原料尺寸对氧化石墨与石墨烯性能的影响

采用改进的Hummers法对不同尺寸的天然石墨进行氧化处理,水合肼还原获得石墨烯。利用红外光谱(FTIR)、拉曼光谱(Raman)、X射线衍射(XRD)等对天然石墨、氧化石墨和石墨烯的化学结构、光谱学及结晶性进行表征。结果表明:天然石墨被充分氧化为氧化石墨,氧化石墨被还原为完美的石墨烯;天然石墨尺寸越小,氧化程度越大,氧化石墨的层间距越大;氧化石墨的D峰和G峰的强度比ID/IG与天然石墨尺寸大小成正比;与同尺寸的氧化石墨相比,石墨烯的ID/IG值比氧化石墨的大,说明石墨烯中sp2杂化碳层平面的平均尺寸小于氧化石墨的平均尺寸,新生成的石墨化区域被一些缺陷分割成尺寸更小的sp2杂化区域。     

Multilayer Stacked Low‐Temperature‐Reduced Graphene Oxide Films: Preparation,Characterization, and Application in Polymer Memory Devices

Highly reduced graphene oxide (rGO) films are fabricated by combining reduction with smeared hydrazine at low temperature (e.g., 100 °C) and the multilayer stacking technique. The prepared rGO film, which has a lower sheet resistance (≈160–500 Ω sq⁻¹) and higher conductivity (26 S cm⁻¹) as compared to other rGO films obtained by commonly used chemical reduction methods, is fully characterized. The effective reduction can be attributed to the large “effective reduction depth” in the GO films (1.46 µm) and the high C1s/O1s ratio (8.04). By using the above approach, rGO films with a tunable thickness and sheet resistance are achieved. The obtained rGO films are used as electrodes in polymer memory devices, in a configuration of rGO/poly(3‐hexylthiophene) (P3HT):phenyl‐C61‐butyric acid methyl ester (PCBM)/Al, which exhibit an excellent write‐once‐read‐many‐times effect and a high ON/OFF current ratio of 10⁶.     

Effects of Pb Intercalation on the Structural and Electronic Properties of Epitaxial Graphene on SiC

The effects of Pb intercalation on the structural and electronic properties of epitaxial single‐layer graphene grown on SiC(0001) substrate are investigated using scanning tunneling microscopy (STM), noncontact atomic force microscopy, Kelvin probe force microscopy (KPFM), X‐ray photoelectron spectroscopy, and angle‐resolved photoemission spectroscopy (ARPES) methods. The STM results show the formation of an ordered moiré superstructure pattern induced by Pb atom intercalation underneath the graphene layer. ARPES measurements reveal the presence of two additional linearly dispersing π‐bands, providing evidence for the decoupling of the buffer layer from the underlying SiC substrate. Upon Pb intercalation, the Si 2p core level spectra show a signature for the existence of Pb? Si chemical bonds at the interface region, as manifested in a shift of 1.2 eV of the bulk SiC component toward lower binding energies. The Pb intercalation gives rise to hole‐doping of graphene and results in a shift of the Dirac point energy by about 0.1 eV above the Fermi level, as revealed by the ARPES measurements. The KPFM experiments have shown that decoupling of the graphene layer by Pb intercalation is accompanied by a work function increase. The observed increase in the work function is attributed to the suppression of the electron transfer from the SiC substrate to the graphene layer. The Pb intercalated structure is found to be stable in ambient conditions and at high temperatures up to 1250 °C. These results demonstrate that the construction of a graphene‐capped Pb/SiC system offers a possibility of tuning the graphene electronic properties and exploring intriguing physical properties such as superconductivity and spintronics.     

Using Graphene Oxide to Enhance the Barrier Properties of Poly(lactic acid) Film

The ultra‐thin (polyethyleneimine/graphene oxide)_n [(PEI/GO)_n]multilayer films on poly(lactic acid) (PLA) were constructed via the layer‐by‐layer assembly. Here, the electrostatic interactions between PEI and GO were used to obtain the nanoscale composite membrane of (PEI/GO)_n on the surface of PLA film. With the number of assembling layers increased, the oxygen permeability (PO₂) of PLA film decreased substantially. As a 0.06 wt% GO solution was used with only four layers, the PO₂ decreased from 53.8 to 0.377 × 10^?4 cm³/m²/d/Pa, only 0.7% of the original PLA film. At the same time, the coated PLA film also presented a good transparency and better mechanical properties. It is a novel way to use GO on biodegradable packaging materials. Copyright © 2014 John Wiley & Sons, Ltd.     

