A conjugation polyimine vitrimer: Fabrication and performance

Although polyimine vitrimers are a promising and invaluable class of self-healing materials owing to their great maneuverability and fast exchange of crosslinks without catalysts, it remains a challenge to improve the mechanical properties and thermal stability of the material by simply designing their internal structures. Herein, we report a conjugation polyimine vitrimer, which was prepared by polycondensation of terephthaldehyde, m-xylylene diamine and tris (2-aminoethyl) amine as crosslinker. The incorporation of m-xylylene diamine endows the materials with an expanded conjugation structure, which greatly improves its mechanical properties and thermal stabilities. On the other hand, m-xylylene diamine is less toxic and irritant than the linear aliphatic ones usually used, which makes the reactions more environment-friendly. Results show that these materials have excellent mechanical properties and thermal stability, perform good flexibilities after immersed in water and show very short relaxation times at elevated temperatures. In addition, especially, they exhibit good self-healing efficiency under the condition of heat, water and amine solvents without the need for any catalyst. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2531–2538     

Conductive and mesoporous single-wall carbon nanohorn/organic aerogel composites

Conductive and mesoporous single-wall carbon nanohorn/resorcinol-formaldehyde aerogel composites were fabricated by embedding organic resorcinol-formaldehyde aerogels with single-wall carbon nanohorns. Samples were characterized with transmission electron microscopy, field emission scanning electron microscopy, nitrogen adsorption at 77 K, and direct-current volume electrical conductivity measurement. It was demonstrated that these composites have important properties, such as controllable nanoporosity and high electrical conductivity in the range of 10-4 S m-1, which enables many potential applications.     

三维二硫化钼/还原氧化石墨烯气凝胶用作宏观可见光催化剂

近年来,光催化技术在解决环境污染和能源短缺方面展现出巨大潜力.二硫化钼(MoS2)作为一种二维层状光催化材料受到广泛关注.MoS2具有可调的带隙(1.2–1.9 eV)、低的成本和高的存储量,是一种可替代铂的理想助催化剂.然而,MoS2本身光催化活性较低.理论和实验已经证明,MoS2只有暴露的边缘具有催化活性,并且MoS2的光生电子-空穴对容易复合,导致其光催化效率低.增加暴露的活性边缘以及有效分离电子-空穴对是提高MoS2光催化活性的关键.而石墨烯气凝胶是一种理想的催化剂载体,其高比表面积和高空隙率可以有效提高催化剂利用率.同时,其高导电性可以促进光生电子-空穴对分离.因此,将MoS2负载到石墨烯气凝胶上制备宏观可回收光催化材料具有广阔的应用前景.然而,目前尚未见到有关MoS2/石墨烯气凝胶光催化产氢以及还原Cr(VI)的报道.本文以钼酸铵为钼源,硫脲为硫源和还原剂,同时加入氧化石墨烯及其还原剂氨水,通过一步水热法制备出二硫化钼/还原氧化石墨烯(MoS2/RGO)水凝胶.最后通过冷冻干燥得到MoS2/RGO气凝胶.经光催化测试发现其产氢达到38.9μmol/g,光还原Cr(VI)达到92%,明显高于MoS2粉体.采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)、紫外-可见-近红外吸收光谱(UV-Vis-NIR)及红外光谱(FTIR)等手段研究了其光催化性能提高的原因.XRD测试显示,过量的NH4+离子插入到MoS2层与层之间增加了(002)面的晶面间距;SEM观察到在形成气凝胶后,MoS2从粉末的片状转变成花状,这是因为氧化石墨烯上的含氧官能团促进MoS2成核同时限制其生长导致的;TEM观察到MoS2上存在大量的脱节和扭曲,这是由于过量硫脲阻碍了MoS2晶体的取向生长而产生缺陷;XPS发现,除了形成MoS2之外,还形成了MoO2,同时大量的暴露边缘导致不饱和硫产生;FTIR表明MoS2与RGO之间通过氢键链接在一起;UV-Vis-NIR吸收光谱显示,MoS2/RGO气凝胶在可见光区具有很强的吸收,这是黑色的RGO以及光在花状结构的不断反射共同作用导致的.综合以上结果,我们提出了MoS2/RGO光催化性能增强的机理.首先,三维的气凝胶网状结构以及花状结构的MoS2所带来的高比表面积(599.7 m2/g)使得材料对H+和Cr(VI)吸附量增加;其次,黑色的RGO以及入射光在花状结构层片间的不断反射增加了MoS2/RGO气凝胶对可见光的吸收;最后,RGO本身的高导电性促进了光生电子-空穴有效分离,电子通过RGO快速转移到材料表面参与光催化反应.因此,将MoS2负载在RGO上可提高光催化效率.另外,低密度的MoS2/RGO气凝胶(56.1 mg/cm3)可以有效吸附有机溶剂且容易回收.综上所述,本文制备的MoS2/RGO气凝胶光催化材料在环境与能源方面表现出潜在的应用前景.     

