还原氧化石墨烯/天然橡胶-丁腈橡胶复合材料的制备与性能

采用水合肼还原氧化石墨烯（GO）制备了还原氧化石墨烯（RGO）,以RGO作为分散介质加入到天然橡胶（NR）和丁腈橡胶（NBR）基体中,通过乳液共混法制备了RGO/NR-NBR复合材料。采用FTIR、Raman、XRD及SEM等手段表征了RGO的结构和形貌,测试结果表明,水合肼还原GO效果较好,基本除去含氧官能团,同时RGO还保留了GO的片层结构。RGO/NR-NBR复合材料的SEM测试结果显示,纳米尺寸的RGO均匀分散在橡胶基体中,且复合材料的拉伸断面粗糙程度显著增加。RGO/NR-NBR复合材料的硫化性能测试结果表明,随RGO的含量增加,复合材料的交联密度、最大扭矩及扭矩差均增大。RGO/NR-NBR复合材料的力学性能随RGO含量的增加而提高,当RGO含量为3.0%时,材料的拉伸强度、100%定伸强度和邵氏硬度分别提高了65.7%、90.3%和21.1%,断裂伸长率降低了13.1%。     

ZnS/还原氧化石墨烯复合材料的制备及光催化性能

水热法一步合成ZnS/还原氧化石墨烯（ZnS/RGO）复合材料,通过XRD、FTIR、Raman、SEM分析溶剂（乙醇、水）对ZnS/RGO复合材料形貌和结构的影响。结果表明,以乙醇为溶剂制备的ZnS颗粒尺寸小、均匀分散在石墨烯片层上,在形成ZnS纳米颗粒的同时将氧化石墨烯（GO）还原成石墨烯。对亚甲基蓝（MB）的光催化结果显示,ZnS/RGO复合材料具有优异的光催化性能,其光催化速率是纯ZnS颗粒的3.7倍,石墨烯作为优良光生电子的传输通道和收集体能够降低光生电子-空穴对的重新结合率,极大提高了ZnS/RGO复合材料的光催化性能。      

Zn还原氧化石墨烯(RGO)和ZnO/RGO自组装复合材料的电磁响应行为

以天然鳞片石墨为原料制备氧化石墨烯（GO）,通过Zn将其还原为石墨烯（RGO）,且生成的ZnO附着在RGO表面。采用XRD、SEM、FTIR、Raman、TEM和矢量网络分析仪（VNA）研究了不同还原温度对ZnO/RGO复合材料形貌、结构、氧化程度、电磁损耗特性、德拜弛豫模型及电磁响应行为的影响。结果表明:还原温度为50℃时RGO还原后结构更加完整,层间距为0.89 nm时ZnO/RGO复合材料的介电常数和磁导率均较高,在17.15 GHz时反射率达到-41.2 dB,反射损耗小于-10 dB的带宽为3.67 GHz。      

RGO/ABS/EPDM复合材料的制备及性能研究

采用改进的Hummer法合成氧化石墨烯(GO),将GO进行热还原得到还原氧化石墨烯(RGO),并通过直接熔融密炼法制备石墨烯/丙烯腈-丁二烯-苯乙烯/三元乙丙橡胶(RGO/ABS/EPDM)复合材料。采用扫描电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪、四探针法等分析手段对复合材料表面形貌、微观结构、导电性能和力学性能进行了表征。结果表明:RGO优先分散于丙烯腈-丁二烯-苯乙烯聚合物(ABS)中,且热还原得到的RGO有效地提高了复合材料的力学性能和导电性能; RGO添加量为2. 5%(wt,质量分数,下同)时,复合材料拉伸强度提高74. 8%,缺口冲击强度提高4. 6%; RGO添加量为1. 5%时,复合材料缺口冲击强度最大,提高19. 8%;随着RGO添加量的增加,复合材料电阻率逐渐下降,当RGO添加量达到2. 5%时,复合材料电阻率下降趋势变缓。     

