离子液体捕集二氧化碳非平衡热力学研究方法学探讨

介绍了应用非平衡热力学研究离子液体捕集二氧化碳（CO2）动力学的思路，分析了其成功应用需解决三大关键科学难题，即可靠的热力学模型，界面传递速率描述以及准确的通量数据．其中，准确通量数据的获得需要可靠的实验动力学数据和离子液体捕集CO2过程传递面积的有效考察．在此基础上系统地总结了该三大关键科学问题最新的研究进展和分析后续开展的工作，并对离子液体捕集二氧化碳非平衡热力学研究提出展望．     

Capsules with polyurea shells and ionic liquid cores for CO2 capture

Many ionic liquids (ILs) have good solubilities of CO₂ but the high viscosity of ILs makes them cumbersome and kinetically limits gas uptake. Encapsulation of ILs is an effective approach to overcoming these limitations. In capsules with a core of IL, the chemical composition of the shell impacts performance. Here, we report the preparation of capsules with a core of the IL [Bmim][PF₆] and polymer composite shell, then evaluate how the identity of the polymer impacts CO₂ uptake. IL-in-oil Pickering emulsions stabilized by nanosheets are used, with capsules formed by interfacial polymerization between different diamines and diisocyanates (e.g., shells are polyurea and nanosheets). The capsules contain 60–80 wt% IL and the composition was verified using Fourier transform infrared spectroscopy. Optical microscopy, scanning electron microscopy, and particle sizing data showed spherical, discrete capsules with 50–125 μm in diameter. All capsules are stable up to 250°C. Brunauer–Emmett–Teller analysis of CO₂ gas uptake data showed that different polymer compositions led to different CO₂ uptake properties, with capacity ranging from 0.065 to 0.025 moles of CO₂/kg sorbent at 760 torr and 20°C. This work demonstrates that the polymer identity of the shell impacts gas uptake properties and supports that shell composition can tailor performance.     

Properties of alkylbenzimidazoles for CO2 and SO2 capture and comparisons to ionic liquids

To date, few reports have been concerned with the physical properties of the liquid phases of imidazoles and benzimidazoles-potential starting materials for a great number of ionic liquids. Prior research has indicated that alkylimidazole solvents exhibit different, and potentially advantageous physical properties, when compared to corresponding imidazolium-based ionic liquids. Given that even the most fundamental physical properties of alkylimidazole solvents have only recently been reported, there is still a lack of data for other relevant imidazole derivatives, including benzimidazoles. In this work, we have synthesized a series of eight 1-n-alkylbenzimidazoles, with chain lengths ranging from ethyl to dodecyl, all of which exist as neat liquids at ambient temperature. Their densities and viscosities have been determined as functions of both temperature and molecular weight. Alkylbenzimidazoles have been found to exhibit viscosities that are more similar to imidazolium-based ILs than alkylimidazoles, owed to a large contribution to viscosity from the presence of a fused ring system. Solubilities of CO2 and SO2, two species of concern in the emission of coal-fired power generation, were determined for selected alkylbenzimidazoles to understand what effects a fused ring system might have on gas solubility. For both gases, alkylbenzimidazoles were determined to experience physical, non-chemically reactive, interactions. The solubility of CO2 in alkylbenzimidazoles is 10%-30% less than observed for corresponding ILs and alkylimidazoles. 1-butylbenzimidazole was found to readily absorb at least 0.333 gram SO2 per gram at low pressure and ambient temperature, which could be readily desorbed under an N2 flush, a behavior more similar to imidazolium-based ILs than alkylimidazoles. Thus, we find that as solvents for gas separations, benzimidazoles share characteristics with both ILs and alkylimidazoles.     

Experimental nibble for computational chemists: On the construction and CO2 capture by different zeolite imidazole ester framework-8 and ionic

The combination of zeolitic imidazolate framework-8 (ZIF-8) and ionic liquids (ILs) to create porous ionic liquids (PILs) is highly significant for efficient carbon dioxide (CO₂) capture and the advancement of carbon capture, utilization, and storage (CCUS) technologies. To further investigate the CO₂ capture characteristics of different PILs, two different-sized ZIF-8 structures and two functionalized ILs were prepared. Additionally, the enhancement factor of the reaction process was calculated using the dual-film theory and mass transfer coefficient. The results demonstrated that the original [PMIm]Cl had low CO₂ absorption capacity at ambient temperature and pressure, whereas the functionalized ILs had a maximum CO₂ capture capacity of approximately .31 mol/mol, with the 20 wt% concentration of tetraethylene pentamine-2-methylimidazole ([TEP][MIm]) exhibiting the highest CO₂ capture capacity of around 1.93 mol/mol. The synthesized PILs demonstrated a maximum CO₂ capture capacity of approximately 2.22 and 2.16 mol/mol at 20 and 10 wt% ionic concentrations, respectively, with a porous ionic liquid addition of 1.0/100 g. The corresponding enhancement factors were 1.53 and 1.59, respectively. These findings have significant implications for CCUS technology.     

