液体、咪唑类酸性离子液体和吡啶类酸性离子液体。 利用核磁共振仪和红外光谱仪对离子液体的结构进行表征。 利用紫外可见光分光光度计结合Hammett指示剂计算Hammett酸度函数,比较了酸强度的大小对反应的影响。 结果表明,离子液体的酸强度对反应有较大影响,在无其它催化剂和溶剂的情况下,离子液体具有较高的催化活性,通过使用1-丁基-3-甲基咪唑氯盐(BmimCl)作为催化剂,当反应温度为120 ℃,反应进行到4 h时,HMF收率可以达到74.97%。     

离子液体中制备无机材料

离子液体作为潜在的“绿色”溶剂,具有许多传统溶剂无法比拟的优异性能,在有机合成、催化、液液分离和萃取等领域引起了广泛的研究。而在离子液体领域无机材料的制备是一个较新的发展分支,现已利用其合成出多种具有独特结构和性能的无机材料。本文就离子液体在无机材料制备方面的应用及发展趋势进行了综述。目前,对于制备无机材料,离子液体主要是作为电解液、表面活性剂或溶剂,本文介绍了其在应用中的优缺点,并指出该领域未来的发展趋势是离子热合成和集模板-溶剂-反应物于一身的离子液体反应。     

功能离子液体/氧化硅基多孔复合材料*

利用有巨大界面特征和发达孔道结构的氧化硅基多孔材料作为功能离子液体的载体,不仅可实现离子液体的固相化从而解决均相离子液体分离难的瓶颈,而且也可增加离子液体的比表面积进而提高离子液体的使用效率和稳定性;探索结合离子液体和氧化硅基多孔材料双重优点的目标功能材料的制备及应用成为近年来的一个研究热点。本文综述了离子液体/氧化硅基多孔复合材料的最新研究进展,探讨了其合成手段的有效性,并对其应用前景进行了展望。     

离子液体催化制备5-羟甲基糠醛的研究进展

本文综述了离子液体催化制备5-羟甲基糠醛的研究进展。运用离子液体作为反应溶剂和催化剂,与常规合成HMF的方法相比,其反应在常压、低温下进行,更易于操作控制;副反应数量明显减少,HMF的产率稳定,可达90%;离子液体催化活性稳定,可重复利用,减少了有机溶剂的使用量;利用离子液体作为媒介,能将反应原料从单一的果糖扩展到葡萄糖和纤维素等廉价原料,降低了生产成本。由此可见,运用离子液体催化制备HMF将是今后研究的重点和发展的必然趋势。     

离子色谱法在离子液体阴阳离子分析中的应用

离子液体作为一种新型绿色环保有机化合物,因具有饱和蒸气压低、溶解性良好以及电导率高等优异性质,而在化学化工领域中得到了较为广泛的应用,并越来越受到人们的关注。该文综述了近年来离子色谱在离子液体阴阳离子分析中的应用,对离子色谱法分析离子液体阳离子、离子液体阴离子以及同时分析离子液体阴阳离子三方面进行讨论,并对离子色谱法分析离子液体的发展趋势进行了展望。     

手性离子液体的合成

近年来,研究者对室温离子液体极为关注,因为这些离子液体可以作为潜在的替代试剂用于有机合成、提取与分离、电化学和材料科学等方面。在离子液体中,手性离子液体由于可用在手性识别、不对称合成、消旋体的拆分、立体选择聚合、气相色谱、NMR位移试剂和液晶等方面而受到特别注意。尽管手性离子液体由于合成困难和费用昂贵而限制了其广泛应用,但其在不对称合成中可作为手性诱导物的应用前景促使研究者不断地去开发新型的手性离子液体。手性离子液体的制备既可以使用手性源（如氨基酸、胺、氮基醇以及生物碱类）,也可以利用不对称合成的手段,其所具有的手性可位于分子的中心、轴或者平面上。本文综述了手性离子液体合成的最新进展,并按照阴离子或阳离子的种类将其分为咪唑类、吡啶类、铵类和噻唑啉盐类,同时简要介绍了一些新的合成技术。     

