PNIPAM/锂藻土/氧化石墨烯近红外光响应水凝胶的制备及其应用初探

以锂藻土（Laponite）为交联剂、氧化石墨烯（GO）为光热转换试剂，通过N-异丙基丙烯酰胺（NIPAM）原位聚合，制备近红外光（NIR）响应水凝胶（Laponite-PNIPAM/GO）。首先考察Laponite的含量对Laponite-PNIPAM水凝胶的断裂伸长率和断裂强度的影响，并考察GO含量对Laponite-PNIPAM/GO水凝胶相关性能的影响，来确定Laponite和GO的合适含量。随后对所制备的水凝胶体积相转变温度（VPTT）及NIR响应性进行表征，并对Laponite-PNIPAM/GO水凝胶在光控流体开关及光控脱附方面的应用进行了初步探索。结果表明：Laponite-PNIPAM/GO水凝胶具有较高强度和良好的韧性, 断裂伸长率可达1100%以上，Laponite-PNIPAM/GO水凝胶的VPTT在36 ℃左右；NIR照射下，Laponite-PNIPAM/GO水凝胶能在3分钟内从20.3 ℃升温至48.5 ℃；由于Laponite-PNIPAM/GO水凝胶具有温敏性和光热效应，其具有作为光控流体开关及光控脱附的潜力。     

表面润湿性可控的碳纳米管负载钯催化剂及其在1,8-二硝基萘选择性加氢中的催化性能

首先通过原子转移自由基聚合技术（atom transfer radical polymerization,ATRP）在碳纳米管（CNT）表面接枝聚N-异丙基丙烯酰胺（PNIPAM）,成功制备出表面润湿性可控的复合载体（CNT-PNIPAM）,并以其为载体制备Pd催化剂（Pd/CNT-PNIPAM）。采用红外光谱仪（FTIR）、热重仪（TGA）、有机元素分析仪（OEA）、差示量热仪（DSC）、X射线衍射仪（XRD）、透射电镜（TEM）和N₂吸附等手段对材料进行表征。制备的催化剂用于1,8-二硝基萘（1,8-DNN）选择性加氢反应,并研究表面化学对催化性能的影响。结果表明,CNT-PNIPAM的最低临界溶液温度（LCST）为37℃左右。利用温敏效应,CNT-PNIPAM在25℃（＜LCST）下负载Pd纳米颗粒,粒径为3.6nm±0.8nm。载体在低温下的亲水表面提高了Pd纳米颗粒在其上的分散。Pd/CNT-PNIPAM在120℃ （＞LCST）下表面润湿性发生转换。PNIPAM接枝引起催化剂表面化学性质的变化,进而使其对底物的吸附性能发生改变。Pd/CNT-PNIPAM上Pd颗粒的高度分散及其对1,8-DNN优良的吸附性能不仅使催化活性得以提高（反应速率常数k=2.1h^-1）,而且对1,8-DAN的选择性也更高（完全反应时1,8-DAN选择性达98%）。     

多孔温敏凝胶的制备及性能测试

N-异丙基丙烯酰胺(NIPA)具有优良的温敏智能特性和记忆效应,目前已在药物缓释、物料分离、酶的固定、生物医学材料等领域得到广泛应用.本文以不同分子量的聚乙二醇(PEG)为致孔剂,在18℃下制备了多孔结构的共聚凝胶,并考察了聚乙二醇(PEG)分子量和用量对凝胶溶胀率的影响.研究表明,PEG的加入使凝胶形成多孔结构,多孔...     

石墨烯/二氧化钛复合材料的制备及催化性能研究

以石墨粉和钛酸四丁酯为原料,通过水热法一步合成了石墨烯/二氧化钛复合材料.采用XRD和SEM对该复合物进行了表征,并研究了光照条件、石墨烯含量、煅烧温度、光催化时间和pH等因素对聚丙烯酰胺降黏性能的影响.实验结果表明:在石墨烯/二氧化钛复合材料中,二氧化钛纳米颗粒均匀地分散在石墨烯层上;当在石墨烯质量分数为10％、煅烧温度为450℃、pH为6～7、光催化30 min等条件下,石墨烯/二氧化钛复合材料在紫外光下对聚丙烯酰胺的光催化降黏率能达到96％以上.     