The fabrication of flower-like graphene/octadecylamine composites

Three-dimensional flower-like nanomaterials have wide application due to the large specific surface area. In this letter, the morphology of octadecylamine (ODA) from several common solvents is studied and it is found that from the chloroform and acetone solution, ODA assembles into petal-like structure, which further forms the spherical or flower-like architecture. Furthermore, the composite materials incorporated reduced graphene oxide (rGO) and ODA could well keep the flower-shaped structure of ODA. XRD results show that the introduction of graphene has little influence on the structure of ODA and contact angle test indicates good hydrophobic performance of the rGO/ODA material.     

纳米纤维素/还原氧化石墨烯复合材料用于高性能超级电容器

以高浓度氧化石墨烯(GO)溶液作为反应前驱体,纳米纤维素(NC)作为物理间隔物和电解液储存器,通过简单的一步水热法制备了纳米纤维素/还原氧化石墨烯(NC/rGO)复合材料,并探究了其作为超级电容器电极材料的潜力。结果如下：NC添加量为1 mL所制备的NC/rGO-1具有最佳电化学性能。基于NC/rGO-1的无黏合剂对称型超级电容器在0.3 A·g^-1的电流密度下显示出了269.33 F·g^-1和350.13 F·cm^-3的高质量和体积比电容,并在10.0 A·g^-1时仍能达到215.88 F·g^-1和280.62 F·cm^-3(其初始值的80.15%)。组装器件还显示出了较高的质量和体积能量密度(9.3 Wh·kg^-1和12.13 Wh·L^-1)和出色的循环性能(10 A·g^-1下10 000次循环后其初始比电容仅减少6.02%)。     

Thiourea aldehyde resin-based carbon/graphene composites for high-performance supercapacitors

Thiourea aldehyde resin-based heteroatom doping carbon and graphene composites (RHDC/GN) were prepared by an in situ polymerization and carbonization. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that thiourea aldehyde resin deposited on lamellar GO flakes during the polymerization and RHDC/GN composites had a hierarchical structure. The specific capacitance of the RHDC/GN composites was high up to 355 F g^?1, much higher than that of the pure thiourea aldehyde resin-based heteroatom doping carbon (RHDC) with specific capacitance of 135 F g^?1 at a current density of 1.0 A g^?1 in 6-M KOH electrolyte. And the hetroatoms in RHDC/GN composites increase the specific capacitance, and GN enhances the conductivity of the electrodes which is beneficial to improving electrochemical cycling stability of the electrode significantly. The specific capacitance retains 90.97% after 5000 charge-discharge processes at 10 A g^?1, which provides potential as supercapacitors.     

纳米纤维素/还原氧化石墨烯复合材料用于高性能超级电容器

以高浓度氧化石墨烯(GO)溶液作为反应前驱体,纳米纤维素(NC)作为物理间隔物和电解液储存器,通过简单的一步水热法制备了纳米纤维素/还原氧化石墨烯(NC/rGO)复合材料,并探究了其作为超级电容器电极材料的潜力。结果如下：NC添加量为1 mL所制备的NC/rGO-1具有最佳电化学性能。基于NC/rGO-1的无黏合剂对称型超级电容器在0.3 A·g^-1的电流密度下显示出了 269.33 F·g^-1和 350.13 F·cm^-3的高质量和体积比电容,并在 10.0 A·g^-1时仍能达到 215.88 F·g^-1和 280.62 F·cm^-3(其初始值的 80.15%)。组装器件还显示出了较高的质量和体积能量密度(9.3 Wh·kg^-1和 12.13 Wh·L^-1)和出色的循环性能(10 A·g^-1下10 000次循环后其初始比电容仅减少6.02%)。     

石墨烯/锌铁氧体复合物的制备及抗菌性能

用氧化还原法和化学共沉淀法分别制备了石墨烯(GE)和石墨烯/锌铁氧体(GE/ZnFe2O4)复合物,通过现代测试技术表征了样品的物相结构、组成和微观形貌.以大肠杆菌、金黄色葡萄球菌和白色念珠菌为测试菌种,分别对样品的抗菌性能进行了研究.结果表明,样品的抗菌活性受GE/ZnFe2O4复合物中GE和ZnFe2O4质量比(mG/Z)以及菌种的影响,其中mG/Z=0.4的复合物对三种菌均有较好的抗菌效果,其最小抑菌浓度分别为25、25和12.5μg/mL;复合物对白色念珠菌的抗菌效果最好,这与菌种的结构有关.此外,对样品的抗菌机理进行了详细研究.     