离子液体中的生物催化反应

本文综述了近年来离子液体中生物催化反应的研究进展。离子液体作为新的绿色溶剂,用于生物催化反应具有以下特点:在离子液体中酶有良好的稳定性、选择性和反应活性。离子液体可溶解极性大的反应物, 产物易分离,酶和离子液体可重复使用。对离子液体中的生物催化进行了展望。     

室温离子液体在分离科学研究中的新进展

室温离子液体作为一种重要的绿色溶剂,由于在金属离子、小分子有机物的萃取分离,气体吸附分离以及作为液相和气相色谱固定相等许多分离过程中体现出高分离效率和高选择性的特点,正在成为分离科学研究的前沿领域.着重总结了从2003—2006年的室温离子液体在分离科学领域中的新进展,并对其应用领域和发展前景做了展望.提出进一步加强离子液体的功能化和固定化技术及其在分离科学中的应用基础研究,探索离子液体有效的回收和再循环利用的新方法,是离子液体今后在分离科学研究中的一系列重要内容.     

功能性离子液体在金属萃取分离中的研究进展

近年来,离子液体在金属萃取领域的研究受到广泛关注,主要集中在两个方面,一是疏水性离子液体作为“绿色”溶剂用于金属离子萃取;二是带有官能团的功能性离子液体作为萃取剂用于金属离子萃取,其中,后者是目前研究的热点。 本文主要对近年来功能性离子液体萃取分离放射性金属、重金属和稀土金属等研究进行综述,并对其未来发展进行了展望。     

泡沫铜基底原位生长的铜基导电金属有机框架作为双功能电催化剂

以泡沫铜为基底生长氢氧化铜纳米线,通过原位转化合成二维导电金属有机框架(MOF)材料Cu_3HITP_2(HITP=2,3,6,7,10,11-六氨基三亚苯)作为双功能催化剂,可直接用作析氧及氧还原反应的工作电极,而无需使用额外的基底或粘合剂,且无需后续热处理。研究发现以氢氧化铜纳米线为模板的Cu_3HITP_2表现出了更大的电化学比表面积,这种新型的电极可在碱性溶液(0.1和1.0 mol·L~(-1) KOH)中可以稳定运行,析氧反应中在电流密度达到10 mA·cm~(-2)时的过电位仅为1.53 V,超越了商业二氧化钌的催化性能。此外,该催化剂在氧还原反应中的半波电位达到0.75 V,优于大多数MOF材料。     

Voltammetric Analysis of Trace Levels of Platinum Group Metals – Principles and Applications

The compelling use of autocatalytic converters, containing platinum group metals (PGMs), has been the cause, in the environmental and biological matrices, of an increasing concentration of such metals. For this reason, in the last decade, the literature has reported several papers regarding analytical procedures for the determination of Pt(II), Pd(II) and Rh(III) in real samples, generally employing spectroscopic methods. The present review intends to highlight the contribution of the voltammetric techniques for the determination of these metals, including also those less investigated, i.e. Iridium, Osmium and Ruthenium.     

A survey of the determination of the platinum group elements

The platinum-group metals (PGMs), Ru, Rh, Pd, Os, Ir and Pt, are widely used as catalysts in petroleum and chemical processes. They find wide applications in automotive exhaust-gas control converters and are of immense importance to the electronics industry. They are found in many items of jewellery and serve to an increasing extent as a form of investment. The PGMs are extracted in minute quantities from a limited number of ores, found mainly in S. Africa and the USSR. They are concentrated and separated from each other by elaborate chemical processes. Because of their great intrinsic value (Pt $650 per oz; Rh $1400 per oz), the recycling of the PGMs from literally hundreds of different forms of scrap is an essential factor in the overall management of the PGM economy. In this survey emphasis is placed on the need to tailor the analytical method according to (a) the environment in which the PGMs occur, (b) the individual PGM concentrations, and (c) the desired sensitivity and precision. The factors which determine the choice of chemical, physicochemical and/or instrumental approaches are discussed. They are further commented on in extensive presentations of dissolution and separation techniques and methods for the final measurement of individual PGMs. Appendices are provided which present the compositions and sources of the products most frequently encountered in PGM analysis, along with information on methods of decomposition, separations required, type of separation, and final determination.     