氧化石墨烯掺杂含量对石墨烯/PEDOT:PSS复合材料电化学性能的影响

采用改进的Hummers法合成氧化石墨烯(GO),利用原位聚合法合成GO/聚3,4-二氧乙烯噻吩∶聚苯乙烯磺酸(GO/PEDOT∶PSS)复合材料,并使用碘化氢整体还原法生成还原氧化石墨烯(RGO)/PEDOT∶PSS复合材料,同时考察了GO掺杂量对RGO/PEDOT∶PSS复合材料电化学性能的影响。通过X射线衍射仪、拉曼光谱仪、扫描电子显微镜、电化学测试等方法对所制材料进行了表征和性能测试。结果表明:GO与PEDOT∶PSS的质量比为6∶20时合成的RGO/PEDOT∶PSS复合材料具有最佳的电化学性能。     

RGO-MIL-68(Fe)复合材料的静电自组装合成及光催化还原Cr(Ⅵ)的性能

采用静电自组装方法制备氧化石墨烯（GO）-MIL-68（Fe）复合物,并通过简单溶剂热处理,将GO还原为还原氧化石墨烯（RGO）,首次制得RGO-MIL-68（Fe）复合物。通过XRD、FESEM、紫外-可见漫反射光谱（UV-Vis DRS）等方法对RGO-MIL-68（Fe）复合催化剂的晶体结构、形貌、光吸收性能等物理化学性质进行表征。在可见光照射下,以草酸铵（（NH₄）₂C₂O₄）为牺牲剂,对RGO-MIL-68（Fe）复合材料进行光催化还原Cr（Ⅵ）性能评价,结果表明,只需复合少量的RGO,MIL-68（Fe）的光催化活性就能显著地提高。当RGO含量为1wt%时,RGO-MIL-68（Fe）复合材料表现出最优的光催化活性,反应60 min,体系中的Cr（Ⅵ）的还原率高达81%。结合电化学分析可知,这主要是由于RGO的引入在增强MIL-68（Fe）光吸收性能的同时也促进了光生载流子的分离。      

Cu/还原氧化石墨烯光催化复合材料的制备及其光催化性能

以乙酸铜和氧化石墨烯（GO）为原料,抗坏血酸为还原剂,采用液相化学法合成Cu/还原氧化石墨烯（Cu/RGO）复合材料。通过XRD、SEM、TEM、FTIR和Raman对材料结构及形貌进行表征,并考察Cu/RGO复合材料在H₂O₂辅助作用下对亚甲基蓝（MB）的光催化作用。结果表明：Cu颗粒均匀分布在RGO片层上,相比于纯Cu,Cu/RGO复合材料的光催化性能明显提高,Cu/RGO复合材料用量为0.06 g/L时,对MB显示出最佳的催化效果,200 min内脱色率达到了92.5%,经过5次循环后脱色率仍有88.0%以上。     

石墨烯/纳米银复合材料的制备、微结构及其导电性能

将不同比例的氧化石墨烯(GO)和硝酸银混合,采用水合肼一步还原制备石墨烯/纳米银(RGO/Ag)复合材料。采用UV-vis、XRD、FTIR和SEM对RGO/Ag复合材料结构组成进行表征分析,并结合热流量和结构变化研究其构成和热处理工艺对导电性的影响。结果表明:Ag基本以类似球形与石墨烯(RGO)复合;RGO/Ag复合材料的导电性与其构成有很大关系,只有当GO加入量小于50wt%时,Ag含量的提高和热处理工艺的优化可以明显改善复合材料的导电性,其中,GO加入量为16wt%的RGO/Ag片方阻值可达到8mΩ/□;当GO加入量高于50wt%时,复合材料导电性与RGO接近,受Ag含量的提高和热处理工艺优化的影响较小。     