Plasma-based preparation of polyaniline/graphene and polypyrrole/graphene composites for dye-sensitized solar cells as counter electrodes

This study presents the preparation of graphene (GR) nanocomposites with polyaniline (PANI) and polypyrrole (PPy) through the fast, versatile and environmentally friendly process of radio frequency (RF)-plasma polymerization. Morphological characterization of the nanocomposites is performed using scanning electron microscopy (SEM) and shows that the PANI and PPy conducting polymers coated the GR surface. The surface properties of the GR nanocomposites are determined using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The prepared GR nanocomposites are then used as counter electrodes in dye-sensitized solar cells (DSSCs). The conversion cell efficiencies for iodine-doped DSSC samples are found to be 0.086%, 5.41%, and 5.60% for I₂-PANI, I₂-PANI-GR and I₂-PPy-GR, respectively, while the corresponding undoped samples reaches power conversion efficiencies of 3.82%, 1.30%, and 0.077% for PPy-GR, PANI-GR and PANI, respectively. The incident photon-to-current efficiency (IPCE) of iodine-doped composite-based DSSCs is significantly enhanced.     

Preparation of nano-structured LiFePO4/graphene composites by co-precipitation method

Graphene materials with superior electrical conductivities and high surface area would be advantageous for application in energy storage. And LiFePO₄ has been a promising electrode material however its poor conductivity limits its practical application. To improve the electronic conductivity, we prepare LiFePO₄/graphene composites in a co-precipitation method, in which graphene nanosheets are used as additives. The composites were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM), and their electrochemical properties were investigated by galvanostatic charge and discharge tests. The experimental results show that the capacity delivery and cycle performances of LiFePO₄ could be improved considerably by adding graphene. Therefore, LiFePO₄/graphene composites are a promising candidate for lithium secondary batteries.     

Electrochemical performance of polypyrrole nanorods/functionalized graphene composites for supercapacitors

Journal of Solid State Electrochemistry - Polypyrrole (PPy) hybrid composites are prepared with nitrogen-functionalized graphene (NFG) via in situ polymerization of pyrrole in the presence of NFG...     

Tri-isocyanate reinforced graphene aerogel and its use for crude oil adsorption

We prepared tri-isocyanate reinforced graphene aerogel with a low bulk density (0.08g/cm(3)), high compressive failure strength (0.24MPa), and good adsorption ability towards crude oil (～169mg/g), through self-assembly of graphene under hydrothermal condition, tri-isocyanate reinforcement and subsequent supercritical CO(2) drying process.     

Gemini surfactant assisted synthesis of two-dimensional metal nanoparticles/graphene composites

We demonstrate the synthesis of 2D metal nanoparticles (MNPs)/graphene nanocomposites using small cationic surfactants as stabilizers. 2D sandwich-like MNPs/graphene nanocomposites with a uniform distribution of MNPs can be achieved via a one-pot in situ growth and reduction protocol.     

Shape memory effect and mechanical properties of graphene/epoxy composites

Graphene/epoxy shape memory composites were fabricated with graphene from a simple and low cost method of chemical oxidation-reduction process. The fine and homogeneous dispersion of graphene throughout the epoxy matrix with different graphene mass fraction were prepared and their properties were investigated. It was found that storage elastic modulus rose with the increase of graphene mass fraction, which indicated that the recovery stress of graphene/epoxy composites would be greater than that of the pure epoxy. The graphene/epoxy composites with lower content graphene showed a good shape memory effect and a recovering speed superior to the pure epoxy.     

Green synthesis of graphene nanosheets/ZnO composites and electrochemical properties

A green and facile approach was demonstrated to prepare graphene nanosheets/ZnO (GNS/ZnO) composites for supercapacitor materials. Glucose, as a reducing agent, and exfoliated graphite oxide (GO), as precursor, were used to synthesize GNS, then ZnO directly grew onto conducting graphene nanosheets as electrode materials. The small ZnO particles successfully anchored onto graphene sheets as spacers to keep the neighboring sheets separate. The electrochemical performances of these electrodes were analyzed by cyclic voltammetry, electrochemical impedance spectrometry and chronopotentiometry. Results showed that the GNS/ZnO composites displayed superior capacitive performance with large capacitance (62.2 F/g), excellent cyclic performance, and maximum power density (8.1 kW/kg) as compared with pure graphene electrodes. Our investigation highlight the importance of anchoring of small ZnO particles on graphene sheets for maximum utilization of electrochemically active ZnO and graphene for energy storage application in supercapacitors.     