CO2 Capture technologies: Current status and new directions using supported ionic liquid phase (SILP) absorbers

Current state-of-the-art techniques for CO2 capture are presented and discussed. Post-combustion capture of CO2 by absorption is the technology most easily retrofitted to existing installations, but at present this is not economically viable to install and run. Using ionic liquids instead of aqueous amine solutions overcomes the major thermodynamic issues. By applying SILP technology further advances, in terms of ease of handling and sorption dynamics, are obtained. Initial experimental studies showed that ionic liquids such as tetrahexylammonium prolinate, [N6666][Pro], provide a good candidate for CO2 absorption using SILP technology. Thus a solid SILP absorber comprised of 40 wt% [N6666][Pro] loaded on precalcined silica quantitatively takes up about 1.2 mole CO2 per mole of ionic liquid in consecutive absorption-desorption cycles in a flow-experiment performed with 0.09 bar of CO2 (9% CO2 in He).     

Supported absorption of CO2 by tetrabutylphosphonium amino acid ionic liquids

A new type of "task specific ionic liquid", tetrabutylphosphonium amino acid [P(C4)4][AA], was synthesized by the reaction of tetrabutylphosphonium hydroxide [P(C4)4][OH] with amino acids, including glycine, L-alanine, L-beta-alanine, L-serine, and L-lysine. The liquids produced were characterized by NMR, IR spectroscopies, and elemental analysis, and their thermal decomposition temperature, glass transition temperature, electrical conductivity, density, and viscosity were recorded in detail. The [P(C4)4][AA] supported on porous silica gel effected fast and reversible CO2 absorption when compared with bubbling CO2 into the bulk of the ionic liquid. No changes in absorption capacity and kinetics were found after four cycles of absorption/desorption. The CO2 absorption capacity at equilibrium was 50 mol % of the ionic liquids. In the presence of water (1 wt %), the ionic liquids could absorb equimolar amounts of CO2. The CO2 absorption mechanisms of the ionic liquids with and without water were different.     

咪唑类离子液体混合物吸收CO2性能研究

结合常规离子液体和功能型离子液体在吸收CO₂方面的优势,将两类咪唑类离子液体进行混合,对其吸收CO₂的效果和再生性能进行了实验研究。结果表明,两类咪唑类离子液体混合后流动性明显改善,与CO₂接触气液传质顺畅;常规离子液体[bmim][BF₄]和[bmim][Tf₂N]与胺功能型离子液体[NH₂e-mim][BF₄]混合物较单一的离子液体吸收CO₂的量大,[bmim][CH₃CO₂]与[NH₂e-mim][BF₄]混合后较单一的[bmim][CH₃CO₂]吸收量有明显的减低;随着常规咪唑类离子液体阳离子碳链增长,混合离子液体吸收CO₂的效果变强;与胺乙基功能型离子液体混合吸收CO₂时,阴离子为[Tf₂N]的常规咪唑类离子液体要比阴离子为[BF₄]的吸收效果好;离子液体混合物吸收CO₂后经再生循环利用10次,混合物质量基本不变,循环使用后吸收CO₂性能为初始吸收性能的75%~85%。     

The polymeric ionic liquids/mesoporous alumina composites: Synthesis,characterization and CO2 capture performance test

The CO₂ capture materials and technology have received much attention in recent years due to the environmental deterioration caused by the greenhouse gas emissions. Several imidazolium polymeric ionic liquids (PILs) were synthesized and immobilized on mesoporous γ-Al₂O₃ (MA) using ultrasonic immersion method. The prepared adsorbents were characterized by FT-IR, ¹H NMR, EA, TGA, SEM, XRD, BET and TEM, indicating the successful synthesis of the desired PILs/MA. The CO₂ adsorption capacity was investigated under different loading ratios, temperatures, pressures and CO₂ flow rates, whose optimal adsorption conditions were 1/1, 313 K, 5 bar and 10 mL/min, respectively. Moreover, the adsorption curves for P[VCIm]Cl/MA were coincident with pseudo-second order model, and the CO₂ adsorption kinetics model was calculated and obtained. Compared with P[VRIm]Cl and P[VEIm]Cl, P[VCIm]Cl/MA demonstrated an outstanding adsorption amount of 0.562 mmol/g under the suitable conditions, and its regeneration efficiency could achieve 94.8% after 5 times cycle.     

