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。     

选择性还原氧化石墨烯(英文)

还原氧化石墨烯已被广泛用于制备基于石墨烯的材料。目前,还原处理方法均是尽可能地将氧化石墨烯中的功能团去除,恢复石墨烯的电子结构。由于氧化石墨烯中氧基功能团(如羟基、羧基及环氧基)不同的反应活性,氧化石墨烯是可能通过分步的方法进行还原。利用醇溶剂如乙醇、乙二醇、丙三醇还原氧化石墨烯,并采用不同分析手段对样品进行表征。结果发现,在一定条件下这些醇可选择性地还原氧化石墨烯。经这些醇的处理后,氧化石墨烯中环氧功能团被大部分去除,而其他的功能团如羟基和羧基仍被保留。这种选择性去除氧化石墨烯表面功能团的方法可利于有效地控制氧化石墨烯的还原程度、获得具有特定功能团的石墨烯衍生物,从而扩大这类材料的使用范围。     

水合肼还原氧化石墨烯的研究

通过改进的Hummers法制备氧化石墨,将获得的氧化石墨进行热剥离以及超声剥离得到双层甚至单层的氧化石墨烯片.然后采用化学还原-水合肼还原的方法去除氧化石墨烯所含的羧基COOH、羟基OH、羰基C=O和环氧基等化学基团.本实验着重研究了还原剂的用量和反应时间对各个化学基团的影响规律.     

利用维生素C和茶多酚还原氧化石墨烯及其表征

采用改进的Hummers法制备氧化石墨烯(Graphene oxide,GO),以环境友好和具有较强还原能力的茶多酚和维生素C为还原剂还原GO制备还原氧化石墨烯(Reduced graphene oxide,RGO).傅里叶变换红外光谱(FT-IR)测得还原后的RGO的含氧官能团吸收峰明显降低,在X射线衍射图谱(XRD)中观察到还原后的RGO的吸收峰位置的变化,原子力显微镜(AFM)观察到样品的厚度.这些表征数据表明实验采用的两种还原剂成功还原了GO制备出RGO.     

高速剪切辅助氧化还原法制备石墨烯

采用改进的Hummers法制备氧化石墨(GO),氧化石墨经高剪切分散乳化机高速剪切处理后进行超声波处理剥离得到氧化石墨烯,然后经水合肼还原得到石墨烯。利用激光粒度仪、扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)、热重分析仪(TGA)、激光拉曼光谱仪(Raman)和四探针测试仪等对氧化石墨和石墨烯的形貌及结构进行表征。将高剪切处理制备的石墨烯和未经高剪切处理制备的石墨烯进行对比,结果表明,高速剪切作用对氧化石墨的减薄和剥离有明显促进作用,有利于氧化石墨的还原,提高了石墨烯的制备效率和质量。     

氧化石墨烯的还原程度对水泥砂浆复合材料性能的影响

该研究制备不同还原程度的还原氧化石墨烯(rGO),研究还原参数对水泥砂浆复合材料的抗折和抗压强度的影响.采用接触角测量仪(CA)、射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)和透射电镜(TEM)对材料结构进行测试和表征.结果表明,rGO的最佳还原参数为0.2?wt％水合肼和15?mi...     

Ni2CoS4/还原氧化石墨烯/多孔还原氧化石墨烯的制备及其在超级电容器中的应用

采用水热法制备Ni_2CoS_4活性材料,通过物理过程和水热反应将其与氧化石墨烯(GO)、水热多孔氧化石墨烯(HHGO)复合得到Ni_2CoS_4/还原氧化石墨烯/多孔还原氧化石墨烯(Ni_2CoS_4/RGO/HRGO)复合电极材料。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、循环伏安测试、恒流充放电测试和交流阻抗测试等,对复合材料的形貌结构、电化学性能进行了表征。研究结果表明:在1 A/g的电流密度下,其比电容为1 684 F/g,在5 A/g的电流密度下循环2 000次后,其比电容保持率为91.8%。Ni_2CoS_4/RGO/HRGO优良的电化学行为归因于这种复合结构使电解液对电极材料的润湿程度提高,进而提高了离子和电荷的传输速率,同时也缓解石墨烯、Ni_2CoS_4的团聚和循环过程中的体积变化。因此,Ni_2CoS_4/RGO/HRGO是一种有良好应用前景的高性能超级电容器电极材料。     

氧化石墨烯的化学还原研究进展

简要介绍了化学法还原氧化石墨烯的主要类型和机理,着重对比了几种常用化学还原法的还原效果,探讨了化学还原法的优缺点,包括还原能力、还原条件及还原机理等方面的内容.认为发挥多种还原剂或制备方法的优势,可以获得性能优异的石墨烯,最后展望了其未来的发展方向及其他潜在应用.     

