Recent advances in high performance donor-acceptor polymers for organic photovoltaics

Organic photovoltaic cells made with semiconducting polymers remain one of the most promising technologies for low-cost solar energy due to their compatibility with roll-to-roll printing techniques. The development of new light-absorbing polymers has driven tremendous advances in the power conversion efficiency of these devices. In particular, the use of alternating electron rich (donor) and electron poor (acceptor) segments along the polymer backbone can produce low optical bandgap materials that capture more of the solar spectrum. As a result, power conversion efficiencies over 10% are increasingly common for this technology. This review summarizes the recent advances in donor-acceptor polymer design and synthesis, highlighting the structural features that are key to providing high efficiency, scalable and stable devices.     

Optimization and simplification of polymer–fullerene solar cells through polymer and active layer design

Polymer–fullerene bulk heterojunction (BHJ) solar cells have consistently been at the forefront of the growing field of organic photovoltaics (OPV). The enduring vision of OPV is the promise of combining a simple, low-cost approach with an efficient, flexible, lightweight platform. While efficiencies have improved remarkably over the last decade through advances in device design, mechanistic understanding, and evolving chemical structural motifs, steps forward have often been tied to a loss of simplicity and a deviation from the central vision of OPV. Within the context of active layer optimization, our focus is to target high efficiency while maintaining simplicity in polymer design and active layer processing. To highlight this strategy, this feature article focuses on our work on random poly(3-hexylthiophene) (P3HT) analogs and their application in binary and ternary blend polymer–fullerene solar cells. These random conjugated polymers are conceptually based on combining simple monomers strategically to influence polymer properties as opposed to the synthesis of highly tailored and synthetically complex monomers. The ternary blend approach further exemplifies the focus on device simplicity by targeting efficiencies that are competitive with complex tandem solar cells, but within the confines of a single active-layer processing step. These research directions are described within the broader context of recent progress in the field of polymer–fullerene BHJ solar cells.     

Photoinitiated polymerization in ionic liquids and its application

Ionic liquids (ILs) are low‐melting organic salts often liquid at room temperature, whose unique properties are the reason of increasing interest for their applications as solvents, reaction media and functional additives. The exceptional properties of ILs have proved to be particularly useful in polymer science giving the potential to produce polymeric materials with improved properties or to immobilize ILs in polymer matrices while keeping their special characteristics. One of the possibilities is polymerization in ILs which can also affect positively polymerization reactions. An especially attractive technique is photopolymerization due to the ease of process control, short reaction time and ambient working temperature. This review gives a literature survey of developments in photopolymerization processes carried out in ILs as well as applications of these processes. It covers both the photopolymerization in ILs as well as photopolymerization of IL monomers. The first part presents a short overview of physicochemical and photochemical properties of ILs; it includes also photochemical reactions and photoinitiation of polymerization in ILs. The second part covers both the basic research (kinetics of photopolymerization including polymerization rate coefficients and polymerization of IL monomers) as well as applications of UV‐induced polymerization in ILs. © 2016 Society of Chemical Industry     

Continuous Transesterification with Acidic Ionic Liquids as Homogeneous Catalysts

Ionic liquids (ILs) are recyclable acid catalysts for transesterification reactions. In the present study, different acidic ILs were examined in this reaction, with special focus on their recyclability. Furthermore, the IL‐catalyzed transesterification reaction was realized in continuous operation. A miniplant reactor with technically representative design and operating characteristics was used for this study. The applied rig has a volume of 5 L and an external thermosyphon reboiler. The miniplant reactor can be operated in batch and in continuous mode. ILs functionalized with a sulfonic acid group were found to be the most suitable IL catalysts for the transesterification reactions under investigation. Using these ILs, reaction rates as high as for H₂SO₄ could be realized. Moreover, the IL catalyst was demonstrated to be active for at least 1000 h of operation time.     

