水热法制备还原氧化石墨烯及其导电性调控

导电性可调控的还原氧化石墨烯(rGO)在结构功能材料和化工新材料等领域具有重要的应用前景。本文利用水热还原法实现了rGO的绿色制备,并通过调控反应温度和时间,获得了电导率可控的rGO产品,其电导率范围为10~(-4)~1 S·cm~(-1)。采用UV-vis、FT-IR、XPS、SEM、XRD和Raman等表征方法系统研究了rGO还原过程中结构与组成的变化。发现GO还原过程中,其含氧官能团于120℃时开始明显分解,高于140℃后含量显著降低,GO片层sp2区域逐渐恢复,电导率逐渐增大到1 S·cm~(-1),同时层间距从8.2?减少到3.6?(1?=0.1 nm)。对比热还原法,水热法有效避免了rGO片层的堆叠,产物分散性较好,有望规模化制备导电性可控的rGO产品。本研究成果对rGO生产和应用具有重要意义。     

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。     

氧化石墨烯的酸性还原及其超级电容性能

采用改进的Hummers法制备氧化石墨烯(GO),在酸性条件(pH=5)下以180°C进行水热还原,通过调节水热反应时间来制备不同还原程度的还原氧化石墨烯(RGO)。研究了不同的水热反应时间对RGO结构及超级电容性能的影响。结果表明：控制水热反应时间可以制备出还原程度不同的RGO,在电化学测试中,随着水热反应时间的延长,RGO电极的比电容呈先上升后下降的趋势。当水热反应时间为6 h时,RGO电极表现出最佳的超级电容性能,其在1 A/g电流密度下比电容达到251 F/g,相对于GO电极提高了225%。经过500次充放电循环后,RGO-6电极比电容保持率达到92%,具有优异的循环稳定性。     

氧化石墨烯改性水泥的制备及力学性能研究

制备了氧化石墨烯改性水泥,并对其力学性能进行研究。以鳞片石墨、硝酸钠、浓硫酸等为原料,采用Hummers改性法制备氧化石墨烯,经过超声、剥离等方法,得到了最终的氧化石墨烯。然后在净浆搅拌锅内倒入均匀分散的氧化石墨烯胶体,并倒入水泥对其进行均匀搅拌,对获取的水泥浆体进行成型养护,并对氧化石墨烯改性水泥进行了力学性能测试,包括抗压强度与抗折强度实验。将水泥的抗压强度与抗折强度实验结果作为对比组,将氧化石墨烯改性水泥的抗压强度与抗折强度实验结果作为实验组。结果显示制备的氧化石墨烯改性水泥在氧化石墨烯掺量逐渐提升的情况下,实现了抗压强度与抗折强度的提升,在氧化石墨烯掺量为1.0%时达到最大抗压强度,掺量为0.06%时抗折强度达到最高。     

石墨烯的氧化还原法制备与表征

采用Hummers法,在浓硫酸、高锰酸钾等氧化剂存在条件下,将石墨粉氧化制备成氧化石墨烯,将氧化石墨溶解于水中,然后用水合肼还原氧化石墨烯后制备得到石墨烯,同时,采用红外光谱、紫外光谱、透射电镜等手段对得到的氧化石墨烯和石墨烯进行了表征。结果表明:制备得到了氧化石墨烯和石墨烯,且二者已经充分剥离。     

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。     

一步水热法制备还原氧化石墨烯改性涤纶无纺布及性能研究

采用无还原剂的一步水热法得到还原氧化石墨烯(rGO)改性涤纶无纺布,研究了改性涤纶无纺布的导电性、耐水洗性、疏水性、导热性和耐磨性,并与传统浸渍法处理后用水合肼还原氧化石墨烯改性的涤纶无纺布进行比较。结果表明:一步水热法在水热反应温度为180℃、反应5 h时的条件下,制备的改性涤纶无纺布具有优异的导电性能,其电阻率为52.6Ω·m;一步水热法制得的rGO改性涤纶无纺布具有良好的耐水洗性能,经过10次水洗涤处理后,其电阻率从52.6Ω·m增加到193.4Ω·m,而传统浸渍法制得的rGO改性涤纶无纺布的电阻率从213.1Ω·m增加到8.1×10⁵Ω·m;一步水热法制得的rGO改性涤纶无纺布具有优异的疏水性、导热性和耐磨性,其水接触角由改性前的47.42°增加到160.85°;经过1 000次磨损实验之后,其电阻率由磨损前的52.6Ω·m增加到1 226.8Ω·m。     

氧化石墨烯还原方法的研究进展

石墨烯的制备对于石墨烯的理论研究和应用研究起着重要的作用,化学氧化还原法是制备石墨烯最为重要的方法之一。综述了近年来氧化石墨烯的还原剂还原法、高温热处理还原法、电化学还原法、溶剂热还原法、催化还原法、微波还原法等多种还原方法,分析了目前各种常用还原方法的优缺点,并进一步提出氧化石墨烯还原方法未来的几个研究方向：还原前后原子结构变化及还原机理研究;新型还原方法或多种还原方法联用的研究;还原氧化石墨烯和制备复合物同时进行的研究。     