Tuning the physicochemical properties of diverse phenolic ionic liquids for equimolar CO2 capture by the substituent on the anion

Phenolic ionic liquids for the efficient and reversible capture of CO(2) were designed and prepared from phosphonium hydroxide and substituted phenols. The electron-withdrawing or electron-donating ability, position, and number of the substituents on the anion of these ionic liquids were correlated with the physicochemical properties of the ionic liquids. The results show that the stability, viscosity, and CO(2)-capturing ability of these ionic liquids were significantly affected by the substituents. Furthermore, the relationship between the decomposition temperature, the CO(2)-absorption capacity, and the basicity of these ionic liquids was quantitatively correlated and further rationalized by theoretical calculation. Indeed, these ionic liquids showed good stability, high absorption capacity, and low absorption enthalpy for CO(2) capture. This method, which tunes the physicochemical properties by making use of substituent effects in the anion of the ionic liquid, is important for the design of highly efficient and reversible methods for CO(2)-capture. This CO(2) capture process using diverse phenolic ionic liquids is a promising potential method for CO(2) absorption with both high absorption capacity and good reversibility.     

Electrocatalytic reduction of CO2 in neat and water-containing imidazolium-based ionic liquids

Energetically efficient electrochemical reduction of CO₂ would offer the possibility of storing electricity from renewables in the form of fuels and other valuable chemicals. It may also help mitigate the increase of atmospheric CO₂ associated with global warming. However, the process suffers from a low energy efficiency because of the large overpotentials required. In aqueous electrolytes, the competing hydrogen evolution reaction also decreases the faradaic efficiency (which contributes to the low energy efficiency of the process). Recent claims of high faradaic efficiency and low overpotentials for the reduction of CO₂ in room-temperature ionic liquids (RTILs) and RTIL–water mixtures have spurred considerable research. Here, we offer a critical review of those claims and of recent work aimed at understanding the details of this important reaction in these nonconventional electrolytes.     

表面活性剂修饰对MCM-41负载离子液体吸附CO2影响的研究

以表面活性剂修饰的MCM-41为载体,采用浸渍法制备了负载离子液体[NH2p-mim][PF6]的二氧化碳吸附剂,考察了表面活性剂对离子液体在MCM-41上分散的影响以及所导致的CO2吸附性能的变化.利用红外光谱(FT-IR),X-射线衍射(XRD),高分辨透射电子显微镜(HRTEM),热重分析(TG)技术对所合成的负载型离子液体吸附剂进行了表征研究,并与其吸附CO2的性能变化、离子液体与表面活性剂相互作用方式等因素进行了关联.结果表明:MCM-41负载离子液体后对CO2的吸附性能略有提高,而经表面活性剂修饰的MCM-41负载离子液体后,对CO2的吸附容量较载体本身提高了2.5倍.这一方面是因为表面活性剂胶束改善了MCM-41上离子液体的分散性,另一方面是表面活性剂胶束对离子液体分子上电荷分布的影响,导致离子液体内部阴阳离子之间的相互作用减弱,从而引起离子液体中-NH2上N原子电子云密度增大,使其与CO2作用更容易.CO2在经表面活性剂修饰后的MCM-41负载离子液体[NH2p-mim][PF6]吸附剂上的吸附受扩散控制,其吸附-脱附CO2所需能量较小,经过5次吸附-脱附循环后,其吸附性能仍保持稳定.热重分析结果表明,经表面活性剂修饰后的MCM-41负载离子液体吸附剂在100℃下氮气气氛再生时不会发生性质改变.     

负载型氨基酸离子液体的制备及其对二氧化碳的吸附性能

采用浸渍蒸发法将四甲基铵甘氨酸([N1111][Gly])和四甲基铵赖氨酸([N1111][Lys])两种离子液体分别负载到硅胶(SG)表面,利用EA、TGA、BET和FT-IR等技术对所得到的吸附剂进行表征,考察了离子液体种类、离子液体负载量和温度等条件对其CO_2吸附性能的影响。结果表明,离子液体成功负载到硅胶表面,所制得的负载型氨基酸离子液体对二氧化碳具有良好的吸附性能。在所考察的温度范围(303.15-323.15 K)内,温度越高,平衡吸附量越小;在负载量为10%-60%,随着负载量的增加,平衡吸附量先增加后减小。对于[N1111][Gly]/SG,当负载量为22.4%(质量分数)、吸附温度为30℃、压力为0.1 M Pa时,二氧化碳的平衡吸附量可达到41 mg/g(相对于1 mol AAILs吸附0.62 mol CO_2),而且,吸附20 min即可达到平衡吸附量的90%。吸附剂在循环使用六次之后,其结构与性能均保持良好。     

