石墨烯/银纳米复合材料的制备及其影响因素研究

以硝酸银、鳞片石墨为原料, 在强碱环境下, 制备得到石墨烯/银纳米复合材料, 采用X射线衍射、红外吸收光谱、透射电子显微镜、紫外可见分光光度计对所制备的石墨 烯/银纳米复合材料进行了表征.结果表明: 氧化石墨烯和银离子在强碱NaOH的作用下, 氧化石墨烯失去部分含氧官能团, 被部分还原为石墨烯(rGO), 银离子被还原为纳米银颗粒, 均匀分布在氧化石墨烯片层表面, 颗粒大小和分布受硝酸银用量、反应温度、NaOH的加入顺序及前驱物混合方式等因素影响, 在GO与Ag粒子质量比为 1:1.08时, 负载在石墨烯片层上的银纳米颗粒集中在12 nm左右. 关键词： 石墨烯/银纳米复合材料 强碱溶液     

二硒化铁/还原氧化石墨烯的制备及其在染料敏化太阳能电池中的应用

通过水热反应合成出二硒化铁/还原氧化石墨烯(FeSe₂/rGO)复合材料, 并将其作为对电极材料应用于染料敏化太阳能电池(DSSC). 利用X射线衍射、拉曼光谱、场发射扫描电子显微镜和高分辨透射电子显微镜对FeSe₂/rGO的结构和形貌进行了表征. 利用循环伏安法、电化学阻抗谱和Tafel曲线测试分析了FeSe₂/rGO对电极的电催化活性. 结果表明: FeSe₂呈纳米棒结构, 长度在100-200 nm之间, 且紧密地附着在rGO 的表面, FeSe₂/rGO对电极对I₃^-的还原具有很好的催化活性. 电池的J-V曲线测试显示: 基于FeSe₂/rGO对电极的DSSC的转换效率达到了8.90%, 相比基于单纯的FeSe₂对电极的DSSC(7.91%)和rGO对电极的DSSC(5.24%)都有了显著提高, 甚至优于铂对电极的DSSC(8.52%).     

氧化石墨烯负载金纳米颗粒SERS活性基底的制备与研究

本文采用湿化学方法制备具有表面增强拉曼散射活性的氧化石墨烯负载纳米金溶胶:通过以柠檬酸三钠为还原剂,在没有稳定剂、温和的液相反应条件下,同时还原氯金酸和深度氧化的石墨烯,原位制备氧化石墨烯负载金纳米颗粒复合物。利用紫外可见分光光度计、激光粒度分析仪、傅里叶变换红外吸收光谱仪、透射电子显微镜对所制得的氧化石墨烯负载金纳米颗粒复合物进行了表征和分析,并且采用拉曼光谱研究其作为增强试剂的性能。结果表明:所得溶胶在波长为540nm左右存在较强的吸收峰,粒径分布在50nm附近范围内;生成的金纳米粒子的大小及其分布受氯金酸用量的影响,并且粒径分布均匀,金纳米颗粒的平均尺寸为20nm,大量金纳米颗粒均匀地附着在氧化石墨烯的片层之间;氧化石墨烯的含氧官能团大幅降低,氧化石墨烯表面基团大部分被还原;以R6G为探针分子验证其拉曼增强效应,在浓度低至10nmol/L时依然具有较强的拉曼信号,增强因子达到2.4×10~5。所以高分散性、高稳定性的氧化石墨烯负载金颗粒溶胶,可作为SERS活性基底(增强试剂),用于快速检测。     