石墨烯/酚醛树脂/炭纤维层次复合材料的制备及其性能

分别以氧化石墨粉(GO)、还原氧化石墨烯乙醇悬浮液(RGO)和热法还原石墨烯粉(TRG)为填料,分散于酚醛树脂(PR)的乙醇溶液中,再将这些基体混合物涂覆于炭纤维(CF)布上,经热压成型工艺制备氧化石墨烯/酚醛树脂/炭纤维、还原氧化石墨烯乙醇悬浮液/酚醛树脂/炭纤维、热法还原氧化石墨烯/酚醛树脂/炭纤维层次复合材料。研究了GO、RGO和TRG对复合材料结构、压缩性能、弯曲性能及磨擦性能的影响。结果表明,与纯酚醛树脂/炭纤维复合材料相比,当纳米填料的质量分数仅为0.1%时,层次复合材料的压缩性能可显著提高,其中,热法还原氧化石墨烯/酚醛树脂/炭纤维的压缩强度和模量分别提高了178.9%,129.5%;弯曲性能也可得到一定的改善。还原氧化石墨烯乙醇悬浮液/酚醛树脂/炭纤维层次复合材料的最大储能模量可提高75.2%。所有改性石墨烯/酚醛树脂/炭纤维层次复合材料的Tg均有所降低。     

两步水热法制备还原氧化石墨烯/纳米TiO_2复合材料及其光催化性能

为研究由还原氧化石墨烯(RGO)和具有高活性晶面的TiO_2组成的复合材料的制备方法及其光催化性能,首先采用两步水热法制备了RGO/纳米TiO_2复合材料:第1步为合成暴露高活性晶面的纳米TiO_2;第2步为将合成的纳米TiO_2与氧化石墨烯(GO)复合,形成RGO/纳米TiO_2复合材料。然后,利用XRD、SEM、X射线光电子能谱仪和紫外-可见漫反射光谱等手段对制备的暴露不同晶面的纳米TiO_2和RGO/纳米TiO_2复合材料进行了表征,评价了其光催化性能。结果表明:在水热法的第1步中,通过调节HF的浓度能可控制备出具有高活性的(001)和(101)晶面的纳米TiO_2,氟原子在纳米TiO_2中以物理吸附态和化学结合态这2种形态存在;在第2步后,GO与纳米TiO_2复合形成RGO/纳米TiO_2复合材料,同时在此过程中GO被转化成RGO。在紫外光照射下,两步水热法合成的RGO/纳米TiO_2复合材料具有很好的光催化性能,明显优于商用TiO_2(P25)和纳米TiO_2的。RGO/纳米TiO_2复合材料的光催化性能有明显的提高,RGO和TiO_2暴露的晶面对光催化活性有影响。     

功能石墨烯/热塑性聚氨酯复合材料膜的制备及性能

采用双十二烷基二甲基溴化铵(DDAB)插层改性氧化石墨烯(DD-GO),再用抗坏血酸进行还原制得功能石墨烯(DDRGO)。采用溶液成形的方法在涂膜机上制备功能石墨烯(DD-RGO)/热塑性聚氨酯(TPU)复合材料膜,并利用FTIR、XRD、FE-SEM、高阻计、氧气透过仪对DD-RGO/TUP复合材料膜结构和性能进行表征。结果表明:经DDAB改性后的石墨烯能在TPU基体中能以褶皱层状的形式均匀的分散,并提高TPU的热稳定性、阻隔性与抗静电性。当DD-RGO的添加量为2%时,复合材料膜的阻隔性与导电性相对于纯TPU分别提高了50%与7个数量级,阻隔性与抗静电性明显提高。     