热处理对还原氧化石墨烯结构和电性能的影响北大核心

以改进Hummers法制备的氧化石墨烯(GO)为原料,通过热解还原剥离得到还原氧化石墨烯(RGO),并考察热解工艺对RGO结构和电性能的影响。研究表明,随着热解温度的升高,RGO的氧含量降低,缺陷密度下降,但过高的热解温度会造成RGO结构的二次塌陷并降低比表面积。通过测试不同热解温度下制备的RGO样品的电导率,发现RGO的缺陷结构和氧含量是影响其导电性的主要因素。在600℃热解还原制备的RGO-600粉体热处理温度适中,片层剥离度高,比表面积大,二次结构坍缩少,导电性能优越,其电导率可达344.8 S/cm。RGO与碳纳米管、导电炭黑复合的石墨烯复合导电浆料用于锂离子电池材料中,能明显提升电极材料的电子传导能力。此方法实现了在较低的热解温度条件下,剥离还原制备高导电性的石墨烯材料。     

一种氧化还原石墨烯的稳定水溶液分散体的合成方法

提供了一种在聚苯乙烯磺酸钠（PSS）的帮助下,合成氧化还原石墨烯稳定水溶液分散体的简单方法。这种方法制备的分散体非常稳定,长达几个星期都没有聚集或者沉淀。通过各种方法对材料进行了表征。扫描电子显微镜（SEM）和紫外-可见光吸收光谱的结果表明PSS紧密地包裹住了石墨烯,形成功能化石墨烯;石墨烯的亲水性大大提高。傅里叶变换红外光谱（FTIR）表明O=S=O官能团的存在,说明石墨烯中存在PSS。X射线光电子能谱（XPS）提供了C/S的原子浓度比等,进一步说明了PSS的存在。结果表明,覆盖有PSS的氧化还原石墨烯能够应用于石墨烯的复合材料中。     

Radiation synthesis of polysilane-modified graphene oxide for improving thermal conductivity and mechanical properties of silicone rubber

Functionalized graphene oxide (named GO-Si) was synthesized with graphene oxide and triethoxyvinylsilane (TEVS) using tetrahydrofuran solution by γ-ray irradiation. TEVS was successfully covered onto GO sheets, and the polysilane content on GO-Si was increased upon increasing the absorbed dose. The structures of GO-Si were verified by atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The resultant GO-Si was dispersed into α,ω-dihydroxypolydimethylsiloxane to prepare room temperature vulcanized silicone rubber composites (named SR/GO-Si) by solution casting. The dispersion of GO-Si was more uniform than that of GO. Compared to that of pure SR, the thermal conductivity of SR/GO-Si-1.95 composites was increased 1.5-fold, and its tensile strength and elongation at break increased 78.6 and 71.4%, respectively. It was expected that SR/GO-Si would have potential application as the thermal interface material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47776.     

In situ preparation of reduced graphene oxide reinforced acrylic rubber by self-assembly

Reduced graphene oxide reinforced acrylic rubber (ACM/RGO) was in situ prepared via self-assembly method in the presence of hydrazine hydrate as reducing agent. X-ray diffraction and X-ray photoelectron spectroscopy confirmed the chemical structure of ACM/RGO, and transmission electron microscope and scanning electron microscope demonstrated that RGO was uniformly dispersed in ACM matrix. Due to the barrier role of RGO sheets, the resistances to heat and water of ACM/RGO were obviously improved. Furthermore, the mechanical properties were also largely affected by the incorporation of RGO. With 2 parts per hundred rubber of RGO, the tensile strength and Shore A hardness of ACM/RGO reached 18.8 MPa and 73, and the elongation at break maintained at 236%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47187.     

Graphene oxide & reduced graphene oxide polysulfone nanocomposite pellets: An alternative adsorbent of antibiotic pollutant-ciprofloxacin

Efficient nanocomposites, GO-Psf and RGO-Psf has been synthesised from polysulfone and graphene oxide. The synthesised nanomaterials were characterised using contact angle measurements, SEM, TEM, XRD, TGA, DSC, Raman and FT-IR analytical techniques. The reported polymeric nanomaterials are attractive due to their high surface area and thermal stability. The maximum adsorption capacity for ciprofloxacin is 82.781 mg/g and 21.486 mg/g on GO-Psf and RGO-Psf, respectively. The kinetic and adsorption analysis identifies the nanomaterials as attractive adsorbents for removal of antibiotic pollutant, ciprofloxacin from aqueous solution.     

Improved output performance of hybrid composite films with nitrogen-doped reduced graphene oxide

In this research, graphene-based ceramic/polymer hybrid composite films for energy harvesting devices were prepared and analyzed. Nitrogen-doped reduced graphene oxide (N-rGO) conductive elements were embedded in a ceramic/polymer matrix as floating electrodes to form a micro-capacitor composite structure. The effects of nitrogen atom substitution on the rGO materials were investigated and their conducting properties improved. The employment of rGO- and N-rGO-based floating electrodes resulted in the formation of micro-capacitors and an increase in the potential energy of the composite films. The increase in the potential energy consequently increased the output energy of the energy harvesters. The highest voltage and energy density of the composite films were 8.5 V and 1.46 mJ/cm³, respectively, for the N-rGO based ceramic/polymer composite film.     