还原温度对氧化石墨烯结构及室温下H_2敏感性能的影响

以氧化石墨凝胶制备的氧化石墨烯(GO)溶胶为前驱体,在100—350℃温度下还原获得不同还原程度的还原氧化石墨烯(rGO)样品,并采用旋涂工艺制备还原氧化石墨烯气敏薄膜元件.采用X射线衍射、拉曼光谱、傅里叶变换红外光谱和气敏测试等手段研究还原温度对样品结构、官能团和气敏性能的影响.结果表明:经热还原处理的氧化石墨烯结构向较为有序的类石墨结构转变,还原温度为200℃时,样品处于GO向rGO转变的过渡阶段,还原温度达到250℃时,则表现出还原氧化石墨烯特性;无序程度随还原温度的升高先由0.85增大至1.59,随后减小至1.41,总体呈现增加趋势;氧化石墨烯表面含氧官能团随还原温度的升高逐渐热解失去,不同含氧官能团的失去温度范围不同;热还原氧化石墨烯具有优异的室温H_2敏感性能,随着还原温度的升高,元件灵敏度逐渐减小,响应-恢复时间逐渐增大,最佳灵敏度为88.56%,响应时间为30 s.     

氧化石墨烯/硒化锌纳米光电材料的制备及其蓝光发射特性

采用一种简单有效的原位水热合成方法,使用石墨烯氧化物（GO）作为反应物和晶体生长基底成功制备出了还原氧化石墨烯/硒化锌（r-GO/ZnSe）纳米复合材料。采用X射线粉末衍射（XRD）、透射电子显微镜（TEM）、高分辨透射电镜（HRTEM）以及红外-可见光谱（FT-IR）等方法对r-GO/ZnSe纳米复合材料进行了检测。结果表明,平均粒径在30 nm的立方闪锌矿晶体结构的ZnSe粒子均匀分散在氧化石墨烯片层上,构成纳米复合结构。 UV-Vis光谱显示,纳米复合材料的光学吸收的起始波长在445 nm附近。PL光谱显示,纳米复合材料在470 nm附近存在一个很强的发射峰。这种石墨烯基纳米复合材料在白光二极管领域中有重要的应用价值。     

界面自组装的金/氧化石墨烯复合材料的表面增强拉曼散射行为研究

采用Frens法制备金纳米粒子溶胶,通过界面自组装技术在掺磷的非晶碳衬底表面构筑三维的金/氧化石墨烯/金复合结构.以罗丹明B为探针分子,考察金/氧化石墨烯/金复合材料的表面增强拉曼散射活性.结果表明,由于氧化石墨烯的化学增强和金纳米粒子的电磁场增强的协同作用,在该三维复合材料上获得了很强的罗丹明B拉曼信号.所设计的三维金/氧化石墨烯/金复合材料在生物分析、环境监测、疾病防控、食品安全等领域具有潜在的应用价值.     

Co_2SnO_4/Graphene复合材料的制备与电化学性能研究

实验首先采用改进的Hummers法制备氧化石墨,然后以氧化石墨烯为前驱体,通过水热法将锡酸钴纳米颗粒均匀镶嵌在石墨烯薄膜基片上,最终获得Co2SnO4/Graphene镶嵌复合材料.采用X射线衍射(XRD)、扫描电子显微镜(SEM)对材料的结构和形貌进行表征,通过恒电流充放电(CC)、循环伏安法(CV)与交流阻抗法(EIS)测试了材料的电化学性能.实验结果表明,石墨烯良好的分散性及较高的电子导电率,可以提高锡酸钴材料的电化学性能,材料首次可逆容量达到1415.2 mA·h/g,50次循环后仍能保持469.7 mA·h/g的放电比容量.     

基于SERS的rGO-TiO_2纳米复合体的电荷转移研究

在还原的氧化石墨烯(rGO)和TiO_2纳米复合体(rGO-TiO_2)中,rGO与TiO_2之间强烈的界面相互作用赋予了该复合体在实际应用中优异的性能。目前为止,对于如何提高rGO-TiO_2纳米复合体实际应用效率的主要理论基础还没有得到充分的探索。采用一种简单且传统的方法制备出rGO-TiO_2纳米复合体,并且,通过表面增强拉曼散射光谱(SERS)作为探测手段,4-MBA作为探针分子,来探测所制备的纳米复合体界面处的电荷转移(CT)过程。结果显示,由于rGO-TiO_2纳米复合材料中接触界面的改变,使得界面处发生CT过程,并且随着rGO量的增加,rGO-TiO_2和4-MBA组装体系统中的CT度随之增加。     

