石墨烯纳米复合材料在光催化应用中的研究进展

石墨烯即"单层石墨片",是近年来人们发现和合成的具有独特的单原子层、二维晶体结构的纳米材料.利用石墨烯与半导体材料复合以提高光催化活性,已成为新型光催化研究的热点之一.对石墨烯及其应用进行了简单的叙述,重点报道了石墨烯在光催化制氢、光催化降解和光电转换应用方面的研究动态,以及用不同方法合成的石墨烯光催化复合材料,为以后石墨烯与其他材料的复合提供了实验依据.     

石墨烯均匀分散问题研究进展

具有优良性能的石墨烯常被作为增强体加入基体材料中以改进其性能。研究发现,石墨烯增强复合材料的性质在很大程度上取决于石墨烯在基体中的均匀分散程度。而石墨烯增强体在基体中的均匀分散问题一直是研究的难点,这就限制了石墨烯增强复合材料性能的提升及其开发应用。总结了石墨烯在基体中均匀分散方法的研究进展,并展望了其研究方向及发展趋势。     

石墨烯纳米复合材料合成及其在光催化氧化降解和还原制备氢能中应用的研究进展

石墨烯因独特的二维纳米结构和优良的物理化学性能已经成为近年来纳米材料研究的热点领域之一。作为一类新型的碳基材料,石墨烯纳米复合材料已经广泛地应用于多相光催化的诸多方面。对石墨烯纳米复合材料的制备、光催化还原制氢原理、光催化氧化染料降解原理、光催化活性的主要影响因素、石墨烯纳米复合材料在光催化氧化污染物降解、光催化还原制氢以及CO2还原制甲醇中的应用等领域的最新研究进展进行了较系统的综述,对一些新的光催化反应以及反应机理进行了归纳总结,提出了石墨烯纳米复合材料存在的问题以及未来的发展方向。     

Synergistic Effect of Aligned Graphene Nanosheets in Graphene Foam for High‐Performance Thermally Conductive Composites

Graphene shows a great potential for high‐performance thermally conductive composite applications because of its extremely high thermal conductivity. However, the graphene‐based polymer composites reported so far only have a limited thermal conductivity, with the highest thermal conductivity enhancement (TCE) per 1 vol% graphene less than 900%. Here, a continuous network of graphene foam (GF), filled with aligned graphene nanosheets (GNs), is shown to be an ideal filler structure for thermally conductive composite materials. Compared to previous reports, a clear thermal percolation is observed at a low graphene loading fraction. The GNs/GF/natural rubber composite shows the highest TCE of 8100% (6.2 vol% graphene loading) ever reported at room temperature, which gives a record‐high TCE per 1 vol% graphene of 1300%. Further analyses reveal a significant synergistic effect between the aligned GNs and 3D interconnected GF, which plays a key role in the formation of a thermal percolation network to remarkably improve the thermal conductivity of the composites. Additionally, the use of this composite for efficient heat dissipation of light‐emitting diode (LED) lamps is demonstrated. These findings provide valuable guidance to design high‐performance graphene‐based thermally conductive materials, and open up the possibility for the use of graphene in high‐power electronic devices.     

磁响应性TiO2/石墨烯纳米复合材料的合成及光催化性能

采用乳液插层水解法成功制备了一种层状磁响应性光催化纳米复合材料.首先通过水热法制备磁性Fe3O4纳米粒子,将其超声分散在溶有钛酸丁酯的无水乙醇中,形成钛酸丁酯包裹Fe3O4纳米粒子的微乳液,然后将该微乳液插层于石墨烯中,利用石墨烯的层状结构作为载体形成一种稳定体系,通过控制水解,使TiO2纳米粒子与磁性Fe3O4纳米粒子共同镶嵌于石墨烯层间,形成一种新型的磁响应TiO2/石墨烯纳米复合材料.通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、震动样品磁强计(VSM)等手段对该复合材料进行表征,并通过模拟太阳光下降解亚甲基蓝(MB)评价复合材料的光催化性能.该复合材料通过磁分离可反复使用,重复使用7次后,对亚甲基蓝的降解率仍大于90％.     

Synthesis of a Pillared Graphene Nanostructure: A Counterpart of Three‐Dimensional Carbon Architectures

Graphene is a single sheet of carbon atoms with outstanding electrical and physical properties and is being exploited for applications in electronics, sensors, photovoltaics, and energy storage. A novel 3D architecture called a pillared graphene nanostructure (PGN) is a combination of two allotropes of carbon, including graphene and carbon nanotubes. A one‐step chemical vapor deposition process for large‐area PGN fabrication via a combination of surface catalysis and in situ vapor–liquid–solid mechanisms is described. A process by which PGN layers can be transferred onto arbitrary substrates while keeping the 3D architecture intact is also described. Single and multilayer stacked PGNs are envisioned for future ultralarge and tunable surface‐area applications in hydrogen storage and supercapacitors.     

