还原法制备石墨烯的研究进展及发展趋势

综述了还原法制备石墨烯的研究现状,主要介绍了金属还原、光催化还原、电化学还原、热还原、化学还原试剂还原等方法的研究进展,并指出了还原法制备石墨烯的发展趋势。     

氧化石墨烯的可控还原及表征

采用Hummers修正法制备氧化石墨烯(GO),用壳聚糖(CS)作为“绿色”无毒还原剂,以反应温度和反应时间来控制氧化石墨烯的还原程度。用红外光谱、紫外可见吸收光谱、拉曼光谱和X射线衍射等多种表征手段研究不同还原程度的还原氧化石墨烯的结构与性能。结果表明,改变温度不能有效地控制氧化石墨烯的还原程度;在50℃低温环境下,控制反应时间可以得到不同还原程度的还原氧化石墨烯,为进一步研究不同还原程度还原氧化石墨烯的非线性光学性质奠定了基础。     

氧化石墨烯还原方法研究进展

综述了当前比较热门和新颖的氧化石墨烯(GO)的还原方法,特别是直接还原剂还原法、微波辅助还原法、紫外辐照还原法等,并对这些还原方法可能存在的问题进行了分析;评述了当前还原氧化石墨烯(RGO)的常用表征方法,如原子力显微镜(AFM)、拉曼光谱(RS)、X射线光电能谱(XPS)、红外(IR)光谱、X射线衍射(XRD)等测试技术。针对当前GO、RGO及石墨烯(GNS)界定不明导致使用较为混乱的状况,通过前期的研究成果及综合分析文献中相关材料的含氧量,提出可通过三者氧含量来大致区分GO、RGO及GNS,即氧含量在20%以上为GO,5%～20%为RGO,5%以下为GNS;此外,还可通过含氧量将GO还原方法划分为温和还原法、强还原法及超强还原法3种类型。文中最后对还原GO的方法进行了展望。     

氧化石墨烯还原方法研究进展

综述了当前比较热门和新颖的氧化石墨烯(GO)的还原方法,特别是直接还原剂还原法、微波辅助还原法、紫外辐照还原法等,并对这些还原方法可能存在的问题进行了分析;评述了当前还原氧化石墨烯(RGO)的常用表征方法,如原子力显微镜(AFM)、拉曼光谱(RS)、X射线光电能谱(XPS)、红外(IR)光谱、X射线衍射(XRD)等测试技术。针对当前GO、RGO及石墨烯(GNS)界定不明导致使用较为混乱的状况,通过前期的研究成果及综合分析文献中相关材料的含氧量,提出可通过三者氧含量来大致区分GO、RGO及GNS,即氧含量在20%以上为GO,5%～20%为RGO,5%以下为GNS;此外,还可通过含氧量将GO还原方法划分为温和还原法、强还原法及超强还原法3种类型。文中最后对还原GO的方法进行了展望。     

基于氢碘酸还原氧化石墨烯的研究

在石墨烯的多种制备方法中,我们选用氧化-还原法制备以保留石墨烯上的某些官能团,获得较高的电导率。我们采用改进Hummers法,以高锰酸钾与石墨粉质量比9∶1为原料,浓硫酸为溶剂更安全高效地制备氧化石墨烯(GO),避免高温氧化时大量破坏石墨的面内共轭结构。采用氢碘酸法、氢碘酸乙醇法、氢碘酸乙酸法三种途径来制备还原氧化石墨烯(r GO),比较发现氢碘酸乙酸还原法是温和高效的还原策略,即在一定量乙酸及55%的氢碘酸的混合液中,氧化石墨烯粉末在40℃下还原2d,其电导率达14600S/m,高于其它两法。通过改进氧化还原条件,制备了仅边缘修饰,面内共轭结构几乎无破坏的石墨烯。制备的r GO在邻二氯苯中能够很好地分散,其后用含溴修饰剂对其进行了边缘修饰,引入了可作为反应位点的溴原子。     