Heteroatom-doped reduced graphene oxide/polyaniline nanocomposites with improved n-type thermoelectric performance

Polyaniline (PANI) is a potential candidate for n-type thermoelectric (TE) materials owing to its intrinsic electrical conductivity, low thermal conductivity, and facile synthesis techniques. However, its low Seebeck coefficient and power factor have limited its widespread usage. In this study, nitrogen-doped, and sulfur-nitrogen co-doped reduced graphene oxide (rGO) were used for tuning the TE properties of PANI. Doped rGO and PANI/doped-rGO nanocomposites were prepared via hydrothermal technique and chemical oxidative polymerization respectively and thereafter characterized. The TE properties of the nanocomposites were also studied and an optimized Seebeck coefficient, power factor and zT value of −1.75 mV K⁻¹, 95 μW m⁻¹ K⁻² and 0.06, respectively were reported for the PANI nanocomposite containing 1 wt% sulfur-nitrogen co-doped rGO. These results suggest that PANI/heteroatom-doped rGO can serve as promising candidates for n-type based TE applications.     

Ultrasound–assisted synthesis and characterization of polymethyl methacrylate/reduced graphene oxide nanocomposites

This article reports ultrasound–assisted synthesis of polymethyl methacrylate (PMMA)/reduced graphene oxide (RGO) nanocomposites by in situ emulsion polymerization coupled with in situ reduction of graphene oxide. The thermal degradation kinetics of the nanocomposites was also assessed with Criado and Coats‐Redfern methods. Intense microconvection generated by ultrasound and cavitation results in uniform dispersion of RGO in the polymer matrix, which imparts markedly higher physical properties to resulting nanocomposites at low (≤1.0 wt %) RGO loadings, as compared to nanocomposites synthesized with mechanical stirring. Some important properties of the PMMA/RGO nanocomposites synthesized with sonication (with various RGO loadings) are: glass transition temperature (0.4 wt %) = 124.5°C, tensile strength (0.4 wt %) = 40.4 MPa, electrical conductivity (1.0 wt %) = 2 × 10^?7 S/cm, electromagnetic interference shielding effectiveness (1.0 wt %) = 3.3 dB. Predominant thermal degradation mechanism of nanocomposites (1.0 wt % RGO) is 1D diffusion with activation energy of 111.3 kJ/mol. © 2017 American Institute of Chemical Engineers AIChE J, 64: 673–687, 2018     

Improved mechanical and barrier properties of starch film with reduced graphene oxide modified by SDBS

Starch is regarded as one of the most promising biopolymers to replace the fossil resources. However, due to the poor mechanical properties, high sensitivity to humidity, and low barrier property, the development of starch‐based materials has been limited. In this study, they improved the mechanical and barrier properties of starch film with reduced graphene oxide (RGO) modified by sodium dodecyl benzene sulfonate (SDBS). The hydrophilia of modified RGO (r‐RGO) was improved and result in a good dispersion in oxidized starch (OS) matrix. The tensile strength of the r‐RGO‐4/OS film increased to 58.5 MPa which was more than three times of the OS film (17.2 MPa). Besides, both the water vapor and oxygen barrier properties of r‐RGO/OS film were improved greatly compared with OS and GO/OS films. Moreover, the r‐RGO/OS film could protect against UV light effectively due to its lightproof performance. In conclusion, the r‐RGO/OS composite film has great potential applications in packaging industry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44910.     

Effect of oxygen functional groups of reduced graphene oxide on the mechanical and thermal properties of polypropylene nanocomposites

Reduced graphene oxide (rGO) with various surface structures was prepared by reducing graphene oxide (GO) with hydrazine hydrate (N₂H₄), sodium borohydride (NaBH₄) and l ‐ascorbic acid, respectively. The resulting rGO were used to fabricate rGO/polypropylene (PP) nanocomposites by a melt‐blending method. The surface structure of rGO as well as multifunctional properties of rGO/PP nanocomposites were thoroughly investigated. It was shown that rGO with highest C/O ratio could be obtained by reducing GO with N₂H₄. The crystallization behaviors, tensile strength, thermal conductivity and thermal stability of rGO/PP nanocomposites were significantly improved with the increase of C/O ratio of rGO. For example, with only 1 phr (parts per hundred PP) rGO reduced by N₂H₄, the degree of crystallinity, tensile strength, maximum heat decomposition temperature and thermal conductivity of PP nanocomposite were increased by 6.2%, 20.5%, 48.0 °C and 54.5%, respectively, compared with those of pure PP. Moreover, the thermal degradation kinetics indicated that the decomposition activation energy of rGO/PP nanocomposites could be enhanced by adding rGO with higher C/O ratio. © 2018 Society of Chemical Industry