核-壳结构界面对纳米Ag掺杂BaTiO3@PDA/P(VDF-HFP)复合膜介电和储能性能影响

为改善聚偏氟乙烯（PVDF）基复合材料界面相容性,提高其电性能,利用聚多巴胺（PDA）成功包覆了纳米钛酸钡（BaTiO₃）,并引入纳米Ag离子制备出具有核-壳结构的Ag镶嵌BaTiO₃@PDA-Ag颗粒。以介电聚合物聚偏氟乙烯-六氟丙烯（P（VDF-HFP））为基体,采用溶液流延法制备了BaTiO₃@PDA-Ag/P（VDF-HFP）复合材料厚膜。利用FTIR和XPS验证了BaTiO₃@PDA-Ag/P（VDF-HFP）复合材料结构和形貌,并用宽频介电频谱仪和铁电测试仪分别比较了PDA包覆前后的不同BaTiO₃含量的BaTiO₃@PDA-Ag/P（VDF-HFP）复合膜在低电场下的介电性能和高电场下的电极化性能。结果表明,BaTiO₃@PDA-Ag质量分数为20wt%的BaTiO₃@PDA-Ag/P（VDF-HFP）复合膜在10 Hz下介电常数（ε_r）达到了25,介电损耗（tanδ）仅为0.1,在175 M·Vm-1电场下电极化强度（D_m）为6.2 μC·cm-2,200 M·Vm-1时储能密度（U_e）达到了6.9 J·cm-3,高于其它界面未处理复合膜。以上结果可为此类介电复合材料界面结构处理和电性能研究提供参考。      

Transparent and high gas barrier films based on poly(vinyl alcohol)/graphene oxide composites

Composites of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were synthesized by a modified Hummers method and a solution-mixing method. GO was fully exfoliated in the PVA/GO composites. GO did not affect the crystallization of PVA during solvent evaporation. GO is itself an excellent gas barrier without any chemical reduction. The oxygen permeability of the PVA/GO (0.3 wt.%) composite coated film was 17 times lower than that of the pure poly(ethylene terephthalate) (PET) film, with 92% light transmittance at 550 nm. Composites of PVA and reduced graphene oxide (RGO) were synthesized by performing chemical reduction using hydrazine monohydrate. The oxygen permeability of the PVA/RGO (0.3 wt.%) composite coated film was 86 times lower than that of the pure PET film, with 73% light transmittance at 550 nm. The reduction of oxygen permeability was mainly attributed to the reduced oxygen solubility in the PVA/GO composite film, while it was attributed to both the reduced oxygen diffusivity and solubility in the PVA/RGO composite film.     

Preparation of reduced graphene oxide/gelatin composite films with reinforced mechanical strength

Graphene oxide (GO) was reduced by chitosan/gelatin solution and added to gelatin (Gel) to fabricate reduced graphene oxide/gelatin (RGO/Gel) films by a solvent-casting method using genipin as cross-linking agent. The structure and properties of the films were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and UV–vis spectroscopy. The addition of RGO increased the tensile strength of the RGO/Gel films in both dry and wet states, but decreased their elongation at break. The incorperation of RGO also decreased the swelling ability of the films in water. Cell cultures were carried out in order to test the cytotoxicity of the films. The cells grew and reproduced well on the RGO/Gel films, indicating that the addition of RGO has no negative effect on the compatibility of the gelatin. Therefore, the reduced graphene oxide/gelatin composite is a promising biomaterial with excellent mechanical properties and good cell compatibility.     

Transparent, luminescent, antibacterial and patternable film forming composites of graphene oxide/reduced graphene oxide

