不同还原方法对氧化还原法制备的功能化石墨烯的影响

利用改进的Hummer法制备氧化石墨,然后分别采用化学还原法和热还原法将氧化石墨还原制得功能化石墨烯。采用X-射线衍射(XRD)、扫描电镜(SEM)、傅立叶红外(FT-IR)和热重(TG)等表征手段对功能化石墨烯制备过程中的原料石墨、氧化石墨和石墨烯进行了表征。结果表明,化学还原法和热还原法都能还原氧化石墨制得功能化石墨烯,但还原程度不同。与化学还原法相比,热还原法制备的功能化石墨烯含有较少含氧基团,且工艺简单,耗时少,是一种高效制备大量功能化石墨烯的方法。     

石墨烯/聚乳酸复合材料的制备与性能研究

目的制备具有优异阻隔性能及热稳定性的聚乳酸薄膜材料。方法在聚乳酸中添加石墨烯对其进行改性。首先采用改进的Hummers法将鳞片状石墨制备成氧化石墨烯,继而采用热剥离法将氧化石墨烯还原剥离为石墨烯,然后以聚乳酸为基材,还原后的石墨烯为增强相,采用流延法制备石墨烯/聚乳酸复合薄膜,并测试了其结构、热稳定性以及阻隔性能。结果红外分析表明,石墨被强氧化剂氧化后形成了以C—OH,—COOH,C—O—C和C=O等官能团形式存在的石墨层间化合物,还原后获得的石墨烯剥离充分;石墨烯/聚乳酸复合薄膜的热稳定性能和阻隔性能随石墨烯含量的增加而逐渐增强。结论在试验参数范围内,石墨烯/聚乳酸复合薄膜的热稳定性和阻隔性能优于聚乳酸薄膜。     

电子受体材料功能化还原氧化石墨烯的结构和光学性能

采用Hummers法制备氧化石墨烯(GO),利用水热法对GO分别还原5 h和10 h制得两种还原氧化石墨烯(5-RGO和10-RGO),进一步用异氰酸苯酯对还原前后的氧化石墨烯材料进行改性,即得功能化氧化石墨烯和功能化还原氧化石墨烯(SPFGO、5-SPFRGO和10-SPFRGO)。以功能化还原氧化石墨烯材料为电子受体,聚3-己基噻吩(P3HT)为电子给体,制备复合膜。结果表明:GO由3-5层组成,经水热还原后样品表面仍含有—CO,—COOH等含氧官能团;功能化后石墨烯在邻二氯苯中分散性良好,与P3HT能级相匹配,满足作为聚合物太阳能电池受体材料要求;以5-SPFRGO做为受体材料与P3HT复合制备的复合膜表面规整致密,光吸收强度高,荧光光谱强度低,性能最优。     

改良氧化还原法制备石墨烯及其电学性能研究

为减少水合肼还原氧化石墨烯带来的污染并获得完整的石墨烯结构,采用改良Hummers法制备氧化石墨烯并通过维他命C对氧化石墨烯进行还原制备石墨烯。采用X射线衍射仪、拉曼光谱仪对制备的石墨烯结构进行表征,通过扫描电子显微镜观察石墨烯形貌,采用同步热分析仪及四探针测试法对石墨烯进行了性能表征;对比了维他命C和水合肼对石墨烯结构及性能的影响。结果表明,改良Hummers法缩短了氧化石墨烯的制备时间,且制备的氧化石墨烯电阻率较小,用维他命C还原法制备的石墨烯表面形貌更为平整,缺陷更少,性能更优,适合用作电极材料。     

功能化洋葱状富勒烯在裸鼠体内的流动

采用L-半胱氨酸盐酸盐,通过化合接枝法对洋葱状富勒烯进行功能化,合成水溶性L-半胱氨酸富勒烯衍生物。利用扫描电子显微镜(SEM)、X射线衍射(XRD)、红外光谱(IR)、热重分析(TGA)及X射线能谱分析(XPS)对所制样品进行表征。结果表明:L-半胱氨酸富勒烯衍生物表面具有-OH、-NH3等亲水性基团,水溶性良好。裸鼠实验表明,合成的L-半胱氨酸富勒烯衍生物在生物体组织细胞中具有很好的分布,可以顺利溶入生物体体液并具备良好的流动性。     