氧化石墨烯还原过程中产生的缺陷表征北大核心

采用Hummer法对鳞片石墨进行氧化得到氧化石墨,之后经过超声剥离制备氧化石墨烯,最后在水合肼的作用下还原制备石墨烯。采用红外光谱、紫外-可见光光谱、拉曼光谱和原子力显微镜对还原前后的氧化石墨烯进行表征。发现化学还原可以除去氧化石墨烯表面一部分含氧官能团,但同时也引入一些缺陷,还原之后石墨烯的sp^2域的平均尺寸减小。AFM照片分析发现含氧官能团去除之后会在原来的位置产生空洞,从而导致石墨烯缺陷增加。     

高导热石墨烯膜的制备及研究

采用改进的Hummers法制备了氧化石墨烯溶液并通过涂膜获得高度取向的氧化石墨烯薄膜,并对氧化石墨烯薄膜进行热处理得到石墨烯薄膜。通过红外、X射线衍射以及激光闪射等方法对所制得的石墨烯膜的结构和导热性能进行了表征。结果表明,经过900℃热处理能够对氧化石墨烯薄膜有效还原,得到的石墨烯薄膜在平面方向上的热导率达到540 W/(m·K)。     

太西无烟煤基石墨制备石墨烯的研究

研究了以太西煤为原料制备石墨烯的技术可行性,对太西无烟煤进行高温煅烧处理,成功制备出煤基石墨;利用氢氧化钠法制备出高纯石墨;在此基础上,利用氧化还原法进行石墨烯的制备研究。     

氧化-还原法制备石墨烯

石墨烯是2004年发现的二维新型碳材料,具有独特的物理性质和广阔的研究前景。作为石墨烯研究的基础,石墨烯的制备一直备受关注,研究进展迅速。简要分析制备石墨烯的四种主要方法(机械剥离、晶体外延生长、氧化还原、化学气相沉积)的原理和特点。重点从还原剂的选择、还原特点及还原效果评述氧化还原法制备石墨烯的研究进展,并对未来氧化-还原法制备石墨烯可能的发展方向进行展望。     

还原氧化石墨烯增强水泥基复合材料微观结构及力学性能

采用水热还原法制备了不同还原程度的还原氧化石墨烯(RGO),并将其添加到水泥浆体中,制得石墨烯增强水泥基复合材料。采用傅里叶变换红外光谱(FT-IR)、力学性能测试仪、扫描电子显微镜(SEM)对氧化石墨烯(GO)还原程度及水泥基复合材料的力学性能和微观结构进行测试。结果表明,在120℃水热条件下,控制不同还原时间可以得到不同还原程度的RGO;随着GO还原程度的提高,复合材料力学强度不断增加;RGO可使水泥更加密实,降低了水泥浆体的孔隙率,对水泥基复合材料起到增强增韧的作用。     

磁性石墨烯复合材料制备与应用研究进展

石墨烯具备多种优异的性能,但容易通过π-π堆积和范德华力作用产生聚集,重新堆叠成石墨。为了改善石墨烯的堆叠问题,提高石墨烯材料的应用性,越来越多的研究者将石墨烯及其衍生物和磁性纳米粒子复合,制备综合性能更优的新型材料。本文结合近年来国内外研究报道,总结了磁性石墨烯纳米复合材料的制备方法（水热/溶剂热、化学接枝法、微波辅助法等）,概述了磁性石墨烯复合材料在环境样品分离富集、催化、涂层耐腐蚀性、吸波材料及能源等方面的应用,指出了目前磁性石墨烯复合材料研究中存在的一些问题,例如磁性颗粒容易发生团聚、生物安全性有待验证、氧化石墨烯的还原导致其表面吸附位点减少等。目前（氧化）石墨烯的制备工艺正在得到改善,而未来最重要的发展方向是加强对磁性石墨烯的表面改性,从而可使其表面具有更丰富的吸附位点,同时也可使石墨烯表面的磁性纳米粒子的形态及分布更均匀,更有利于稳定发挥磁性石墨烯的功能性。     