Effect of 1-butyl-3-methylimidazolium tetrafluoroborate on the formation rate of CO2 hydrate

The effect of the addition of 1-butyl-3-methylimidazolium tetrafluoroborate （[C4mim][BF4]） on the formation rates of CO2 hydrates was investigate. The isothermal and isobaric methods were used to measure the formation rates of CO2 hydrates. As compared to those of pure water, the data of phase equilibrium changed greatly. The effects of pressure, temperature, and the concentration of [C4mim][BF4] aqueous solution on the formation rates of CO2 hydrates were investigated. With a constant concentration of [C4mim][BF4], the rate of gas consumption was enhanced with the lowering of experimental temperature. However, a decrease in pressure exerted an opposite effect on the rate of gas consumption. Moreover, the addition of [C4mim][BF4] raised the equilibrium pressure of hydrate formation at the same temperature.     

Poly(Ionic Liquid)-Derived Carbon with Site-Specific N-Doping and Biphasic Heterojunction for Enhanced CO2 Capture and Sensing

CO₂ capture is a pressing global environmental issue that drives scientists to develop creative strategies for tackling this challenge. The concept in this contribution is to produce site-specific nitrogen doping in microporous carbon fibers. Following this approach a carbon/carbon heterojunction is created by using a poly(ionic liquid) (PIL) as a “soft” activation agent that deposits nitrogen species exclusively on the surface of commercial microporous carbon fibers. This type of carbon-based biphasic heterojunction amplifies the interaction between carbon fiber and CO₂ molecule for unusually high CO₂ uptake and resistive sensing.     

Separation of ionic liquids from dilute aqueous solutions using the method based on CO2 hydrates

Ionic liquids (ILs) have been regarded as the potential novel solvents for improved analytical-and process-scale separation methods. The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydr...     

离子液体捕集CO2

CO₂是导致温室效应的最主要成分,因此碳捕集技术的研究受到学术界和产业界的高度重视。离子液体具有不挥发、不燃烧、热稳定性好、溶解能力强、结构和性质可调节并可循环使用等特性,在CO₂的吸收/分离领域展现了广阔的应用前景。本文系统地综述了近年来常规离子液体、功能化离子液体、支撑离子液体膜、聚合离子液体以及离子液体与分子溶剂的混合物在捕集CO₂方面的研究进展;讨论了离子液体的阳离子结构、阴离子类型、烷基链长度、阴/阳离子的氟化程度和功能化、离子液体的负载作用和聚合效应以及体系的温度和压力对CO₂选择性捕集性能的影响;分析了可能的捕集机理以及各种捕集方法的优点和缺点;提出了目前需要进一步研究的若干重要问题,并对其发展前景进行了展望。     

功能离子液体[NH2p-bim]BF4吸收CO2的密度泛函研究

用密度泛函理论对功能化离子液体[NH2p-bim]BF4吸收CO2的作用机制进行了理论研究。在RB3LYP/6-311 G**的计算水平对离子液体[NH2p-bim]BF4的结构以及CO2与该离子液体反应可能生成的产物进行了全优化,获得了优化结构的振动频率和热力学数据。计算结果表明,离子液体[NH2p-bim]BF4吸收CO2主要是通过离子液体的阳离子[NH2p-bim] 自偶解离的[NHp-bim]与CO2分子结合生成[O2C-NHp-bim],其结合能为238-260 kJ/mol。     

Propagation kinetics of free‐radical polymerizations in ionic liquids

Propagation rate coefficients, k_p, of methyl methacrylate (MMA) and glycidyl methacrylate (GMA) homopolymerizations were measured at ambient pressure in four ionic liquids (ILs): 1‐ethyl‐3‐methylimidazolium ([emim]) ethyl sulfate and [emim] hexyl sulfate as well as butyl‐3‐methylimidazolium ([bmim]) hexafluorophosphate and [bmim] tetrafluoroborate via the pulsed‐laser polymerization size‐exclusion chromatography technique. In passing from bulk polymerization at 40 °C polymerization in IL solution containing 20 vol % monomer, k_p is enhanced by up to a factor of 4 with MMA and by a factor of 2 with GMA. This enhancement of k_p primarily results from a lowering of activation energy upon partial replacement of monomer by ionic liquid species. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1460–1469, 2008