三维多孔结构聚苯胺/石墨烯复合材料的制备及电化学性能

以自制聚苯胺水凝胶和氧化石墨烯为原料采用原位聚合法和溶液灌注法制备三维多孔结构的聚苯胺/氧化石墨烯复合材料,然后在氢碘酸的还原下制备聚苯胺/石墨烯复合材料。采用红外光谱法、场发射扫描电子显微镜和热重分析法对制备的复合材料的结构、形貌和组成进行表征,并采用三电极测试方式对其电化学性能进行测试。结果表明,氧化石墨烯的掺入能有效防止聚苯胺和氧化石墨烯的团聚和堆叠问题,获得了具有良好三维多孔结构的聚苯胺/氧化石墨烯复合物;聚苯胺/氧化石墨烯复合材料被氢碘酸还原后,得到的聚苯胺/石墨烯复合材料的热稳定性有所降低,但其比电容和导电性等有了很大的提高,在电流密度为0.5 A/g时,PANI/GO和PANI/r GO的比电容分别为240.38 F/g和321.91F/g。     

石墨烯还原度对P25/石墨烯复合材料光催化活性的影响（英文）

采用高温热剥离和溶剂热过程分别还原氧化石墨和氧化石墨制备出石墨烯,进一步使用所合成的石墨烯与P25通过一步水热过程合成出石墨烯/P25复合材料。样品的光催化活性通过可见光下降解罗丹明B进行评测,其中P25和热剥离还原得到的石墨烯复合比P25和溶剂热还原的石墨烯复合显示出更优异的光催化活性,这是由于热剥离还原的石墨烯具有更高的还原度和更强的电子—空穴分离效率所致。进一步在不同温度下通过热剥离法制备了还原石墨烯,探讨的石墨烯/P25复合材料的光催化活性。较高的剥离温度有利于石墨烯还原程度的改善,导致光催化活性的提高。     

热还原法制备氧化石墨烯/TiO_2复合材料及其光催化性能研究

采用Hummers法制得氧化石墨烯,以钛酸丁酯为钛源,采用原位溶胶-凝胶技术制备了氧化石墨烯/TiO2复合材料,进一步经过加热还原的方法,制备热还原氧化石墨烯/TiO2复合光催化剂,通过FT-IR、XRD、Raman、SEM、TEM和UV-Vis光谱等对产物进行了表征,并测试了该复合光催化剂在可见光下对甲基橙的光催化降解性能。结果表明,制备的复合光催化剂主晶相为锐钛矿型TiO2,热还原氧化石墨烯表面富集的颗粒尺寸15nm左右,颗粒分布均匀。热还原氧化石墨烯/TiO2复合光催化剂在可见光下具有优异的光催化性能。     

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。     

氧化石墨烯的还原研究进展

石墨烯自首次被Novoselov和Geim等发现和报道后,因其特殊的光、电、热及力学等优异性能而受到广泛研究。在众多制备石墨烯的方法中,还原氧化石墨烯是目前最有希望实现大规模生产石墨烯的方法。鉴于此,重点回顾和比较了国内外氧化石墨烯的还原方法,其间介绍了部分还原机理,并预测了未来发展的趋势。     

In situ fabrication of platinum/graphene composite shell on polymer microspheres through reactive self-assembly and in situ reduction

We present a simple method to fabricate a uniform-sized graphene–metal–polymer composite microsphere of core–shell structure. On the surface of amine-functionalized polymer microsphere, graphene oxide (GO) sheets were affixed to give a core–shell structure by self-assembly process followed by the immobilization of platinum (Pt) ions to the assembled GO shell. Subsequently, they were chemically reduced in situ converting both GO and Pt ions to reduced GO (RGO) and Pt nanoparticles (NPs), respectively. As a result, a robust RGO-Pt composite shell, composed of RGO sheets and well-distributed Pt NPs, was fabricated on the microsphere surface. Meanwhile, the insulative GO shell was converted to the conductive RGO-Pt shell giving 24.0 S m^?1 of electrical conductivity. We demonstrated that the electrical property of the shell was significantly improved by the incorporation of Pt NPs.     