利用氧化石墨烯复合膜吸附去除水中重金属离子的研究进展

氧化石墨烯作为一种独特的碳纳米材料,具有很高的比表面积,且其表面含有丰富的羟基、羧基等含氧基团,被认为是一种得天独厚的吸附材料,在净化水体方面有着广阔的发展前景。目前,为进一步提高氧化石墨烯对重金属离子的选择吸附性,氧化石墨烯被辅之以其他功能化材料,来制备复合材料。此外,膜分离技术在解决水环境问题上效果显著,因此将氧化石墨烯复合材料与膜分离技术相结合,来制备氧化石墨烯复合膜,对净化水体起到了事半功倍的效果。本文综述了氧化石墨烯复合膜材料的制备方法,并对其去除水中重金属离子的研究进展与吸附机理进行了综述,也对后续研究方向进行了展望。     

石墨烯纳米片/AZ91镁基复合材料的显微组织与力学性能

采用铸造工艺制备了石墨烯纳米片(GNPs)增强的AZ91镁基复合材料,测试了复合材料的力学性能,并利用光学显微镜、X射线衍射仪、透射电子显微镜、扫描电子显微镜和能谱仪对复合材料的微观组织、界面结合和断口形貌进行了表征和分析,讨论了复合材料的强化机理。结果表明:石墨烯纳米片可有效细化镁基体的晶粒组织,在添加少量石墨烯纳米片时(0.1%),复合材料的屈服强度、延伸率和显微硬度分别为(164±5)MPa、(7.7±0.1)%和(74.2±2)HV,比基体分别提高了37.8%、13.2%和24.7%。GNPs与镁基体形成了强界面结合,这更有利于发挥应力转移强化、细晶强化等作用,提高镁合金强度、塑性等力学性能。     

One‐Step Transfer and Integration of Multifunctionality in CVD Graphene by TiO2/Graphene Oxide Hybrid Layer

We present a straightforward method for simultaneously enhancing the electrical conductivity, environmental stability, and photocatalytic properties of graphene films through one‐step transfer of CVD graphene and integration by introducing TiO₂/graphene oxide layer. A highly durable and flexible TiO₂ layer is successfully used as a supporting layer for graphene transfer instead of the commonly used PMMA. Transferred graphene/TiO₂ film is directly used for measuring the carrier transport and optoelectronic properties without an extra TiO₂ removal and following deposition steps for multifunctional integration into devices because the thin TiO₂ layer is optically transparent and electrically semiconducting. Moreover, the TiO₂ layer induces charge screening by electrostatically interacting with the residual oxygen moieties on graphene, which are charge scattering centers, resulting in a reduced current hysteresis. Adsorption of water and other chemical molecules onto the graphene surface is also prevented by the passivating TiO₂ layer, resulting in the long term environmental stability of the graphene under high temperature and humidity. In addition, the graphene/TiO₂ film shows effectively enhanced photocatalytic properties because of the increase in the transport efficiency of the photogenerated electrons due to the decrease in the injection barrier formed at the interface between the F‐doped tin oxide and TiO₂ layers.     

用于表面增强拉曼散射的石墨烯/纳米粒子复合基底材料的研究现状

表面增强拉曼散射(Surface enhanced Raman scattering,SERS)自从被发现以来在单分子检测、生物医学体系、环境科学、纳米材料以及传感器等领域获得了广泛的应用,而其SERS增强因子、物质吸附能力等性能的好坏主要取决于SERS的基底材料及结构。相比于纳米粒子的SERS基底,石墨烯/纳米粒子复合材料的SERS基底由于石墨烯额外的化学增强作用、表面分子富集和荧光淬灭等功能而受到各国研究人员的重视。首先分析了石墨烯/纳米粒子复合材料的SERS增强机理,然后从材料制备和基底结构两个方面综述了石墨烯/纳米粒子复合材料在SERS上的研究现状,最后对其未来的发展方向进行了展望。     

Graphene/Half-Metallic Heusler Alloy: A Novel Heterostructure toward High-Performance Graphene Spintronic Devices

Graphene-based vertical spin valves (SVs) are expected to offer a large magnetoresistance effect without impairing the electrical conductivity, which can pave the way for the next generation of high-speed and low-power-consumption storage and memory technologies. However, the graphene-based vertical SV has failed to prove its competence due to the lack of a graphene/ferromagnet heterostructure, which can provide highly efficient spin transport. Herein, the synthesis and spin-dependent electronic properties of a novel heterostructure consisting of single-layer graphene (SLG) and a half-metallic Co₂Fe(Ge_0.5Ga_0.5) (CFGG) Heusler alloy ferromagnet are reported. The growth of high-quality SLG with complete coverage by ultrahigh-vacuum chemical vapor deposition on a magnetron-sputtered single-crystalline CFGG thin film is demonstrated. The quasi-free-standing nature of SLG and robust magnetism of CFGG at the SLG/CFGG interface are revealed through depth-resolved X-ray magnetic circular dichroism spectroscopy. Density functional theory (DFT) calculation results indicate that the inherent electronic properties of SLG and CFGG such as the linear Dirac band and half-metallic band structure are preserved in the vicinity of the interface. These exciting findings suggest that the SLG/CFGG heterostructure possesses distinctive advantages over other reported graphene/ferromagnet heterostructures, for realizing effective transport of highly spin-polarized electrons in graphene-based vertical SV and other advanced spintronic devices.     