Multifunctional graphene oxide/reduced graphene oxide (GO/RGO) composites were prepared through electrostatic interaction using biocompatible ingredients. Different functionalities were added to GO/RGO by anchoring materials such as native lactoferrin (NLf), NLf protected Au clusters (designated as Au@NLf), chitosan (Ch) and combinations thereof. Anchoring of Ch and NLf enhances the antibacterial property of RGO/GO. The addition of Ch to RGO/GO not only helped in forming stable dispersions but also helped in fabricating large (cm(2)) area films through a simple solvent evaporation technique. Functionalities such as photoluminescence were added to Ch-RGO/GO composites by anchoring Au@NLf on it. The composites thus formed showed stable luminescence in presence of various metal ions in the solid state. The composite showed reasonable stability against pH and temperature variations as well. The as-prepared films were transparent and the transparency could be modulated by controlling the concentration of RGO/GO in the composite. The antibacterial property and ability to form stable thin films may provide an opportunity to use such composites for medical and environmental remediation applications as well. Erasable patterns were fabricated on the film by stamping required patterns under compressive pressure. Luminescent patterns can be inscribed on the film and can be erased by simply wetting it. Such films with erasable information may be useful for security applications.     

L-半胱氨酸还原氧化石墨烯的研究

采用改进Hummers法合成氧化石墨,在水中超声分散获得氧化石墨烯水溶胶,并加入L-半胱氨酸于95℃进行回流反应后得到还原氧化石墨烯。采用X射线衍射仪、傅里叶变换红外光谱仪和热重-差热扫描仪等探讨氧化石墨烯还原前后的结构与性能变化。结果表明,L-半胱氨酸能有效还原氧化石墨烯,且还原后的氧化石墨烯在乙醇中有较好的分散性,其所制薄膜的导电率为500S/m。由此法制备的石墨烯有望广泛应用于电子、光电、电容器和传感器等器件中。     

Conducting polymer and reduced graphene oxide Langmuir–Blodgett films: a hybrid nanostructure for high performance electrode applications

In this work, we prepared a reduced graphene oxide (RGO)/poly(3,4-ethylenedioxythiophene) (PEDOT) hybrid composite with well defined nanostructure. The graphene oxide (GO) was first deposited on substrate through the Langmuir–Blodgett (LB) deposition, which provided a tunable and ordered GO arrangement on substrate. Then the GO LB films were reduced to RGO by following thermal treatment, and a ultrathin conducting polymer (CP) PEDOT was directly coated on RGO through a vapor phase polymerization process. The RGO/PEDOT nanocomposite exhibits excellent electrical conductivity about 377.2 S/cm. Electrochemical activity investigation revealed that this nanocomposite exhibits 213 F/g high specific capacitance at a 0.5 A/g current density and shows better capacitance retention rate than pure PEDOT. The detailed study also confirmed that the arrangement of RGO shows distinct influence on the electrical and electrochemical properties of obtained nanocomposite. Large area RGO/PEDOT nanocomposite with high conductivity and electrochemical activity can be deposited on different substrates. Such high conductivity and electrochemical activity RGO/CP nanocomposite shows promising application future in organic and flexible electrode materials for sustainable energy storage.     

氮掺杂石墨烯的制备及其电催化氧气还原性能

通过改良Hummers法制备氧化石墨(Graphite oxide,GO),采用爆炸辅助还原法将GO还原剥离并原位掺杂得到氮掺杂石墨烯(Nitrogen-doped graphene,N-RGO)。采用TEM、SEM、FI-IR、XPS、XRD及Raman等分析手段对N-RGO的形貌、组成以及结构进行了表征,利用旋转环盘电极技术测试了其电催化氧气还原活性。TEM和SEM结果表明,爆炸条件下GO被很好地剥离开来,得到只有几层厚度的石墨烯;FI-IR及XPS结果表明,GO中大部分含氧官能团被脱除,C/O原子比达到26.2,是目前所得GO还原程度非常高的方法之一,且氮元素成功掺杂进石墨烯晶格中,掺杂氮的原子质量分数约为2.11%;电化学测试结果显示,氧气还原的极限扩散电流由非氮掺杂石墨烯(Reduced graphene oxide,RGO)的0.24mA提高到N-RGO的0.49 mA,尽管爆炸辅助还原得到的RGO对氧气还原也显示出较好的催化活性,但掺杂之后的N-RGO具有更高的催化活性。