以氧化石墨烯为氧化介质制备石墨烯/聚苯胺导电复合材料

采用超声辅助Hummers法制得厚度约为1 nm的氧化石墨烯, 以其为氧化介质与苯胺反应合成了石墨烯/聚苯胺(RGO/PANI)导电复合材料。利用AFM、SEM、XRD和FTIR对反应所得产物进行了表征。结果表明: 苯胺在略高于室温的酸性水溶液中可以对氧化石墨烯(GO)进行还原, 而苯胺自身则被氧化石墨烯中大量的含氧基团氧化并发生聚合反应, 最终生成RGO/PANI导电复合材料, 当苯胺用量为1 mL, 氧化石墨烯用量为0.1 g, 在水浴温度为70 ℃下剧烈搅拌24 h时, 获得的RGO/PANI复合材料导电性最佳, 约为10 S/cm。     

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.     

A green approach to the synthesis of reduced graphene oxide nanosheets under UV irradiation

We present a totally green approach towards the synthesis and stabilization of aqueous graphene dispersions through UV-irradiated reduction of exfoliated graphene oxide (GO). Polyvinyl pyrrolidone (PVP) is used to enhance the dispersibility of reduced graphene oxide (RGO) by one-step functionalization. The proposed method is low cost and easy without using any photocatalysts or reducing agents, which can open up a new possibility for green preparation of stable RGO dispersions in large-scale production.     

一步法合成十二烷基苯磺酸钠稳定的石墨烯分散液

采用改进Hummer法用石墨制备了氧化石墨烯（GO）,在十二烷基苯磺酸钠存在的情况下用水合肼还原形成较高浓度的石墨烯分散液。该分散液可以稳定悬浮超过一个月。XRD、UV—vis和Raman光谱分析结果表明,所得到的石墨烯为化学反应形成的还原石墨烯（RGO）;TEM和AFM观察发现单片和多层的石墨烯并存于产物之中,说明该方法能够使RGO均匀分散于水中。     

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。     

A UV-light induced photochemical method for graphene oxide reduction

Chemical reduction of graphene oxide (GO) has been considered as a promising route towards the large scale production of graphene. Herein, a rapid, efficient photochemical method for preparing reduced graphene oxide (RGO) by ultraviolet (UV) irradiation of a mixture solution containing a photoinitiator and Monoethanolamine (MEA) compound in ethanol has been developed. In this route, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (GR-XBPO) was used as the reductant and MEA as the oxygen inhibition agent. After UV irradiation, oxygen-containing groups (OCGs) on GO plane and edges are being largely removed due to the reduction of GO by free radicals generated by photoinitiator decomposition. X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and ultraviolet and visible spectrophotometer showed that GR-XBPO can efficiently reduce GO at room temperature. It is also found that the electrical conductivity of RGO fabricated by this rapid route (~10 min) is more competitive compared to other reported works. Moreover the corresponding reduction mechanism was being discussed. This work puts forward a novel method for preparing graphene, and has great potential in scaling up graphene production and developing graphene materials.     

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.     

Graphene/thermoplastic polyurethane nanocomposites: Surface modification of graphene through oxidation,polyvinyl pyrrolidone coating and reduction

Herein, oxidation, polyvinyl pyrrolidone (PVP) coating and reduction are used to modify the surface of graphene in thermoplastic polyurethane (TPU)/graphene nanocomposites. It is demonstrated that graphene could be easily dispersed in TPU with PVP absorbed on reduced graphene oxide (RGO) as stabilizer during reduction. In the stress–strain curves for these composites containing GO, PVP coated GO (GO/PVP) and reduced GO/PVP (RGO/PVP) as filler, PVP coating and reduction can largely enhance the stress in low modulus region. It is thought to largely related with enhanced interfacial interaction between filler and matrix and healing of graphene structure during reduction. Consequently, the modulus of TPU/GO/PVP and TPU/RGO/PVP is significantly increased. Meanwhile, an electrical percolation threshold of 0.35 wt.% is obtained for TPU/RGO/PVP. Comparing with the results in literature, the filler surface modification used in this study has created nanocomposites with a good balance between electrical conductivity and mechanical properties.     

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.