聚合物基氧化石墨烯纳米复合材料研究进展

氧化石墨烯作为石墨烯的重要衍生物,原料来源广泛,制备过程简单,成本低廉,具有优异力学性能、耐磨性能以及吸附性能等,其还原产物具有优良的导电性能和导热性能等,是聚合物基纳米复合材料的理想填料。近年来,随着复合材料制备方法的不断革新,聚合物基氧化石墨烯纳米复合材料得到了快速发展,并在储能、阻燃等领域实现了规模化应用,有助于引领聚合物基氧化石墨烯纳米复合材料相关产品的进一步开发和应用。本文系统介绍了氧化石墨烯的改性方法,综述了聚合物基氧化石墨烯纳米复合材料的研究进展,展望了聚合物基氧化石墨烯纳米复合材料的发展前景。     

石墨烯在复合防腐涂层中的应用研究进展

基于石墨烯和氧化石墨烯不同的改性方法综述了石墨烯在防腐复合涂层中应用的研究进展,探讨了石墨烯防腐蚀机理,论述了石墨烯和氧化石墨稀复合防腐涂层的合成方法。其中石墨烯的改性方法有：原位改性石墨烯、电化学沉积方法和原位还原氧化石墨烯,而氧化石墨稀的改性方法包括有机改性剂改性氧化石墨烯、无机改性剂改性氧化石墨烯和微胶囊技术改性氧化石墨;并对石墨烯复合防腐涂层的发展前景进行了展望。     

Exploring the methods of synthesis,functionalization, and characterization of graphene and graphene oxide for supercapacitor applications

Graphene and graphene oxide, are attracting more attention over the last decades in the area of supercapacitor research and researchers concentrate on extensive exploration, owing to their dominating electrical conductivity, combined with mechanical properties. This review is a panoramic approach, giving insights into various aspects related to graphene and graphene oxide such as their properties, production methods, functionalities, and their applications in supercapacitors. The study ought to be beneficial to novice as well as to the domain experts. Various properties of both materials are explored and both synthesis methods are elaborated. Extra emphasis is given to bring out the role of graphene and graphene oxide in promoting the performance of supercapacitors. Synthesis methods are tabulated based on the evaluation metrics like specific capacitance and capacitance retention. Finally, the application of graphene and graphene oxide in supercapacitors are highlighted. Before concluding, perspectives along with challenges for further development are proposed and are expected to facilitate researchers in shedding light on further studies in this explorative area.     

The reduction of graphene oxide

Graphene has attracted great interest for its excellent mechanical, electrical, thermal and optical properties. It can be produced by micro-mechanical exfoliation of highly ordered pyrolytic graphite, epitaxial growth, chemical vapor deposition, and the reduction of graphene oxide (GO). The first three methods can produce graphene with a relatively perfect structure and excellent properties, while in comparison, GO has two important characteristics: (1) it can be produced using inexpensive graphite as raw material by cost-effective chemical methods with a high yield, and (2) it is highly hydrophilic and can form stable aqueous colloids to facilitate the assembly of macroscopic structures by simple and cheap solution processes, both of which are important to the large-scale uses of graphene. A key topic in the research and applications of GO is the reduction, which partly restores the structure and properties of graphene. Different reduction processes result in different properties of reduced GO (rGO), which in turn affect the final performance of materials or devices composed of rGO. In this contribution, we review the state-of-art status of the reduction of GO on both techniques and mechanisms. The development in this field will speed the applications of graphene.     