三维金属有机骨架/石墨烯水凝胶均相降解纤维素为小分子酸的研究

通过在三维还原氧化石墨烯孔径中原位生长ZIF-8纳米粒子,制备了三维金属有机骨架/石墨烯催化剂.这种ZIF-8/rGO纳米复合材料同时具有介孔和微孔,并且拥有高比表面积和大量催化位点,是生物质转化的理想催化剂.将纤维素溶解于氢氧化钠水溶液中,在水热条件下,使用这种催化剂,纤维素可以被充分降解转化.纤维素转化率可以达到100%,其主要产物是甲酸,产率最高可达93.66%.催化剂还可以被回收,重复使用依然具有很好的催化效果.     

基于石墨烯的Au纳米颗粒增强染料随机激光

石墨烯和纳米颗粒的复合材料具有新颖的光学和电学特性,被广泛应用于信息传感、光电转换、医学诊断等领域,具有十分广阔的发展前景.虽然石墨烯拥有优异的光电性能,可以实现对随机激光性质的调控,但目前实现特殊结构的石墨烯与金属纳米结构的复合过程复杂繁琐,利用石墨烯有效降低随机激光阈值仍存在挑战.本文利用便捷的化学还原及吸附法制备Au/石墨烯结构,以染料DCJTB为增益介质,使用旋涂法制备了均匀的薄膜样品;研究对比Au纳米颗粒和Au/石墨烯结构随机激光特性,分析了石墨烯的作用机理.研究结果表明,Au/石墨烯复合材料透射峰与增益介质的光致发光光谱峰最为接近,对于染料分子的能级迁跃起到了促进作用.在相同的增益介质中,石墨烯的加入不仅使得光子在无序介质中散射频次增加,促进了增益效果,而且增强了Au纳米颗粒表面的等离子体共振效应.二者相互协同,展现出了优异的随机激光特性,阈值降低至2.8μJ/mm~2;对样品重复测量可得样品的激射重复性较强、品质较高.本研究对促进随机激光应用、实现高性能的光电器件起到了一定的推动作用.     

Enhanced Fluorescence of Graphene Oxide by Well-Controlled Au@SiO2 Core-Shell Nanoparticles

Graphene and graphene derivatives, including graphene oxide (GO) and reduced GO (rGO), have attracted remarkable attention in different fields due to their unique electronic, thermal, and mechanical properties, whereas the fluorescence property is rarely been studied. This paper reports on metal-enhanced fluorescence Au@SiO₂ composite nanoparticles adsorbed graphene oxide nanosheets, where the silica-shell is used to control the distance between gold-core and fluorophore GO, and a positively charged polyelectrolyte poly(allylamine hydrochloride) (PAH) is used to adsorb the negatively charged silica-shell and GO by layer-by-layer assembly (LbL) approach. The silica-shell around the 80 nm gold-core can be well-controlled by ending the reaction at different times. Various analytical techniques were applied to characterize the morphology and optical characters of the as-prepared particles. A more than three-fold increase of the fluorescence intensity of GO was obtained.     

In situ growth of ultrashort rice-like CuO nanorods supported on reduced graphene oxide nanosheets and their lithium storage performance

A facile refluxing strategy in aqueous solution was engaged to synthesize ultrashort rice-like CuO nanorods/reduced graphene oxide (CuO-NRs/rGO) composite. The result of the high-resolution transmission electron microscopy shows that the as-synthesized rice-like CuO nanorods have a uniform size of about 8 nm in width and 28 nm in length and are homogenously dispersed on rGO nanosheets. The CuO nanorods are uniformly dispersed and immobilized by the graphene nanosheets reduced from GO. The resultant CuO-NRs/rGO composite as anode material for lithium-ion batteries displays better electrochemical properties than those of pure CuO-NRs and rGO nanosheets. The high reversible capacity and good stability can be ascribed to the presence of rGO nanosheets.     