一步法制备石墨烯复合花状钨酸铋光催化剂

采用一步水热法合成石墨烯复合花状钨酸铋高效可见光光催化剂。降解甲基橙的性能实验结果表明, 与单纯的Bi₂WO₆相比, 所有Bi₂WO₆-rGO复合光催化剂表现出更高的光催化性能。其中, Bi₂WO₆-rGO (0.5wt%)具有最高的光催化活性, 其速率常数达到5.0×10^-2 /min, 是纯Bi₂WO₆的1.7倍。增强光催化性能的原因归结为以下两方面的协同作用: 还原石墨烯在复合光催化剂中起到了电子快速传输作用; 石墨烯提供了有利于吸附有机污染物的大比表面积。本研究可以为设计与合成高性能石墨烯基光催化剂提供新的思路。     

Conjugated‐Polyelectrolyte‐Functionalized Reduced Graphene Oxide with Excellent Solubility and Stability in Polar Solvents

Conjugated‐polyelectrolyte (CPE)‐functionalized reduced graphene oxide (rGO) sheets are synthesized for the first time by taking advantage of a specially designed CPE, PFVSO₃, with a planar backbone and charged sulfonate and oligo(ethylene glycol) side chains to assist the hydrazine‐mediated reduction of graphene oxide (GO) in aqueous solution. The resulting CPE‐functionalized rGO (PFVSO₃‐rGO) shows excellent solubility and stability in a variety of polar solvents, including water, ethanol, methanol, dimethyl sulfoxide, and dimethyl formamide. The morphology of PFVSO₃‐rGO is studied by atomic force microscopy, X‐ray diffraction, and transmission electron microscopy, which reveal a sandwich‐like nanostructure. Within this nanostructure, the backbones of PFVSO₃ stack onto the basal plane of rGO sheets via strong π–π interactions, while the charged hydrophilic side chains of PFVSO₃ prevent the rGO sheets from aggregating via electrostatic and steric repulsions, thus leading to the solubility and stability of PFVSO₃‐rGO in polar solvents. Optoelectronic studies show that the presence of PFVSO₃ within rGO induces photoinduced charge transfer and p‐doping of rGO. As a result, the electrical conductivity of PFVSO₃‐rGO is not only much better than that of GO, but also than that of the unmodified rGO.     

石墨烯和石墨烯基纳米复合材料的制备及在生物医疗领域的应用

抗菌材料在各个应用领域的广泛使用,有效地保障着公众的身体健康.然而,在抗菌材料合成过程中要使用大量有机溶剂,不仅在很大程度上限制了合成抗菌剂在各个领域的应用,而且残留的有机溶剂也会对环境造成极大危害.因此,新型抗菌剂的开发及复合抗菌剂的合成方法和路线的改进是抗菌材料专家们研究的重点问题之一.首先介绍了新型抗菌材料——石墨烯及石墨烯基复合材料的制备及性能,随后结合石墨烯基复合材料的特性,阐述了其在抗菌、药物控释、生物传感、组织工程材料等方面的应用.     

氧化石墨烯增强水泥基复合材料的研究现状及展望

水泥水化进程复杂,所形成的水化产物缺陷较多,因而导致水泥基复合材料的力学性能及耐久性较差,如何对水泥水化行为进行调控成为了研究的热点。氧化石墨烯(GO)是由石墨氧化制备石墨烯的中间产物,因其存在大量的活性基团,在水泥基复合材料领域具有广阔的应用前景。概述了氧化石墨烯的选择及制备,论述了氧化石墨烯增强水泥基复合材料的流变性、微结构、物理力学性能及耐久性,重点阐述了氧化石墨烯对水泥基复合材料水化及性能调控的作用机理,针对当前研究中存在的问题进行了总结,并对未来的研究工作进行了展望。     

石墨烯复合材料的制备及应用研究进展

石墨烯是碳原子以sp2杂化连接而成的单原子层结构,这一独特的二维结构使得石墨烯具有优异的光电性能、热稳定性以及化学性能.石墨烯复合材料的制备、性能和应用成为近年的研究热点.本文综述了石墨烯复合材料的制备方法,包括石墨烯/高分子复合材料、石墨烯/金属(金属氧化物)复合材料、石墨烯三元复合材料,以及石墨烯复合材料在锂电池、电容器、光伏材料、传感器等方面的应用研究进展,指出了石墨烯复合材料研究的重要方向.