快速响应的温敏性PNIPAAm／粘土复合水凝胶的合成及性能研究

以碳酸钠为制孔剂合成了快速响应的温敏性PNIPAAm／粘土复合水凝胶(NNC水凝胶),DSC分析表明,其体积相转变温度在33℃左右,与传统的PNIPAAm水凝胶没有很大的偏差。动力学研究表明,该水凝胶在温敏膨胀或收缩时,具有快速的响应速率,在5 min内的失水率达90％以上,这与扫描电镜观察到水凝胶具有大而连贯的孔洞结构相一致。     

PVA-g-PNIPA温敏凝胶纤维的制备及性能研究

以过硫酸钾（KPS）为引发剂,以二甲基亚砜（DMSO）为溶剂,通过自由基聚合的方法制备PVA接枝NIPA共聚物（PVA-g-PNIPA）。用丙酮做凝固浴,通过湿法纺丝工艺,制得PVA-g-PNIPA凝胶纤维,用甲醛后交联该纤维。结果表明该纤维具有良好的温度响应性能。     

石墨烯/棉织物制备及其电热性能研究

采用丝网印刷方式将氧化石墨烯浆料印制在棉织物表面,再经还原方法得到了电热性能优良的石墨烯棉织物。综合分析织物表面形貌、表面电阻及发热性能,探究了印制次数、还原浓度、还原时间及还原剂种类对石墨烯棉织物发热性能影响。结果表明,印制次数为10次,还原浓度为5 mg/mL,时间6 h,施加在两端电压为24 V时,织物的表面电阻为4.0 kΩ/cm,表面温度为46.8℃,电热性能达到最佳。     

含PEG组分的聚(N-异丙基丙烯酰胺)水凝胶的制备研究

首先合成了二丙烯酰基封端的聚乙二醇(PEG)大分子交联剂,然后使其与N,N-亚甲基双丙烯酰胺(BIS)和(N-异丙基丙烯酰胺)(NIPAM)单体进行交联反应,制备了PNIPAM-co-PEG-co-BIS水凝胶。与通常的PNIPAM-co-BIS凝胶比较,PNIPAM-co-PEG-co-BIS凝胶显示了明显加速的去溶胀动力学。这种加速的去溶胀性能归因于凝胶中的PEG组分为凝胶提供了亲水通道,在缩水过程中有利于凝胶的脱水。     

含β-环糊精单元温敏性聚合物的制备及其温敏性能测试

文章通过N-异丙基丙烯酰胺(NIPAAm)同马来酸酐(MAH)改性的β-环糊精发生共聚反应得到一种新型温敏性共聚物,表征确认其结构,并对其温敏性能进行了研究。结果:由于环糊精单元的引入,产品较NIPAAm均聚物有更高的最低临界共溶温度(LCST),环糊精单元在产品中所占的比例越多,其LCST值越大,并且在高pH和低离子浓度环境下,产品有更高的LCST。     

磺化石墨烯固体酸催化剂的制备及活性评价

石墨烯是由碳原子以sp₂杂化连接的单原子层构成的新型二维碳原子晶体,由于含有众多具有反应活性的碳碳双键,石墨烯纳米片表面很容易进行化学修饰键合有机官能团而改变其性质。采用改良Hummers法制备氧化石墨烯,通过磺化反应制备磺化石墨烯固体酸催化剂,通过FT-IR、元素分析和XPS等对其结构进行表征。将制备的氧化石墨烯和磺化石墨烯应用于催化纤维二糖的水解反应,以纤维二糖糖苷键的水解反应为模型考察其酸催化性能。结果表明,氧化石墨烯和磺化石墨烯中含有-COOH、-OH和-SO₃H等官能团,磺酸根密度分别为1.0 mmol·g^-1和2.2 mmol·g^-1,氧化石墨烯和磺化石墨烯具有与H₂SO₄相比拟的酸催化活性,尽管酸性强度和密度较低,但催化活性与H₂SO₄相当。     