Synthesis of RGO/Cu8S5/PPy Composite Nanosheets with Enhanced Peroxidase‐Like Activity for Sensitive Colorimetric Detection of H2O2 and Phenol

In this paper, a novel strategy for the fabrication of reduced graphene oxide (rGO)/Cu₈S₅/polypyrrole (PPy) composite nanosheets with Cu₈S₅ nanoparticles and PPy layer anchored on the surface of rGO as peroxidase‐like nanocatalyst is reported. During the synthesis, graphene oxide (GO)/CuO composite nanosheets are prepared first and used as templates, then the sulfuration of CuO and polymerization of pyrrole are accompanied with the reduction of GO, resulting in ternary rGO/Cu₈S₅/PPy composite nanosheets. The synthesized Cu₈S₅ nanoparticles with a diameter in the range from tens to hundreds of nanometers are dispersed within PPy decorated rGO nanosheets. The resultant ternary rGO/Cu₈S₅/PPy composite nanosheets exhibit a higher peroxidase‐like catalytic activity toward the oxidation of 3,3′,5,5′‐tetramethylbenzidine in the presence of H₂O₂ than GO/CuO and rGO/CuS composite nanosheets, revealing a synergistic effect on their activity. The as‐prepared rGO/Cu₈S₅/PPy platform provides a simple colorimetric approach for the detection of H₂O₂ and phenol with a high sensitivity. This work offers a new way for the fabrication of rGO‐based nanocomposite with superior enzyme‐like activity, which displays great potential applications in biocatalysis and environmental monitoring.     

Microwave-assisted covalent modification of graphene nanosheets with chitosan and its electrorheological characteristics

Biofunctionalization and manipulating of graphene nanosheets (GNS) are important for biomedical research and application. Chitosan (CS) modified graphene nanosheets have been successfully prepared under microwave irradiation in N,N-dimethylformamide medium, which involved the reaction between the carboxyl groups of graphene oxide nanosheets (GONS) and the amido groups of chitosan followed by the reduction of graphene oxide nanosheets into graphene nanosheets using hydrazine hydrate. The as-prepared graphene nanosheets-chitosan (GNS-CS) nanocomposites have been characterized by FTIR, TEM, FESEM, XRD and TG. The results showed that chitosan was covalently grafted onto the surface of graphene nanosheets via amido bonds. Solubility measurements indicated that the resultant nanocomposites dispersed well in aqueous acetic acid. Especially, the electrorheological (ER) properties of the GNS-CS nanocomposites have been investigated. It is believed that this new nanocomposites may be promising for biomedical applications.     

Self-assembly of metal–organic frameworks and graphene oxide as precursors for lithium-ion battery applications

We fabricated composites of Fe₂O₃/reduced graphene oxide as lithium-ion batteries anode material with controlled structures by employing self-assembly of metal–organic frameworks (MOFs) and polymer-functionalized graphene oxide as precursors. By electrostatic interaction, the negatively charged MOFs, Prussian Blue (PB), are assembled on poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene oxide (positive charge). Then the PB cubes become FeOOH nanosheets when treated with sodium hydroxide. Upon further annealing, the FeOOH nanosheets transform to Fe₂O₃ nanoparticles while the graphene oxide become reduced graphene oxide simultaneously. It was found that the composites have good performance as anode of lithium-ion battery. This work shows a new way for self-assembling MOFs and 2D materials.     

