Design and synthesis of pyromellitic diimide‐based donor–acceptor conjugated polymers for photovoltaic application

Three of conjugated polymers based on pyromellitic diimide (PMDI) as the acceptor unit and thienothiophene (TT) as the donor unit were successfully synthesized by Stille coupling. The effect of the side chain length and thiophene π‐bridge on the polymers' optical and electrochemical properties was investigated. Electrochemical characterization indicated that these polymers have deep highest occupied molecular orbital energy levels between ?5.7 and ?5.8 eV. Polymer solar cells were fabricated by using these PMDI‐based polymers as the donor and [6,6]‐phenyl‐C61‐butyric acid methyl ester as the acceptor. The polymer P1 whose PMDI unit was functionalized with 2‐ethylhexyl side chain shows the higher short‐circuit current (J_sc) and fill factor (FF) compared with that of P2 with a 2‐octyldodecyl side chain on the PMDI unit. The results also illustrate that the insertion of a thiophene π‐bridge between PMDI and TT (the polymer P3) leads to the broader absorption and better photovoltaic performance. The best performance was obtained from the cell based on the polymer P3 with a power conversion efficiency of 0.43% under the illumination of AM 1.5 G, 100 mW/cm². Copyright © 2014 John Wiley & Sons, Ltd.     

Recycling ground tire rubber (GTR) scraps as high‐impact filler of in situ produced polyketone matrix

A sustainable procedure for recycling powdered rubber coming from scrap tires (ground tire rubber [GTR]) is proposed as based on the dispersion in polyketone (PK) matrix, obtained in situ by CO/ethylene copolymerization. Three types of catalysts are used operative in solvents of different polarities. The catalyst productivity and the hybrids morphology are evaluated and optimized to final composites features. The obtained products are characterized by scanning electron microscopy, atomic force microscopy, and solvent extractions in order to investigate the occurrence and the extent of interactions between PK macromolecular chains and the GTR components; and their effects on the final properties were tested by differential scanning calorimetry, thermogravimetric analysis, and rheological measurements. For comparison purpose, a composite with GTR included into the matrix through blending is prepared. The results evidenced the key role exerted by the catalyst that, when operative in apolar solvent (able to swell the rubber phase), provides composites with good interfacial adhesion and breaking up of the particles with beneficial effects on final properties particularly thermal features and processability. Copyright © 2014 John Wiley & Sons, Ltd.     

Super‐fast oil uptake using porous ultra‐high molecular weight polyethylene sheets

This paper presents the oil uptake of porous sorbent polymer sheets consisting of ultra‐high molecular weight polyethylene. A comprehensive set of experiments are performed showing the saturation contact time, retention value, mechanical properties, oil pick‐up ratio, pick‐up density, and dynamic dripping profile. Kinetic modeling of the oil sorption is also provided. The experimental results show a good correlation with the pseudo‐second order model. The sheets exhibit high oil uptake speeds, requiring less than 2 min in contact with the oil to reach saturation. The sheets fulfill the criteria of high uptake kinetics, high sorption capacity, and high mechanical strength simultaneously. Those characteristics enable their use in practical spill response. Copyright © 2014 John Wiley & Sons, Ltd.     

Phenylboronate‐diol crosslinked polymer/SWCNT hybrid gels with reversible sol–gel transition

This work demonstrates the successful incorporation of functionalized single‐walled carbon nanotubes (f‐SWCNTs) into the phenylboronate‐diol crosslinked polymer gel to create a hybrid system with reversible sol–gel transition. The phenylboronic acid‐containing and diol‐containing polymers were first separately prepared by the reversible addition–fragmentation chain transfer polymerization. Covalent functionalization of single‐walled carbon nanotubes (SWCNTs) with an azide‐derivatized, diol‐containing polymer was then accomplished by a nitrene addition reaction. Subsequently, the hybrid gels were prepared by crosslinking the mixture of f‐SWCNTs and diol‐containing polymer with the phenylboronic acid‐containing polymer. The hybrid gel has been characterized by scanning electron microscopy (SEM) and rheological analysis. The SEM measurement demonstrated a homogeneous dispersion of f‐SWCNTs within the gel matrices. Rheological experiments also demonstrated that the hybrid gel exhibited storage moduli significantly higher than those of the native gel obtained from the phenylboronic acid‐containing and diol‐containing polymers. The hybrid gel can be switched into their starting polymer (f‐SWCNTs) solutions by adjusting the pH of the system. Moreover, the hybrid gel revealed a self‐healing property that occurred autonomously without any outside intervention. By employing this dynamic character, it is possible to regenerate the used gel, and thus, it has the potential to perform in a range of dynamic or bioresponsive applications Copyright © 2013 John Wiley & Sons, Ltd.     

Electropolymerized coatings of poly(o‐anisidine) and poly(o‐anisidine)‐TiO2 nanocomposite on aluminum alloy 3004 by using the galvanostatic method and their corrosion protection performance

Poly(o‐anisidine) (POA) and poly(o‐anisidine)‐TiO₂ (POA‐TiO₂) nanocomposite coatings on aluminum alloy 3004 (AA3004) have been investigated by using the galvanostatic method. The electrosynthesized coatings were characterized by FT ‐ IR spectroscopy, XRD, SEM ‐ EDX and SEM. The corrosion protection performance of POA and POA‐TiO₂ nanocomposite coatings was investigated in the 3.5% NaCl solution by using potentiodynamic polarization technique and electrochemical impedance spectroscopy. The results show that the corrosion rate of the nanocomposite coatings is about 900 times lower than the bare AA3004 under optimal conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

Antimicrobial silica particles loaded with quaternary ammonium polyethyleneimine network

Silica particles functionalized with quaternary ammonium groups were prepared by interpenetrating polyethylenimine (PEI) into silica particles and crosslinking with diiodopentane, followed by octyliodide alkylation and methyliodide quaternarization (S‐QA‐PEI). The synthesized S‐QA‐PEI particles were identified with a slight particle size increase of 2–3 µm. Different ratios of PEI:silica particles were prepared and analyzed. While silica particles are negatively charged, ?16.7 ± 5.11 mV, the prepared S‐QA‐PEI particles are positively charged, +50–60 mV. These particles were embedded in poly(ethylene vinyl acetate) and poly(ethylene methacrylic acid) coatings which exhibited strong antibacterial activity. Copyright © 2014 John Wiley & Sons, Ltd.     