Recovery of Pd(II) and Ru(III) from aqueous waste using inorganic ion-exchanger

The applicability of mica minerals and zeolites for the efficient removal of valuable platinum group metals (PGMs), Pd(II) and Ru(III) from aqueous waste by sorption has been investigated. The sorption of PGMs Pd(II) onto mica-mineral, muscovite and Ru(III) onto natrolite as zeolite have been studied as a function of (i) exchanger composition, (ii) temperature at which sorption process takes place and (iii) the presence of competing cations such as Na⁺, K⁺, Mg²⁺. These three factors have remarkable effect on the sorption process. The synthesized gel was characterized by X-ray powder diffraction, energy dispersive spectrometry, thermogravimetric analysis and scanning electron microscopy.     

Application of fluoroxidants for the decomposition and analysis of platinum metals and gold in black shale ores

In order to develop a reliable method for the platinum group metals (PGMs) determination in ores of organic origin like carbonaceous black shale a decomposition method with fluoroxidants like BrF₃ and KBrF₄ was established which avoids the commom losses of PGM organometallic compounds by volatilazation or chemisorption. The recovery from different trapping solutions is discussed. Platinum metals are evidently found in the carbonaceous black shale ores from the “Natalka” deposit situated in the Magadan area. PGMs are very inhomogenously distributed in the ores and ore concentrates and their total contents in ore are 5–18 g/t. The carbonaceous concentrate of black shale ore contains up to 23 g/t of the sum of platinum metals. ≥ 8% of the sum of platinum and palladium contained in this carbonaceous concentrate are soluble in organic solvents. Received: 16 July 1998 / Revised: 16 April 1999 / Accepted: 5 May 1999     

Application of fluoroxidants for the decomposition and analysis of platinum metals and gold in black shale ores

In order to develop a reliable method for the platinum group metals (PGMs) determination in ores of organic origin like carbonaceous black shale a decomposition method with fluoroxidants like BrF₃ and KBrF₄ was established which avoids the commom losses of PGM organometallic compounds by volatilazation or chemisorption. The recovery from different trapping solutions is discussed. Platinum metals are evidently found in the carbonaceous black shale ores from the “Natalka” deposit situated in the Magadan area. PGMs are very inhomogenously distributed in the ores and ore concentrates and their total contents in ore are 5–18 g/t. The carbonaceous concentrate of black shale ore contains up to 23 g/t of the sum of platinum metals. ≥ 8% of the sum of platinum and palladium contained in this carbonaceous concentrate are soluble in organic solvents. Received: 16 July 1998 / Revised: 16 April 1999 / Accepted: 5 May 1999     

Comparison of some analytical performance characteristics in inductively coupled plasma spectrometry of platinum group metals and gold

The limits of detection, precision and matrix effects in the inductively coupled plasma spectrometry of platinum group metals (PGMs) and gold were measured and evaluated for four ICP-AES and one ICP-MS instrument. The sample matrix was a cationic surfactant used for the PGMs and gold preconcentration on a modified silica gel (C18). A sorption of ion associates of PGMs and gold chlorocomplexes with the cation of onium salt N(1-carbaethoxypentadecyl)-trimethyl ammonium bromide was considered. The calibration curves, limits of detection and matrix effects were evaluated in the presence of 0.003 mol dm(-3) of onium salt (1.3 mg cm(-3)) and 0.1 mol dm(-3) HCl. The values of limits of detection (3 sigma(bl)) of PGMs for all axial ICP instruments were mostly below 10 ng cm(-3). Lateral observation on dual view ICP instrument yielded only 3 times higher detection limits in comparison to the axial mode of the same spectrometer and the detection limits for ICP-MS instrument were on the levels of units or tens of pg cm(-3). These limits of detection did not significantly differ from values obtained with pure solutions. Matrix effects in the presence of onium salt did not exceed 12% depression in the analytical signals. Besides the coefficients of correlation, the uncertainties on centroids of concentrations were calculated for calibration graphs obtained by linear regression.     