Electrostatic transparency of graphene oxide sheets

The interaction of graphene oxide of varying reduction degrees with dielectric and metallic surfaces is probed in this study, in order to assess the influence that the supporting substrate has on the electronic properties of as-produced graphene oxide and its reduced form. Lateral inhomogeneities in the distribution of substrate trapped charged impurities are found to affect the electronic properties of reduced graphene oxide, giving rise to significant in-plane variations of the local electrostatic potential on reduced one-layer sheets supported on dielectric substrates. On the contrary, no such surface potential fluctuations are identified on as-produced graphene oxide sheets, or on graphene oxide layers deposited on a metallic substrate. Thicker, two-layer reduced graphene oxide sheets show effective screening of the electrostatic effects caused by charge impurities trapped in the substrate. The current study provides a useful account of the limitations that device performance could face when attempting to tune the electronic structure of graphene oxide via functionalization, highlighting the role of substrate-related disorder affecting the behaviour of nanodevices. The role of the substrate is particularly important for applications where electronic properties of graphene oxide are especially targeted, such as transparent conducting films, sensors and electrochemical devices.     

氧化石墨烯改性吸水树脂的制备及应用

氧化石墨烯改性吸水树脂综合了氧化石墨烯和吸水树脂的优势,在水处理吸附、药物缓释、组织工程等领域有广阔的应用前景。目前有关氧化石墨烯改性吸水树脂的制备方法、性能及应用缺少相关的综述。因此,本文主要分四部分来综述近几年氧化石墨烯改性吸水树脂的研究进展。第一部分简要介绍了氧化石墨烯的结构特性及作为吸水树脂改性剂的特点;第二部分主要综述了氧化石墨烯改性吸水树脂的主要聚合工艺;第三部分主要介绍了氧化石墨烯对吸水树脂微观结构和宏观性能的影响;最后,介绍了氧化石墨烯改性吸水树脂在废水处理、缓解“热岛效应”、柔性器件及医用材料等领域的应用,并分析了其存在的问题,为后续开展氧化石墨烯改性吸水树脂的相关研究及应用提供了参考。     

石墨烯导电油墨的研究进展

石墨烯因具备着超高的电荷迁移率,近年来在导电油墨领域备受关注,它赋予了石墨烯导电油墨优异的导电性能、耐腐蚀性以及耐候性等优点。本文通过查阅文献的方式,简要介绍了导电相石墨烯的制备方法及导电油墨的导电机理,着重介绍了石墨烯导电油墨的制备工艺,其中包含氧化还原法、机械剥离法、液相剥离法等制备工艺。综述了石墨烯导电油墨在能源、电子器件、功能传感器方面的应用。提出了石墨烯导电油墨未来研究的关键性问题,如石墨烯导电油墨分散稳定性问题、配方环保问题、氧化石墨烯（GO）导电油墨的还原技术问题等。最后提出,石墨烯导电油墨应朝着低成本、绿色化、产业化的方向发展。     

Green Carbon Nanostructures for Functional Composite Materials

Carbon nanostructures are widely used as fillers to tailor the mechanical, thermal, barrier, and electrical properties of polymeric matrices employed for a wide range of applications. Reduced graphene oxide (rGO), a carbon nanostructure from the graphene derivatives family, has been incorporated in composite materials due to its remarkable electrical conductivity, mechanical strength capacity, and low cost. Graphene oxide (GO) is typically synthesized by the improved Hummers’ method and then chemically reduced to obtain rGO. However, the chemical reduction commonly uses toxic reducing agents, such as hydrazine, being environmentally unfriendly and limiting the final application of composites. Therefore, green chemical reducing agents and synthesis methods of carbon nanostructures should be employed. This paper reviews the state of the art regarding the green chemical reduction of graphene oxide reported in the last 3 years. Moreover, alternative graphitic nanostructures, such as carbons derived from biomass and carbon nanostructures supported on clays, are pointed as eco-friendly and sustainable carbonaceous additives to engineering polymer properties in composites. Finally, the application of these carbon nanostructures in polymer composites is briefly overviewed.