Long‐Term Stability,Regeneration and Recycling of Imidazolium‐based Ionic Liquids

Ionic liquids (ILs) are discussed in many current research papers extensively in terms of their potential use in the chemical industry, as process aids and novel materials. The long‐term stability of the IL is for industrial applications as important as to know which species arise during the degradation due to thermal, mechanical, chemical or electrochemical stress. The investigation of the long‐term stability of two selected ILs over several months under process‐like conditions is presented with a subsequent analysis by LC‐MS to identify the resulting decomposition products. Knowledge about the occurring species and their analytical quantification are basis for the selection of appropriate processes for the separation of the decomposition products and the development of recycling processes for ILs. Particularly melt crystallization processes are suitable for separating structurally similar decomposition products that typically occur in the IL degradation.     

Use of ionic liquids for biocatalytic synthesis of sugar derivatives

Sugar‐based compounds are widely used in pharmaceuticals, cosmetics, detergents and food. They are mainly produced by chemical methods, but the use of enzymes as ‘a greener alternative’ to organic synthesis has been investigated for more than 20 years. Due to the low polar substrate solubility in organic solvents compatible with enzymes, research has focused on the application of substitutes for biocatalysis, especially ionic liquids (ILs). After introducing the main properties of ILs and especially their ability to solubilize sugars, this review focuses on one of their applications, the biocatalytic synthesis of carbohydrate derivatives. In this context, they can be used in pure IL systems, in IL/IL systems or in IL/organic solvent systems. Finally, this review provides an update on the environmental fate of ILs. Their exploitation in ‘green’ processes is still limited due to their low degradability but research is currently under way to design new more ‘eco‐friendly’ ILs. Copyright © 2012 Society of Chemical Industry     

Methods for stabilizing and activating enzymes in ionic liquids—a review

Ionic liquids (ILs) have evolved as a new type of non‐aqueous solvents for biocatalysis, mainly due to their unique and tunable physical properties. A number of recent review papers have described a variety of enzymatic reactions conducted in IL solutions; on the other hand, it is important to systematically analyze methods that have been developed for stabilizing and activating enzymes in ILs. This review discusses the biocatalysis in ILs from two unique aspects (1) factors that impact the enzyme's activity and stability, (2) methods that have been adopted or developed to activate and/or stabilize enzymes in ionic media. Factors that may influence the catalytic performance of enzymes include IL polarity, hydrogen‐bond basicity/anion nucleophilicity, IL network, ion kosmotropicity, viscosity, hydrophobicity, the enzyme dissolution, and surfactant effect. To improve the enzyme's activity and stability in ILs, major methods being explored include the enzyme immobilization (on solid support, sol–gel, or CLEA), physical or covalent attachment to PEG, rinsing with n‐propanol methods (PREP and EPRP), water‐in‐IL microemulsions, IL coating, and the design of enzyme‐compatible ionic solvents. It is exciting to notice that new ILs are being synthesized to be more compatible with enzymes. To utilize the full potential of ILs, it is necessary to further improve these methods for better enzyme compatibility. This is what has been accomplished in the field of biocatalysis in conventional organic solvents. Copyright © 2010 Society of Chemical Industry     

Polymer electrolytes integrated with ionic liquids for future electrochemical devices

The global energy crisis and an increase in environmental pollution in the recent years have drawn the attention of the scientific community towards the development of efficient electrochemical devices. Polymers containing charged species have the potential to serve as electrolytes in next‐generation devices and achieving high ion transport properties in these electrolytes is the key to improving their efficiency. In this article, we explore ways to improve the ion transport properties of solid polymer electrolytes by focusing on the use of ionic liquids (ILs). The application of IL‐incorporated polymer electrolytes in lithium batteries, high temperature fuel cells, and electro‐active actuators is summarized. For each system, the current level of understanding of the diverse factors affecting the transport properties of polymer electrolytes integrated with ILs is presented, in addition to the challenges encountered and strategies toward obtaining significantly improved device performances. The creation of self‐assembled morphologies in IL‐containing polymer electrolytes by the use of block copolymers is particularly highlighted as a novel prospective technique geared towards obtaining next‐generation electrochemical devices with enhanced performances. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Computer‐aided design of ionic liquids as solvents for extractive desulfurization