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。     

氢氧化镍/还原氧化石墨烯复合物的超级电容性能

采用共沉淀法制备了氢氧化镍/还原氧化石墨烯复合材料,并以此为电极研究了其超级电容性能。实验发现,六方氢氧化镍纳米片被成功插入到还原氧化石墨烯的层间,这有效抑制了还原氧化石墨烯和氢氧化镍的团聚,提高了电极的稳定性。当氢氧化镍和还原氧化石墨烯的质量比为5.5∶1时,显示了最佳的电化学性能:在-0.1~0.37V的电位窗口,1A/g的电流密度下,比电容高达1 036F/g;4A/g的电流密度下快速循环3 000次后,仍然保持70%的比电容。     

Tailor made exfoliated reduced graphene oxide nanosheets based on oxidative-exfoliation approach

This study presents a versatile and scalable strategy of ‘oxidation controlled exfoliation’ of rGO nanosheets synthesized from both Hummers and modified Hummers method. A co-relation between degree of oxidation of graphite oxide (GO) sheets and exfoliation of resulting synthesized rGO nanosheets has been successfully developed which in turn reflects in various properties of rGO sheets. The extent of exfoliation of rGO sheets has been well analyzed by XRD, SEM, BET and TEM techniques. Moreover, the quantitative analysis of degree of oxidation of GO has been estimated from FTIR spectra using quotient law method. The variations in number of rGO layers, defect density and sp² domain size have been investigated in detail by Raman spectroscopic technique. Both qualitative-quantitative analysis of rGO nanosheets have been discussed from their SAED pattern and HR-TEM images. The optical characterization of GO and corresponding rGO nanosheets has been studied in detail by UV- Vis spectroscopic technique.     

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。      

还原氧化石墨烯/MnO_2气凝胶对甲醛的去除

为制备新型高效去除甲醛材料,采用水热法制备了还原氧化石墨烯(RGO)/MnO_2气凝胶,通过SEM、TEM、TGA、XPS和BET对RGO/MnO_2气凝胶的形态结构及性能进行了表征,并研究了RGO/MnO_2气凝胶对甲醛的去除能力。结果表明:在RGO/MnO_2气凝胶的前驱体中,氧化石墨烯(GO)为单层二维纳米材料;MnO_2气凝胶由MnO_2纳米线组成,MnO_2纳米线的直径在40nm左右,长度达5μm以上,且属于隐钾锰矿型结构。RGO/MnO_2气凝胶是一种由片状材料组成的具有三维多孔结构的材料,该片状材料是由均匀分布的RGO纳米片和MnO_2纳米线组成的,RGO将MnO_2纳米线隔开,起到隔板的作用,使MnO_2纳米线在RGO中均匀分布。RGO/MnO_2气凝胶在100℃以下具有良好的热学稳定性。RGO/MnO_2气凝胶对低浓度甲醛具有较好的去除能力,去除率为62.5%,与MnO_2气凝胶相比,相同条件下RGO/MnO_2气凝胶对甲醛的去除率提高了30.0%,证实RGO有助于提高MnO_2对甲醛的去除能力。     

溶剂热法制备Fe_3O_4/氧化石墨烯复合材料及其性能研究

以氧化石墨和二茂铁为原料,采用溶剂热法原位一步合成了Fe3O4/还原氧化石墨烯(Fe3O4/RGO)复合物,通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)、振动样品磁强计(VSM)、循环伏安测试等手段对复合材料的形貌、结构、磁性能和电化学性能进行了表征。结果表明,该方法具有简单、可控的优点,通过调变前驱物中氧化石墨和二茂铁的比例,可以控制复合物中Fe3O4纳米粒子的负载量。所制备Fe3O4/RGO复合材料由平均粒径约20nm的Fe3O4纳米颗粒高度分散在还原氧化石墨烯片层上组成,具有较好的超顺磁性,电化学稳定性和良好的倍率性能。     

Coupling of short DNAs with reduced graphene oxide for electronic and sensing applications

Abstract

In this article, we described an approach for coupling of short DNAs with reduced graphene oxide and thus formation of transducer layer for biological sensors. We investigated the dependence of coupling ratio on the graphene oxide reduction level. We found optimal reduction parameters and showed successful conjugation of aptamers with reduced graphene oxide. We have revealed a trend to increase aptamer conjugation efficiency with a decrease of graphene oxide reduction rate. Finally, we made biosensor structures with Π-shaped reduction pattern and showed excellent sensitivity of the sensor during thrombin exposure. These results are important for the development of flexible low-cost biosensors of a new generation.     

Wearable gas/strain sensors based on reduced graphene oxide/linen fabrics

Multifunctional wearable e-textiles have been a focus of much attention due to their great potential for healthcare, sportswear, fitness, space, and military applications. Among them, electroconductive textile yarn shows great promise for use as the next-generation flexible sensors without compromising properties and comfort of usual textiles. Recently, a myriad of efforts have been devoted to improving performance and functionality of wearable sensors. However, the current manufacturing process of metal-based electroconductive textile yarn is expensive, unscalable, and environmentally unfriendly. In this work, we report the preparation of multifunctional reduced graphene oxide/linen (RGO/LN) fabrics through the reduction and the followed suction filtration. As-prepared RGO/LN fabric could serve as the methane gas sensor, which exhibited high sensitivity, remarkable reliability and feasibility. Furthermore, the RGO/LN fabric sensor exhibited good moisture permeability and air permeability. The present work reveals that RGO/LN fabric has great potential as wearable smart devices in personal healthcare applications.     