水热合成rGO负载的MoS2催化剂及其催化蒽加氢性能

采用水热法制备了一系列还原氧化石墨烯（rGO）负载的MoS₂催化剂（MoS₂/rGO）。通过SEM、XRD、EDX、拉曼光谱、HRTEM等手段表征了不同钼源制备的MoS₂/rGO催化剂中MoS₂的堆积层数、片层尺寸、分散性等纳米结构。表征结果显示水热法可以成功地将MoS₂高分散、均匀地负载在rGO表面,且可以通过调控钼源种类调变MoS₂/rGO催化剂中MoS₂催化加氢活性位。采用蒽作为重质油模型化合物评价了MoS₂/rGO催化剂的催化加氢性能,结果表明以四硫代钼酸铵为钼源水热法制备的MoS₂/rGO-ATTM催化剂蒽加氢率和八氢蒽选择性分别是浸渍法制备IM-MoS₂/rGO催化剂的2.0倍和4.2倍。MoS₂/rGO催化剂的催化加氢活性与比表面积无关,主要取决于其上MoS₂纳米片的堆积层数和片层长度。MoS₂/rGO-ATTM催化剂的高催化加氢活性可以归结于其上MoS₂纳米片的高催化加氢活性位暴露量、催化剂的高分散性和高悬浮性。     

Preparation and characterization of graphene composites with conducting polymers

We report a new route for preparing electro‐conductive composites based on reduced graphene oxide (RG‐O) and poly(3,4‐ethylenedioxythiophene) (PEDOT). The composites were prepared by in situ polymerization of EDOT in aqueous mixture containing RG‐O platelets modified with poly(sodium 4‐styrenesulfonate) (PSS). In the synthetic process, PSS molecules stabilize RG‐O in the aqueous phase and function as a polymerization template to hybridize PEDOT chains along RG‐O platelets. Compared with the RG‐O platelets, the resulting composites show an enhanced electrical conductivity of 9.2 S cm^?1 with good thermal stability. Copyright © 2011 Society of Chemical Industry     

Fabrication and characterization of poly(vinyl alcohol)/graphene oxide nanofibrous biocomposite scaffolds

Nanofibrous biocomposite scaffolds of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were prepared by using electrospinning method. The microstructure, crystallinity, and morphology of the scaffolds were characterized through X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The mechanical properties were investigated by tensile testing. Moreover, Mouse Osteoblastic Cells (MC3T3‐E1) attachment and proliferation on the nanofibrous scaffolds were investigated by MTT [3‐(4,5‐dimeth‐ylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide] assay, SEM observation and fluorescence staining. XRD and FTIR results verify the presence of GO in the scaffolds. SEM images show the three‐dimensional porous fibrous morphology, and the average diameter of the composite fibers decreases with increasing the content of GO. The mechanical properties of the scaffolds are altered by changing the content of GO as well. The tensile strength and elasticity modulus increase when the content of GO is lower than 1 wt %, but decrease when GO is up to 3 and 5 wt %. MC3T3‐E1 cells attach and grow on the surfaces of the scaffolds, and the adding of GO do not affect the cells' viability. Also, MC3T3‐E1 cells are likely to spread on the PVA/GO composite scaffolds. Above all, these unique features of the PVA/GO nanofibrous scaffolds prepared by electrospinning would open up a wide variety of future applications in bone tissue engineering and drug delivery systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

