石墨烯基高分子复合材料的研究进展

自2004年石墨烯被发现以来,石墨烯优异的机械、热学、电学及光学性能引起广大学者的浓厚兴趣,许多石墨烯基高分子复合材料被相继合成和表征,研究显示,石墨烯基高分子复合材料有着广泛的应用前景。本文对石墨烯基高分子复合材料的研究进展进行了综述,重点对石墨烯基高分子复合材料的制备方法和性能进行了阐述,并对其在传感器、太阳能电池、超级电容器及其他方面的应用做了相关介绍,并对石墨烯／高分子复合材料的发展前景进行了展望。     

Electrodeposited Graphene and Silver Nanoparticles Modified Electrode for Direct Electrochemistry and Electrocatalysis of Hemoglobin

By using a 1‐butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the working electrode, graphene (GR) nanosheets and silver nanoparticles (Ag NPs) were step by step electrodeposited on the surface of the CILE with potentiostatic method. The fabricated Ag/GR/CILE was used as a new platform for protein electrochemistry and hemoglobin (Hb) was immobilized on its surface with chitosan (CTS) as film forming material. In 0.1 mol/L phosphate buffer solution, a pair of well‐defined and quasi‐reversible redox peaks appeared on the CTS/Hb/Ag/GR/CILE with a formal peak potential of ?0.202 V (vs. SCE) and a peak‐to‐peak separation (ΔE_p) of 68 mV, which indicated that direct electrochemistry of Hb was realized on the modified electrode. The results could be attributed to the synergistic effects of Ag NPs and GR nanosheets on the electrode surface, which provided a specific three‐dimensional structure with high conductivity and good biocompatibility. The Hb modified electrode showed excellent electrocatalysis to the reduction of trichloroacetic acid in the concentration range from 0.8 to 22.0 mmol/L with a detection limit of 0.42 mmol/L (3σ). Moreover, the modified electrode exhibited favorable reproducibility, long term stability and accuracy, with potential applications in the third‐generation electrochemical biosensor.     

石墨烯负载高活性Pd催化剂对乙醇的电催化氧化

以石墨粉为原料, 采用Hummers法液相氧化合成了氧化石墨(GO), 然后用化学一步还原制得石墨烯负载钯催化剂. X射线衍射(XRD)、透射电镜(TEM)表征表明, Pd在石墨烯载体上有较好的分散度, 粒径为3-5 nm. 电化学活性面积(EASA)、循环伏安(CV)、计时电流(CA)和计时电位(CP)等电化学测试表明, 与传统Pd/Vulcan XC-72相比, Pd/石墨烯催化剂对碱性介质中乙醇电催化氧化的催化活性有了很大的提高.     

Ultrasound assisted reduction of graphene oxide to graphene in l-ascorbic acid aqueous solutions: Kinetics and effects of various factors on the rate of graphene formation

The reduction of graphene oxide (GO) to graphene (rGO) was achieved by using 20 kHz ultrasound in l-ascorbic acid (l-AA, reducing agent) aqueous solutions under various experimental conditions. The effects of ultrasound power, ultrasound pulse mode, reaction temperature, pH value and l-AA amount on the rates of rGO formation from GO reduction were investigated. The rates of rGO formation were found to be enhanced under the following conditions: high ultrasound power, long pulse mode, high temperature, high pH value and large amount of l-AA. It was also found that the rGO formation under ultrasound treatment was accelerated in comparison with a conventional mechanical mixing treatment. The pseudo rate and pseudo activation energy (E_a) of rGO formation were determined to discuss the reaction kinetics under both treatment. The E_a value of rGO formation under ultrasound treatment was clearly lower than that obtained under mechanical mixing treatment at the same condition. We proposed that physical effects such as shear forces, microjets and shock waves during acoustic cavitation enhanced the mass transfer and reaction of l-AA with GO to form rGO as well as the change in the surface morphology of GO. In addition, the rates of rGO formation were suggested to be affected by local high temperatures of cavitation bubbles.     