Although ionic liquids (ILs) have been widely explored as solvents for extractive desulfurization (EDS) of fuel oils, systematic studying of the optimal design of ILs for this process is still scarce. The UNIFAC‐IL model is extended first to describe the EDS system based on exhaustive experimental data. Then, based on the obtained UNIFAC‐IL model and group contribution models for predicting the melting point and viscosity of ILs, a mixed‐integer nonlinear programming (MINLP) problem is formulated for the purpose of computer‐aided ionic liquid design (CAILD). The MINLP problem is solved to optimize the liquid‐liquid extraction performance of ILs in a given multicomponent model EDS system, under consideration of constraints regarding the IL structure, thermodynamic and physical properties. The top five IL candidates preidentified from CAILD are further evaluated by means of process simulation using ASPEN Plus. Thereby, [C₅MPy][C(CN)₃] is identified as the most suitable solvent for EDS. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1013–1025, 2018     

金属基离子液体催化生物质转化研究进展

生物质是自然界中含量丰富且唯一可再生的有机碳资源,可以经过化学反应转化为高附加值碳基化学品和燃料,被认为是传统化石资源的理想替代品。催化材料的设计开发是生物质资源开发和利用的关键所在,离子液体因其独特的可设计性,在生物质资源利用过程中得到广泛应用。鉴于金属活性中心的催化活性以及离子液体的可设计性,将金属活性中心引入离子液体中制备金属基离子液体催化剂在生物质领域受到广泛关注,并取得一定进展。基于上述背景,本文综述了近年来金属基离子液体催化剂在生物质催化转化过程中的研究进展,重点介绍金属氯化物型、多金属氧酸盐型金属基离子液体在生物质基碳水化合物、木质素催化转化制备平台化学品,以及油脂催化（转）酯化制备生物柴油方面的研究进展;同时还综述了金属螯合物型金属基离子液体以及离子液体金属盐在生物质催化转化方面的研究工作。此外,对金属基离子液体在生物质资源方面的应用进行了总结和展望,并对金属基离子液体催化剂的设计提出建议,以期有助于生物质资源的开发和利用。     

Metal nanoparticles in ionic liquid‐cosolvent biphasic systems as active catalysts for acetylene hydrochlorination

Ionic liquid (IL)‐stabilized metal nanoparticles (NPs) have attracted increased attention as novel catalysts for various reactions due to their excellent stability and high activity. However, the high viscosity of ILs limits their applications. Here, for the first time, we reported an NPs@IL‐cosolvent liquid–liquid biphasic system for metal NPs catalysis. The NPs were successfully confined to IL phase, and abundant IL droplets containing NPs were generated under the reactant flow. The NPs@IL droplets served as microreactors for the catalysis; while the low viscosity organic phase enabled the rapid mass transfer of substances. The biphasic system exhibited improved performance for acetylene hydrochlorination than that of the pure IL system. An acetylene conversion of 98% and a selectivity of 99.5% were achieved along with a 90% decrease on IL usage. The tolerable gas hourly space velocity in the biphasic system for a satisfactory conversion was almost double that of the pure IL system. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2536–2544, 2018     

Computer‐aided design of tailor‐made ionic liquids

Ionic liquids (IL), with their negligible vapor pressure, have the potential to replace volatile organic solvents in several processes. They also exhibit other unique characteristics, such as high thermal stability, wide liquid range, and wide electrochemical window, which make them attractive for many important applications. In addition, millions of ILs can be formed through different combination of cations, anions, and other functional groups. Till now, majority of work on IL selection, for a given application, is guided by trial and error experimentation. In this article, we present a computer‐aided IL design framework, based on semiempirical structure‐property models and optimization methods, which can consider several IL candidates and design optimal structures for a given application. This powerful methodology has great potential to act as a knowledge‐based framework to aid synthetic chemists and engineers develop new ILs. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4627–4640, 2013     