Reactivity of CO2 traps in aerogel–wollastonite composites

Synthetic wollastonite has been used as the active phase embedded into two different silica aerogel composites. These composites are different in respect of the route used for the synthesis of the wollastonite powder. Texture and composition of both types of composite have been characterized. In addition, several factors (pH, reaction time, CO₂ saturation, etc.) that could help to optimize the carbonation process at room temperature and pressure have been studied. Under the same conditions, both composites confirm previous results showing efficiencies as CO₂ sequesters between 80% and 100% in only 15 min of gas flow. The textural characteristics of the aerogel, together with the grain size of the synthetic wollastonite powder, not only increase the speed of the reaction, but also inhibit the appearance of a passivating layer on the surface of the wollastonite grains attacked by the CO₂. This is an outstanding feature as it insists on a cutting-edge challenge of the CO₂ research: its economical availability.     

整体式三氧化钨/氧化石墨烯气凝胶增强可见光光催化氧化NO性能（英文）

近年来,光催化技术在去除以NO为代表的诸多室内气体污染物方面展现出巨大的潜力.单质铋和铋系氧化物,非金属氧化物以及钙钛矿等众多半导体光催化材料均具有优异的NO降解效率,但很难控制氧化产物.因而会生成大量毒性更强的中间产物NO2造成二次污染.因此,寻求一种清洁、高效,且具有良好选择性的光催化材料成为了亟待解决的问题.六方相三氧化钨(h-WO_3)的价带位置较正,氧化电位较高,具有很强的氧化能力,是一种良好的氧化性光催化半导体材料.然而,WO_3催化材料多为粉末状,不仅容易团聚,难以回收利用并且会堵塞检测气路.同时,WO_3本身存在的电子-空穴复合率高,弱的可见光响应性等问题使其光催化活性较低.因而,制备具有良好可见光响应,高电子-空穴分离效率的一体化WO_3材料是其广泛应用前急需解决的问题.而石墨烯气凝胶是理想的催化剂载体,其较高的比表面积以及多孔状结构可有效地增加催化剂的暴露面积,提升催化剂利用率;更重要的是,氧化石墨烯(GO)具有极高的导电率,可作为电子受体加速电子-空穴对的分离而提升光催化活性.因此,以GO作为基体材料,构建WO_3/GO气凝胶一体化材料有良好的应用前景.然而,现在还鲜见有关宏观WO_3/GO气凝胶光催化降解NO的报道.本文以偏钨酸铵为钨源,利用体积分数为25%的冰醋酸在180ⅹC条件下制备六方相三氧化钨.通过机械搅拌以及冷冻干燥法制备WO_3/GO气凝胶.经光催化氧化NO测试发现其可见光下降解率可达51%,是WO_3粉体的3.3倍,并且NO_2生成率仅为0.5%,远远低于其他相关光催化材料.采用了X射线衍射(XRD),透射电镜(TEM),X射线光电子能谱(XPS),紫外-漫反射分光光度计(UV-DRS),傅里叶红外光谱(FTIR)和荧光光谱(PL)等手段研究了其光催化性能提高的原因.XRD测试显示,复合材料主体为h-WO_3,说明GO的引入并未破坏材料晶体结构;TEM和BET测试发现,在加入GO之后h-WO_3分散性变好,比表面积变大,从而可暴露更多的光催化活性位点.UV-DRS吸收光谱可以看到WO_3/GO气凝胶材料的吸收边发生了显著的红移,其禁带宽度从3.44 eV减小到3.16 eV,这可能是GO影响了WO_3的能带结构所致.同时PL结果表明,引入了GO之后,气凝胶材料的非辐射跃迁程度明显减小表明其电子-空穴对的复合得到了显著抑制,电子迁移显著加强.综合以上结果,可以得到WO_3/GO光催化性能提升以及良好的产物选择性的原因.首先,三维气凝胶材料的结构提升了催化剂的有效利用率,较大的比表面积暴露了更多的活性位点.其次,GO的引入减小了复合材料的禁带宽度,并使其吸光性能有所改善,产生了更多的光生电子和空穴.最后,GO本身极高的导电性,使光生电子-空穴对得以有效的分离,一方面,电子通过GO迅速转移到材料表面来参与光催化反应;另一方面,电子的快速转移抑制了电子-空穴对的复合,进而提高光催化性能,而且较正的价带位置保证了NO较为彻底的氧化为NO3–.因此,相比传统粉末WO_3催化材料,一体化的WO_3/GO气凝胶不仅显著提升了NO降解率,同时严格抑制了毒副产物NO2的生成,同时更具有容易回收利用,不存在二次污染的优点.综上所述,WO_3/GO一体化气凝胶光催化材料有望在环境净化与能源领域表现出良好的应用前景.