Extraction and scattering analyses of 2D and bulk carriers in epitaxial graphene-on-SiC structure

Hall effect measurements of a graphene-on-SiC system were carried out as a function of temperature (1.8–200 K) at a static magnetic field (0.5 T). With the analysis of temperature dependent single-field Hall data with the Simple Parallel Conduction Extraction Method (SPCEM), bulk and two-dimensional (2D) carrier densities and mobilities were extracted successfully. Bulk carrier is attributed to SiC substrate and 2D carrier is attributed to the graphene layer. For each SPCEM extracted carrier data, relevant three-dimensional or 2D scattering analyses were performed. Each SPCEM extracted carrier data were explained with the related scattering analyses. A temperature independent mobility component, which may related to an interaction between graphene and SiC, was observed for both scattering analyses with the same mobility limiting value. With the SPCEM, effective ionized impurity concentration of SiC substrate, extracted 2D-mobility, and sheet carrier density of the graphene layer are calculated with using temperature dependent static magnetic field Hall data.     

Anisotropic quantum transport in monolayer graphene in the presence of Rashba spin–orbit coupling

We have studied spin-dependent electron tunneling through the Rashba barrier in a monolayer graphene lattices. The transfer matrix method, have been employed to obtain the spin dependent transport properties of the chiral particles. It is shown that graphene sheets in the presence of Rashba spin–orbit barrier will act as an electron spin-inverter.     

Investigating the effect of gas absorption on the electromechanical and electrochemical behavior of graphene/ZnO structure,suitable for highly selective and sensitive gas sensors

Graphene/ZnO hybrid was used, for the first time, to fabricate a highly selective and sensitive graphene based gas sensor by a combination of electromechanical and electrochemical characteristics of the graphene. ZnO nanowires in our fabricated sensor have two important roles: as the reductant of graphene oxide to obtain graphene and as an efficient electromechanical actuator due to their piezoelectric properties. To investigate the operation of the fabricated sensor as a gas sensor, a selected set of chemical vapors were introduced to the structure. It was found that chemical vapors change the resonance frequency of the graphene/ZnO structure, as well as the electrical resistivity of the sensor. The observed variation of the mechanical and electrical characteristics of the graphene/ZnO in response to gas exposure entitles the graphene/ZnO based sensor as a highly selective/sensitive device for gas sensing applications with distinctive signatures for different gas species.     

Confinement–deconfinement transitions for two-dimensional Dirac particles

We consider a two-dimensional massless Dirac operator coupled to a magnetic field B and an electric potential V growing at infinity. We find a characterization of the spectrum of the resulting operator H in terms of the relation between B and V at infinity. In particular, we give a sharp condition for the discreteness of the spectrum of H beyond which we find dense pure point spectrum.     

Comparative studies on electrochemical activity of graphene nanosheets and carbon nanotubes

This study compares the electrochemical activity of four kinds of carbon materials, i.e. single-walled carbon nanotubes (SWNTs), pristine graphene oxide nanosheets (GONs), chemically reduced GONs, and electrochemically reduced GONs, with potassium ferricyanide (K₃Fe(CN)₆), β-nicotinamide adenine dinucleotide (NADH) and ascorbic acid (AA) as the redox probes. Cyclic voltammetry (CV) results demonstrate that the electron transfer kinetics of the redox probes employed here at the carbon materials essentially depend on the kind of the materials, of which the redox processes of the probes at SWNTs and electrochemically reduced GONs are faster than those at the pristine and chemically reduced GONs. The different electron transfer kinetics for the redox probes at the carbon materials studied here could be possibly ascribed to the synergetic effects of the surface chemistry (e.g., C/O ratio, presence of quinone-like groups, surface charge, and surface cleanness) and conductivity of the materials. This study could be potentially useful for understanding the structure/property relationship of the carbon materials and, based on this, for screening and synthesizing advanced carbon materials for electrochemical applications.     

In situ chemical synthesis of SnO2–graphene nanocomposite as anode materials for lithium-ion batteries

An in situ chemical synthesis approach has been developed to prepare SnO₂–graphene nanocomposite. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (4–6 nm in size) on graphene matrix. The electrochemical reactivities of the SnO₂–graphene nanocomposite as anode material were measured by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂–graphene nanocomposite exhibited a reversible lithium storage capacity of 765 mAh/g in the first cycle and an enhanced cyclability, which can be ascribed to 3D architecture of the SnO₂–graphene nanocomposite.