Adsorption properties and behavior of the platinum group metals onto a silica-based (Crea + TOA)/SiO2–P adsorbent from simulated high level liquid waste of PUREX reprocessing

To separate platinum group metals (PGMs) from high level liquid waste (HLLW), a novel silica-based (Crea + TOA)/SiO₂–P adsorbent was synthesized by impregnating Crea (N′,N′-di-n-hexyl-thiodiglycolamide) and TOA (trioctylamine) two extractants into the macroporous SiO₂–P support with a mean diameter of 60 μm. Adsorption properties and behavior of PGMs from simulated HLLW onto the novel silica-based (Crea + TOA)/SiO₂–P adsorbent were investigated by batch method. It was found that (Crea + TOA)/SiO₂–P adsorbent exhibited good adsorption selectivity for PGMs over the other tested fission product element in a wide HNO₃ concentration. This adsorbent showed strong affinity to Pd(II) but almost no adsorption for rare earth elements. Adsorption process of PGMs could be expressed by Langmuir monomolecular layer adsorption mode and be governed by the chemisorption process. In addition, the adsorption isotherms and thermodynamic parameters of tested elements were calculated by Langmuir equation, Freundlich equation and van’t Hoff equation, respectively.     

铂族金属催化剂低温 CO氧化研究近期进展

CO氧化可能是多相催化领域最常见的反应,它不仅能作为探针反应研究催化剂结构、反应活性位等,而且在诸多实际过程如空气净化、汽车尾气污染物控制、燃料电池所用氢源净化等扮演重要角色.最早的 CO氧化催化剂为霍加拉特剂,其组分主要为 CuO与 MnO2混合氧化物,然而在实际应用过程中存在低温活性低、吸湿易失活等缺点.1987年, Haruta等发现湿化学法制备的氧化物负载 Au催化剂表现出非常高的低温 CO氧化活性及耐水稳定性,其 Au粒子以纳米尺度分散,进而引发了催化研究领域的“淘金热”及纳米催化研究热潮.而 CO氧化通常作为考察 Au催化剂结构性质的探针反应,也成为考核其它金属催化剂是否具有高活性的判据之一. Pt族金属上 CO氧化反应从 Langmuir等研究开始至今已有100多年,然而低温下该金属催化剂活性与 Au催化剂相比要低一个数量级.本质原因为 Pt族金属上 CO吸附较强, O2吸附与活化受到抑制,而该步骤被认为是 CO氧化的速控步,因而表现出较低的催化活性.通常 Pt族金属催化剂需要100oC以上 CO才能脱附, O2进而得以吸附.目前研究人员采取多种策略,其基本原则为削弱 Pt族金属上 CO吸附强度或者提供其它活性位供 O2吸附与活化.本综述将概括近十年来Pt族金属催化剂 CO氧化研究进展,主要总结室温甚至超低温条件下的研究成果.高活性 CO氧化催化剂主要是通过采用可还原氧化物为载体或助剂,或者改变催化剂表面性质如使表面富 OH基物种来形成. Au催化剂的研究发现,改变金属粒子尺寸极有可能获得不同寻常的催化性能,而常规的 Pt族金属催化剂研究主要是在纳米尺度.近期人们发现逐渐减小 Pt族金属粒子尺寸,从纳米到亚纳米甚至单原子时,其电荷状态逐渐呈正价形式,这有利于削弱其 CO吸附强度.此外,可通过增强金属载体间的相互作用,改变金属载体接触方式,如从核壳到交叉结联结构,构筑出更多的金属载体界面,使得 O2更容易吸附与活化或稳定更多的 OH基物种进而在此界面与吸附的 CO反应.伴随着表征技术的发展, CO氧化机理的认识也更加深入,这给催化剂的设计带来更多新的思路.(1)改变 CO吸附活化位,将 CO吸附活化位从金属转移到载体上,从而大大降低 CO吸附强度,活化的 CO物种在反应过程中容易溢流到金属载体界面处,这甚至有利于超低温度下(–100oC左右) CO氧化.(2)改变 O2活化形式. O2通常在 Pt族金属上容易以解离氧原子形式存在,通过改变载体、金属载体界面性质使得 O2以分子氧形式活化,如形成超氧或过氧物种,这有利于降低 CO氧化的活化能垒,进而提高其低温甚至超低温下 CO氧化活性.今后,设计并合成出在超低温度下能够氧化 CO的 Pt族金属催化剂将成为 CO氧化催化剂研究的重要方向之一.