原位反应制备ZnS/还原氧化石墨烯复合材料及其光催化性能

以氧化石墨烯和ZnAc2为反应前驱物,采用二甲基亚砜(DMSO)作为硫源和反应溶剂,通过一步溶剂热法原位制备出负载ZnS的还原氧化石墨烯(RGO)复合材料(ZnS/RGO)。采用SEM、XRD、激光拉曼(Raman)和荧光光谱对样品的微观形貌和化学结构进行表征。结果显示:原位反应制备的ZnS/RGO复合材料是由呈圆球状并均匀负载的纳米ZnS和6~7层RGO层状结构组成;在模拟紫外光照射下,对甲基橙污染物的光催化结果表明,ZnS/RGO复合材料的降解效率明显高于纯ZnS;同时,在多次循环催化过程中,ZnS/RGO复合材料的光催化效率仍基本保持不变,表明原位反应使ZnS与RGO结合增强。荧光光谱结果表明,ZnS/RGO复合材料光催化效率增强的主要原因在于ZnS中光生电子通过RGO得到有效的分离,进而延长了电子-空穴的复合效率。     

Converting graphene oxide monolayers into boron carbonitride nanosheets by substitutional doping

To realize graphene-based electronics, bandgap opening of graphene has become one of the most important issues that urgently need to be addressed. Recent theoretical and experimental studies show that intentional doping of graphene with boron and nitrogen atoms is a promising route to open the bandgap, and the doped graphene might exhibit properties complementary to those of graphene and hexagonal boron nitride (h-BN), largely extending the applications of these materials in the areas of electronics and optics. This work demonstrates the conversion of graphene oxide nanosheets into boron carbonitride (BCN) nanosheets by reacting them with B(2) O(3) and ammonia at 900 to 1100 °C, by which the boron and nitrogen atoms are incorporated into the graphene lattice in randomly distributed BN nanodomains. The content of BN in BN-doped graphene nanosheets can be tuned by changing the reaction temperature, which in turn affects the optical bandgap of these nanosheets. Electrical measurements show that the BN-doped graphene nanosheet exhibits an ambipolar semiconductor behavior and the electrical bandgap is estimated to be ≈25.8 meV. This study provides a novel and simple route to synthesize BN-doped graphene nanosheets that may be useful for various optoelectronic applications.     

High-performance asymmetric supercapacitors based on reduced graphene oxide/polyaniline composite electrodes with sandwich-like structure

The sandwich-like structure of reduced graphene oxide/polyaniline(RGO/PANI) hybrid electrode was prepared by electrochemical deposition. Both the voltage windows and electrolytes for electrochemical deposition of PANI and RGO were optimized. In the composites, PANI nanofibers were anchored on the surface of the RGO sheets, which avoids the re-stacking of neighboring sheets. The RGO/PANI composite electrode shows a high specific capacitance of 466 F/g at 2 m A/cm~2 than that of previously reported RGO/PANI composites. Asymmetric flexible supercapacitors applying RGO/PANI as positive electrode and carbon fiber cloth as negative electrode can be cycled reversibly in the high-voltage region of 0–1.6 V and displays intriguing performance with a maximum specific capacitance of 35.5 m F cm~(-2). Also, it delivers a high energy density of 45.5 m W h cm~(-2) at power density of 1250 m W cm~(-2). Furthermore, the asymmetric device exhibits an excellent long cycle life with 97.6% initial capacitance retention after 5000 cycles.Such composite electrode has a great potential for applications in flexible electronics, roll-up display,and wearable devices.     

Ultrathin Co3O4 nanosheets highly dispersed on reduced graphene oxide: An efficient bi-functional catalyst for Li-O2 battery

Ultrathin Co₃O₄ nanosheets grown on the reduced graphene oxide (Co₃O₄/rGO) was synthesized by a simple hydrothermal method and was investigated as a cathode in a Li-O₂ battery. Benefited from the synergistic effect between Co₃O₄ and rGO, the hybrid exhibits a high initial capacity of 10,528 mAh g^?1 along with a high coulombic efficiency (84.4%) at 100 mA g^?1. In addition, the batteries show an enhanced cycling stability and after 113 cycles, the cut-off discharge voltage remains above 2.5 V. The outstanding performance is intimately related to the high surface area of rGO, which not only provide carbon skeleton for the uniform distribution of Co₃O₄ nanosheets but also facilitate the reversible formation and decomposition of insoluble Li₂O₂. The results of electrochemical tests confirm that the Co₃O₄/rGO hybrid is a promising candidate for the Li-O₂ batteries.