氧化石墨烯薄膜厚度对元件湿敏性能的影响

以改进Hummers法获得的氧化石墨为原料制备氧化石墨烯,采用旋涂法通过使用不同浓度的氧化石墨烯水相分散液制备不同厚度的氧化石墨烯薄膜湿敏元件。采用X射线衍射仪(XRD)、红外光谱仪(FT-IR)、扫描电子显微镜(SEM)、扫描探针显微镜(SPM)和湿度测试仪对氧化石墨烯薄膜的结构、形貌和湿敏性能进行分析。结果表明,在室温下随氧化石墨烯薄膜厚度减小(139nm、102nm、65nm、35nm和18nm),湿敏元件响应时间由10s缩短至2s,恢复时间由37s缩短至8s;在11.3%~93.6%RH范围内,湿敏元件电阻随湿度增加而显著减小,从兆欧级减小至千欧级,变化达到3个数量级;湿敏元件的最佳响应时间为2s,恢复时间为8s,最高灵敏度可达96.06%,具有较好的湿敏性能。     

Synergism of Water Shock and a Biocompatible Block Copolymer Potentiates the Antibacterial Activity of Graphene Oxide

Graphene oxide (GO) is promising in the fight against pathogenic bacteria. However, the antibacterial activity of pristine GO is relatively low and concern over human cytotoxicity further limits its potential. This study demonstrates a general approach to address both issues. The developed approach synergistically combines the water shock treatment (i.e., a sudden decrease in environmental salinity) and the use of a biocompatible block copolymer (Pluronic F‐127) as a synergist co‐agent. Hypoosmotic stress induced by water shock makes gram‐negative pathogens more susceptible to GO. Pluronic forms highly stable nanoassemblies with GO (Pluronic‐GO) that can populate around bacterial envelopes favoring the interactions between GO and bacteria. The antibacterial activity of GO at a low concentration (50 μg mL^?1) increases from <30% to virtually complete killing (>99%) when complemented with water shock and Pluronic (5 mg mL^?1) at ≈2–2.5 h of exposure. Results suggest that the enhanced dispersion of GO and the osmotic pressure generated on bacterial envelopes by polymers together potentiate GO. Pluronic also significantly suppresses the toxicity of GO toward human fibroblast cells. Fundamentally, the results highlight the crucial role of physicochemical milieu in the antibacterial activity of GO. The demonstrated strategy has potentials for daily‐life bacterial disinfection applications, as hypotonic Pluronic‐GO mixture is both safe and effective.     

氧化石墨烯及其聚合物复合材料制备的研究进展

石墨烯是一种具有单层蜂窝状二维网格结构的新型材料,具有优异的力学、化学性能。氧化石墨烯(GO)作为氧化-还原法制备石墨烯的中间体,具有较高的比表面积以及石墨烯所不具备的丰富官能团。鉴于官能团的存在,GO具有优良的化学修饰性能,以此可制备性能更高的或具备新性能的GO/聚合物复合材料。文中综述了氧化石墨烯的结构、性能及制备方法,主要介绍了制备GO的Hummers法,比较了GO/聚合物复合材料的不同制备方法,列举了复合材料的性能特点,最后对GO复合材料制备方法的发展和GO/聚合物复合材料的应用前景进行了展望。     

Preservation of Surface Conductivity and Dielectric Loss Tangent in Large‐Scale,Encapsulated Epitaxial Graphene Measured by Noncontact Microwave Cavity Perturbations

Regarding the improvement of current quantized Hall resistance (QHR) standards, one promising avenue is the growth of homogeneous monolayer epitaxial graphene (EG). A clean and simple process is used to produce large, precise areas of EG. Properties like the surface conductivity and dielectric loss tangent remain unstable when EG is exposed to air due to doping from molecular adsorption. Experimental results are reported on the extraction of the surface conductivity and dielectric loss tangent from data taken with a noncontact resonance microwave cavity, assembled with an air‐filled, standard R100 rectangular waveguide configuration. By using amorphous boron nitride (a‐BN) as an encapsulation layer, stability of EG's electrical properties under ambient laboratory conditions is greatly improved. Moreover, samples are exposed to a variety of environmental and chemical conditions. Both thicknesses of a‐BN encapsulation are sufficient to preserve surface conductivity and dielectric loss tangent to within 10% of its previously measured value, a result which has essential importance in the mass production of millimeter‐scale graphene devices demonstrating electrical stability.     