Synthesis of NiCo2S4 nanospheres/reduced graphene oxide composite as electrode material for supercapacitor

The NiCo₂S₄ nanospheres arrayed on the surface of reduced graphene oxide (rGO) was fabricated via one-step hydrothermal method. The effect of initial feeding mass of Ni(NO₃)₂·6H₂O and Co(NO₃)₂·6H₂O to rGO on the microstructure and electrochemical performance of the as-prepared composites was studied. The results indicated that the specific capacitances of the composites were first increased and then reduced due to the aggregation of NiCo₂S₄ nanospheres. NiCo₂S₄ nanospheres/rGO composites exhibited a remarkable specific capacitance of 1406 F/g and excellent cyclic stability of 82.36% at the current density of 1 A/g, which were better than those of individual NiCo₂S₄ (792 F/g and 64.77%) counterpart. These results showed that the as-prepared NiCo₂S₄ nanospheres/rGO composites were outstanding candidate for electrode material of supercapacitors.     

原位聚合纳米Ni/聚苯乙烯复合材料及其热力学性能

 磁性聚苯乙烯(PS)材料有利于实现惯性约束聚变靶丸在辐射场中的无接触支撑。采用液相还原法制备了粒度为75~200 nm的Ni球形粒子,用原位聚合的方法制备了纳米Ni/PS复合材料。利用X射线衍射仪、傅氏转换红外线光谱分析仪、扫描电子显微镜及热重差示扫描量热仪分别研究了所得纳米Ni的特性、复合材料的结构及掺杂量对纳米Ni/PS复合材料的热力学行为的影响。研究结果表明：纳米Ni的掺杂能提高玻璃转变温度;纳米Ni的掺杂可以增大PS热分解焓变,在掺杂质量分数为1%~2%之间焓变达到最大;纳米Ni的掺杂降低了纳米Ni/PS复合材料热分解的比热容。     

Hydrothermal synthesis of graphene oxide/multiwalled carbon nanotube/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> ternary nanocomposite for removal of Cu (II) and methylene blue

In this work, highly activated graphene oxide/multiwalled carbon nanotube/Fe₃O₄ ternary nanocomposite adsorbent was prepared from a simple hydrothermal route by using ferrous sulfate as precursor. For this purpose, the graphene oxide/multiwalled carbon nanotube architectures were formed through the π-π attractions between them, followed by attaching Fe₃O₄ nanoparticles onto their surface. The structure and composition of as-prepared ternary nanocomposite were characterized by XRD, FTIR, XPS, SEM, TEM, Raman, TGA, and BET. It was found that the resultant porous graphene oxide/multiwalled carbon nanotube/Fe₃O₄ ternary nanocomposite with large surface area could effectively prevent the π-π stacking interactions between graphene oxide nanosheets and greatly improve sorption sites on the surfaces. Thus, owing to the unique ternary nanocomposite architecture and synergistic effect among various components, as-prepared ternary nanocomposite exhibited high separation efficiency when they were used to remove the Cu (II) and methylene blue from aqueous solutions. Furthermore, the adsorption isotherms of ternary nanocomposite structures for Cu (II) and methylene blue removal fitted the Langmuir isotherm model. This work demonstrated that the graphene oxide/multiwalled carbon nanotube/Fe₃O₄ ternary nanocomposite was promising as an efficient adsorbent for heavy metal ions and organic dye removal from wastewater in low concentration.     

合成Pb(OH)2/rGO催化剂用于催化转化糖为乳酸

Pb²⁺离子可以作为高效的催化剂用于降解糖为乳酸, 但是为了降低暴露Pb²⁺离子于环境中的风险,最好的办法是把铅固定在一个固体催化剂上．报道了一个简单的制备Pb(PbO₂)/石墨烯复合固体催化剂的方法,可以得到石墨烯负载的纳米铅催化剂,铅颗粒的尺寸在2～5 nm．获得的催化剂可以在水中用于降解葡萄糖、果糖甚至纤维素,产物主要为乳酸．对于果糖、乳酸的产率为58.7% (433 K,2.5 MPa N₂);当直接使用纤维素为原料,无额外酸、碱催化剂时,乳酸的产率可以达到31.7%.