Protein stabilization and enzyme activation in ionic liquids: specific ion effects

There are still debates on whether the hydration of ions perturbs the water structure, and what is the degree of such disturbance; therefore, the origin of the Hofmeister effect on protein stabilization continues to be questioned. For this reason, it is suggested to use the ‘specific ion effect’ instead of other misleading terms such as Hofmeister effect, Hofmeister series, lyotropic effect, and lyotropic series. This review first discusses the controversial aspect of inorganic ion effects on water structures, and several possible contributors to the specific ion effect of protein stability. Due to recent overwhelming attraction of ionic liquids (ILs) as benign solvents in many enzymatic reactions, this paper further evaluates the structural properties of ILs and molecular‐level interactions in neat ILs and their aqueous solutions. Next, the specific ion effects of ILs on enzyme stability and activity are systematically compared and it is concluded that (a) the specificity of many enzymatic systems in diluted aqueous IL solutions is roughly in line with the traditional Hofmeister series albeit some exceptions; (b) however, the specificity follows a different track in concentrated or neat ILs because other factors (such as hydrogen‐bond basicity, nucelophilicity, and hydrophobicity, etc.) are playing leading roles. In addition, some examples of biocatalytic reactions in IL systems that are guided by the empirical specificity rule are demonstrated. © 2015 Society of Chemical Industry     

Ionic Liquids‐Based Membranes for Carbon Dioxide Separation

Ionic liquids (ILs) have gained wide‐spread focus owing to its negligible vapor pressure, low heat capacity, high thermal stability, and structural diversity. The solubility and selectivity toward carbon dioxide has made ILs a unique platform that possess the potential in gas separations. In particularly, combining functional ILs with membranes and porous supports is an efficient way to design task‐specific materials for CO₂ separations. This minireview summarizes the developments and advances of ionic liquids‐based membranes for CO₂ separations in recent three years, with an emphasis on the strategy of incorporating ionic liquids and CO₂ separation performance.     

Photothermal materials for efficient solar powered steam generation

Solar powered steam generation is an emerging area in the field of energy harvest and sustainable technologies. The nano-structured photothermal materials are able to harvest energy from the full solar spectrum and convert it to heat with high efficiency. Moreover, the materials and structures for heat management as well as the mass transportation are also brought to the forefront. Several groups have reported their materials and structures as solutions for high performance devices, a few creatively coupled other physical fields with solar energy to achieve even better results. This paper provides a systematic review on the recent developments in photothermal nanomaterial discovery, material selection, structural design and mass/heat management, as well as their applications in seawater desalination and fresh water production from waste water with free solar energy. It also discusses current technical challenges and likely future developments. This article will help to stimulate novel ideas and new designs for the photothermal materials, towards efficient, low cost practical solar-driven clean water production.     

Understanding the influence of the ionic liquid composition and the surrounding phase nature on the stability of supported ionic liquid membranes

The industrial application of supported liquid membranes (SLMs) is still limited due to concerns about their stability. In a previous work, the selective separation of the substrates and products of a transesterification reaction was successfully carried out using Nylon membranes impregnated with ionic liquids (ILs). This article analyses the effect of both the IL composition and the nature of the surrounding phase on the stability of these SLMs to design highly stable supported ionic liquid systems. For this purpose, the stability of SLMs based on several ILs after immersion for a week in different feed/receiving phases was characterized using scanning electron microscopy combined with energy dispersive X‐ray (SEM‐EDX). The differential migration of the ILs observed from the membrane toward the surrounding phases was found to be correlated with the solubility of the ILs in the contacting phases. It was observed that SLM stability increased as the polarity of the solvent used as receiving phase decreased and as the hydrophilic character of the ILs used as liquid phase increased. Furthermore, the polymeric support was found to have a strongly stabilizing effect because losses of IL after immersion in a given surrounding phase were much lower than that derived from the solubility of the IL in this phase. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Shear stability of inverse latexes during their polymerization process