The Effect of Thermal Reduction on the Water Vapor Permeation in Graphene Oxide Membranes

In the present study, the influence of the thermal reduction on the water vapor transmission properties of thin graphene oxide (GO) membranes is evaluated. The macroscopically measured property of the Water Vapor Transmission Rate (WVTR) exhibits step like dependence contrary to the gradual microscopic structural alterations identified by several techniques (XPS, FTIR and XRD) applied in situ during the thermal annealing process. Three distinct regions of WVTR‐values associated with distinct interlayer distances i.e., >7.5 Å, ∼6 Å and <6 Å are essentially observed which may be compared to the findings of the recently reported first principle calculations. Our experimental results enable the understanding of the water vapor unimpeded transmission through the layers of the oxygen rich GO nanostructured membranes and consequently facilitate the design of functional membranes for separation applications.     

单点缺陷氧化石墨烯电子结构与光学特性的第一性原理研究

本研究采用基于密度泛函理论的第一性原理方法,在局域密度近似和广义梯度近似下,研究了单点缺陷下不同结构氧化石墨烯的电子结构和光学特性。研究结果表明:文中四种构型的氧化石墨烯为力学稳定结构,其中包含不饱和氧原子的氧化石墨烯结构在水裂解及制氢中具有重要应用潜力。能带及分波态密度计算结果表明,包含不饱和氧原子的构型为间接带隙半导体,其余构型均为直接带隙半导体,且掺杂类型和带隙值随结构不同而改变。氧化石墨烯的光学吸收表现为各向异性,且在垂直于平面方向上的吸收边蓝移到近紫外可见光区。包含sp3杂化形式的结构光学吸收系数比包含sp2杂化的结构高,说明碳氧双键和悬挂键的存在对吸收光谱有重要影响。     

聚氯乙烯/氧化石墨烯薄膜的力学性能和热稳定性能

通过溶液共混法制备了氧化石墨烯(GO)分散均匀的聚氯乙烯(PVC)/GO纳米复合薄膜,研究了薄膜的力学性能和热稳定性能。结果表明,微量GO能大幅度提高PVC的模量和拉伸强度,且保持较高的断裂伸长率。在PVC中添加质量分数为0.12%的GO,PVC的拉伸强度提高63%,杨氏模量提高20%;添加量为0.60%时,PVC的拉伸强度提高125%,杨氏模量提高126%.添加GO还能提高PVC的起始分解温度、最大分解温度以及PVC的成碳量。GO片层具有较高的强度和模量、GO在高分子基体内的均匀分散、GO和PVC之间较强的相互作用、GO与PVC的层状结构,是其力学性能提高的主要原因.     

Implications of Chemical Reduction Using Hydriodic Acid on the Antimicrobial Properties of Graphene Oxide and Reduced Graphene Oxide Membranes

The antimicrobial properties of graphene‐based membranes such as single‐layer graphene oxide (GO) and modified graphene oxide (rGO) on top of cellulose ester membrane are reported in this study. rGO membranes are made from GO by hydriodic acid (HI) vapor treatment. The antibacterial properties are tested after 3 h contact time with selected model bacteria. Complete bacterial cell inactivation is found only after contact with rGO membranes, while no significant bacterial inactivation is found for the control i) GO membrane, ii) the mixed cellulose ester support, and the iii) rGO membrane after additional washing that removes the remaining HI. This indicates that the antimicrobial effect is neither caused by the graphene nor the membrane support. The antimicrobial effect is found to be conclusively linked to the HI eliminating microbial growth, at concentrations from 0.005%. These findings emphasize the importance of caution in the reporting of antimicrobial properties of graphene‐based surfaces.     

Spin‐Polarized Semiconductors: Tuning the Electronic Structure of Graphene by Introducing a Regular Pattern of sp3 Carbons on the Graphene Plane

First‐principles calculations (generalized gradient approximation, density functional therory (DFT) with dispersion corrections, and DFT plus local atomic potential) are carried out on the stability and electronic structures of superlattice configurations of nitrophenyl diazonium functionalized graphene with different coverage. In the calculations, the stabilities of these structures are strengthened significantly since van der Waals interactions between nitrophenyl groups are taken into account. Furthermore, spin‐polarized and wider‐bandgap electronic structures are obtained when the nitrophenyl groups break the sublattice symmetry of the graphene. The unpaired quasi‐localized p electrons are responsible for this itinerant magnetism. The results provide a novel approach to tune graphene's electronic structures as well as to form ferromagnetic semiconductive graphene.