表面修饰氧化石墨烯纳米带增强PMMA的研究

以多壁碳纳米管(MWNTs)为原料,使用纵向氧化切割法制备了氧化石墨烯纳米带(GONR),通过物理吸附作用制备了聚醚型苯并咪唑(OPBI)非共价修饰GONR(FGONR)。采用溶液浇注法制得了聚丙烯酸甲酯(PMMA)/FGONR复合材料薄膜,对FGONR及其PMMA复合材料的结构与性能进行了研究,同时对比了以MWNTs,GONR,OPBI改性MWNTs(FCNTs)增强的PMMA复合材料的力学性能。结果表明:OPBI成功地物理吸附到GONR的表面,且FGONR在PMMA中具有良好的分散性能;在PMMA/FGONR复合材料中,当FGONR的质量分数为0.5%时,复合材料的拉伸强度达到49.50 MPa,杨氏模量达到2.27 GPa,其增强效果比MWNTs,GONR,FCNTs的要好,FGONR有望作为制备高性能复合材料的一种良好的纳米填料。     

氮化碳负载钯催化剂催化苯酚加氢制环己酮

为了开发苯酚加氢制环己酮高效催化剂,将脲在550 ℃高温聚合,制备了片层状氮化碳催化剂载体g-CN;负载钯纳米粒子后,得到Pd/g-CN催化剂。采用红外光谱、X射线粉末衍射、透射电镜和X射线光电子能谱对催化剂进行表征。将Pd/g-CN催化剂用于催化苯酚水相加氢,考察了不同载体和反应温度对催化性能的影响,并对催化剂重复使用性能进行研究。结果表明,载体g-CN含有大量的含N基团,能有效稳定金属纳米粒子,从而获得粒径较小、分散较好的Pd纳米粒子;同时,g-CN具有较强碱性,有利于苯酚的吸附,可提高苯酚的反应速率和环己酮选择性。采用负载Pd质量分数2%的Pd/g-CN催化剂,在反应温度80 ℃、反应压力0.1 MPa、n(Pd)∶n(苯酚)=0.02、苯酚1 mmol、水3 mL和反应时间3 h条件下,苯酚可完全转化,环己酮选择性高达99%。Pd/g-CN催化剂制备工艺简单,原料价廉,催化性能优异。     

氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能

针对甲醇气相氧化羰基化直接合成碳酸二甲酯（DMC）反应中催化剂活性低和稳定性差的问题，制备了一系列氧化石墨烯复合金属催化剂，并对其进行活性评价。结果表明：催化剂PdCl₂-CuCl₂-KOAc/AC@GO-HCl表现出最佳的催化活性和稳定性：DMC的空时收率（STY）为800~900 g·(L cat)^-1·h^-1，且反应16 h内活性无明显下降；甲醇选择性保持在95%以上，CO选择性为35%~40%。结合XRD和XPS表征发现，活性物种Cu₂Cl(OH)₃的生成，提高了催化剂催化活性，而CuO和KCl均可导致催化剂的失活。     

Crystallization kinetics,structure, and rheological behavior of poly(ethylene terephthalate)/multilayer graphene oxide nanocomposites

This work aims to produce poly(ethylene terephthalate)/multilayer graphene oxide (mGO) nanocomposites via continuous melt mixing in twin-screw extrusion, and to study the changes in crystallization and melt flow behavior. Three mGO contents (0.05, 0.1, and 0.3 wt%) were used. Differential scanning calorimetry analyses showed that at 0.1 wt%, mGO acted best as nucleating agent, increasing the crystallization kinetics as well as the melt crystallization temperature (T_mc) by more than 20%. It was also observed that mGO increases the crystals perfection. The nucleating behavior was confirmed by X-ray diffraction and small angle X-ray scattering analyses, which showed a decrease in the composites' crystalline lamella thickness (l_c) and long period. X-ray microtomography data confirms that this behavior is significantly affected by the mGO agglomerates distribution and specific surface area inside the polymer matrix. The rheological behavior was studied under two different conditions. It was noticed that under lower shear stresses the mGO particles hinder the polymer flow, increasing the composites viscosity and the pseudo-solid character. However, under higher shear stresses, for example, when flowing through a die, the nanomaterial enters its “superlubricity state,” acting as a lubricant to the flow. This is industrially interesting, because it may allow the use of less severe processing parameters to produce the nanocomposites.