Performance Enhancement of Bulk Heterojunction Solar Cells with Direct Growth of CdS‐Cluster‐Decorated Graphene Nanosheets

Two‐dimensional graphene–CdS (G–CdS) semiconductor hybrid nanosheets were synthesized in situ by graphene oxide (GO) quantum wells and a metal–xanthate precursor through a one‐step growth process. Incorporation of G–CdS nanosheets into a photoactive film consisting of poly[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b]dithiophene‐2,6‐diyl]‐alt‐[2‐(2‐ethyl‐hexanoyl)‐thieno[3,4‐b]thiophen‐4,6‐diyl] (PBDTTT‐C‐T) and [6,6]‐phenyl C₇₀ butyric acid methyl ester (PC₇₀BM) effectively decreases the exciton lifetime to accelerate exciton dissociation. More importantly, the decreasing energy levels of PBDTTT‐C‐T, PC₇₀BM, and G–CdS produces versatile heterojunction interfaces of PBDTTT‐C‐T:PC₇₀BM, PBDTTT‐C‐T:G–CdS, and PBDTTT‐C‐T:PC₇₀BM:G–CdS; this offers multi‐charge‐transfer channels for more efficient charge separation and transfer. The charge transfer in the blend film also depends on the G–CdS nanosheet loadings. In addition, G–CdS nanosheets improve light utilization and charge mobility in the photoactive layer. As a result, by incorporation of G–CdS nanosheets into the active layer, the power‐conversion efficiency of inverted solar cells based on PBDTTT‐C‐T and PC₇₁BM is improved from 6.0 % for a reference device without G–CdS nanosheets to 7.5 % for the device with 1.5wt % G–CdS nanosheets, due to the dramatically enhanced short‐circuit current. Combined with the advantageous mechanical properties of the PBDTTT‐C‐T:PC₇₀BM:G–CdS active layer, the novel CdS‐cluster‐decorated graphene hybrid nanomaterials provide a promising approach to improve the device performance.     

对硝基苯酚分子印迹聚合物最佳功能单体的筛选及其水样固相萃取中的应用

以对硝基苯酚(4-NP)为对象,采用非印迹聚合物(NIP)库筛选法选出乙烯基咪唑为最佳功能单体,通过实验选出乙腈为最合适的聚合溶剂、三甲氧基丙基三甲基丙烯酸酯(TRIM)为交联剂制备分子印迹聚合物。对固相萃取进行了优化,用pH=2.5的磷酸盐缓冲溶液上样、体积比为45∶55的乙腈和磷酸盐缓冲溶液淋洗、甲醇洗脱条件下,聚合物具有最佳印迹效果。4-NP分子印迹聚合物的表观吸附量达到5.8 mg/g。该印迹聚合物对4-NP及其结构类似物苯酚和对氯苯酚的萃取回收率分别为96.0%、78.8%和77.8%,表明具有较高的选择性,还成功地用于自来水样品中4-NP的固相萃取,回收率达到93.1%。由此可得该方法快速、有效,可用于分子印迹聚合物优化制备。     

基于膦酸基的高温质子交换膜的研究进展

提高质子交换膜燃料电池(PEMFCs)的工作温度,不但可以提高电催化剂的活性以及电催化剂对原料气中CO等杂质气体的耐受能力,少用甚至不用Pt 等贵金属作电催化剂,还可以简化PEMFCs的水热管理系统,提高PEMFCs的综合能量转化效率. 实现高温PEMFCs的核心是开发能够适用于高温PEMFCs的高温质子交换膜(HT-PEM),是PEMFCs的研究热点. 在众多HT-PEM候选材料中,基于膦酸基的质子交换膜材料是最具前途的候选材料之一,是制备HT-PEM的主要研究方向. 本文综述了基于膦酸基的HT-PEM的研究进展,讨论了膦酸基参与的质子传导机理,比较了纯聚合物膦酸膜、膦酸基接枝改性膜、酸-碱两性膜、掺杂型复合膜的电导率、物理化学稳定性、机械性能等. 最后,展望了基于膦酸基的HT-PEM的发展趋势.     

碱性固体燃料电池碱性聚合物电解质膜的最新研究进展

最近,碱性聚合物电解质膜燃料电池(APEMFC)因具有电极反应动力学快以及不依赖于贵金属铂催化剂等诸多优点而成为一个热门话题.作为其中一个关键部件,碱性聚合物电解质膜直接影响燃料电池的性能和成本.然而,迄今为止,仍然没有令人满意的碱性电解质膜材料.为此,大量研究被开展和报道.本文综述了近三年内文献中关于燃料电池碱性聚合物电解质膜的最新研究进展:包括各种各样的合成策略,构效关系,水管理以及非原位或原位稳定性测试等等.尤其是一些新的金属离子基阴离子交换膜和冠醚基阴离子交换膜首次被提及和评论.此外,还进一步预测了将来的发展趋势.