The shear‐stability of inverse latexes (IL) during their polymerization process is studied. The IL is made of water droplets containing a copolymer of acrylamide and dimethyl‐aminoethyl‐methylenechloride emulsified in a paraffin oil. It is found for the first time that the shear stability of the ILs is a nonmonotonic function of the monomer conversion. At low conversions the shear stability increases as the conversion increases, but at a certain conversion value it reaches a local maximum and then decreases with conversion. Moreover, at the final stage of the conversion, the shear stability can increase again. A proper interpretation of this behavior is proposed and related to the combined effects of the polymer properties, fractal aggregation, and coalescence. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1380–1384, 2015     

Separation and recovery of cellulose and lignin using ionic liquids: a process for recovery from paper‐based waste

BACKGROUND: The production of paper makes use of cellulose and lignin as a raw material, and almost all cellulose and lignin production comes from raw wood materials, contributing to deforestation and resulting in potential environmental harm. It is therefore beneficial to develop technologies for cellulose and lignin recovery for re‐use and sustainability of resources. RESULTS: Three imidazolium based ionic liquids (ILs), 1‐(2‐cyanoethyl)‐3‐methylimidazolium bromide (cyanoMIMBr), 1‐propyl‐3‐methylimidazolium bromide (propylMIMBr) and 1‐butyl‐3‐methylimidazolium chloride (butylMIMCl), were synthesised by microwave technology and fully characterised by mass spectrometry, thermogravimetric differential scanning calorimetry, thin layer chromatography, nuclear magnetic resonance and Fourier transform infrared spectroscopies. Cellulose and lignin were soluble in all three ILs with solubility being greatest in cyanoMIMBr. Regeneration of cellulose and lignin was achieved from saturated solutions of cellulose in IL and lignin in IL for all three ILs. The ILs propylMIMBr and butylMIMBr have been used for the first time in the separation and recovery of cellulose and lignin and regeneration of the IL from a mixture of cellulose and lignin in IL. FTIR analysis confirms successful recovery. CONCLUSIONS: This work demonstrates the ability of ILs to separate and recover cellulose and lignin from a mixed system. Copyright © 2009 Society of Chemical Industry     

Crystallographic Investigation of Imidazolium Ionic Liquid Effects on Enzyme Structure

We present the first crystallographic insight into the interactions of an ionic liquid (IL) with an enzyme, which has widespread implications for stabilizing enzymes in IL media for biocatalysis. Structures of Bacillus subtilis lipase A (lipA) and an IL‐stable variant (QM‐lipA) were obtained in the presence of increasing concentrations of 1‐butyl‐3‐methylimidazolium chloride ([BMIM][Cl]). These studies revealed that the [BMIM] cation interacts with surface residues through hydrophobic and cation–π interactions. Of specific interest was the disruption of internal stacking interactions of aromatic side chains by [BMIM], which provides structural evidence for the mechanism of enzyme denaturation by ILs. The interaction of [BMIM] and Cl ions with lipA was reduced by the stabilizing mutations Y49E and G158E in QM‐lipA. Ultimately, these findings present the molecular basis for stabilizing enzymes from IL‐induced inactivation, as well as the selection of ILs that are less denaturing.     

Conjugated polymers with tethered electron‐accepting moieties as ambipolar materials for photovoltaics

Conjugated polymers are of increasing interest as semiconductors for soft (opto)electronic devices, including photovoltaic elements. A promising conversion of solar energy into electrical energy is possible with blends of soluble electron donor‐type conjugated polymers and fullerenes as electron‐acceptor, transporting component. This approach, called bulk‐heterojunction, suggested the preparation of intrinsic ambipolar materials to control simultaneously the electronic and morphological properties. On these bases, the covalent grafting of acceptor moieties onto conjugated backbones seemed attractive for the preparation of intrinsically ambipolar polymeric materials (‘double‐cable’ polymers) as an alternative to donor–acceptor composites. The design, characterisation and application of this novel class of polymers are reviewed taking into account the current understanding of organic photovoltaics. Copyright © 2007 Society of Chemical Industry