H2S在氧化石墨烯表面的吸附和分解的理论研究

用周期性密度泛函方法对H₂S在氧化石墨烯(GO)上的吸附和分解进行了理论计算, 讨论了H₂S和GO上的羟基和环氧基团的反应过程．结果表明,反应过程是通过H₂S或-SH上的H转移使得GO的环氧基开环和羟基氢化,当GO相反面存在羟基时有助于环氧基团的开环和羟基氢化反应．H₂S在GO上吸附和分解到S原子的反应机理中引入了相应的中间态,计算两次脱氢过程能垒分别为3.2和10.4 kcal/mol,第二个H原子的转移是GO还原过程的速率决定步骤．结果还表明GO上的羟基和环氧基团有助于加强S原子和石墨烯的结合．     

Physical properties and device applications of graphene oxide

Graphene oxide (GO), the functionalized graphene with oxygenated groups (mainly epoxy and hydroxyl), has attracted resurgent interests in the past decade owing to its large surface area, superior physical and chemical properties, and easy composition with other materials via surface functional groups. Usually, GO is used as an important raw material for mass production of graphene via reduction. However, under different conditions, the coverage, types, and arrangements of oxygen-containing groups in GO can be varied, which give rise to excellent and controllable physical properties, such as tunable electronic and mechanical properties depending closely on oxidation degree, suppressed thermal conductivity, optical transparency and fluorescence, and nonlinear optical properties. Based on these outstanding properties, many electronic, optical, optoelectronic, and thermoelectric devices with high performance can be achieved on the basis of GO. Here we present a comprehensive review on recent progress of GO, focusing on the atomic structures, fundamental physical properties, and related device applications, including transparent and flexible conductors, field-effect transistors, electrical and optical sensors, fluorescence quenchers, optical limiters and absorbers, surface enhanced Raman scattering detectors, solar cells, light-emitting diodes, and thermal rectifiers.     

A new approach to solar flare prediction

Frontiers of Physics - Graphene oxide (GO), the functionalized graphene with oxygenated groups (mainly epoxy and hydroxyl), has attracted resurgent interests in the past decade owing to its large...     

First-principles insight into Li and Na ion storage in graphene oxide

The structural, electronic, and adsorption properties of Li/Na ions on graphene decorated by epoxy groups are investigated by first-principles calculations based on density functional theory.Our results show that the concentration of epoxy groups remarkably affects the structural and electronic properties of graphene.The bandgaps change monotonically from0.16 eV to 3.35 eV when the O coverage increases from 12.5% to 50%(O/C ratio).Furthermore, the highest lithiation potential of 2.714 V is obtained for the case of graphene oxide(GO) with 37.5 % O coverage, while the highest sodiation potential is 1.503 V for GO with 12.5% O coverage.This clearly demonstrates that the concentration of epoxy groups has different effects on Li and Na storage in GO.Our results provide a new insight into enhancing the Li and Na storage by tuning the concentration of epoxy groups on GO.     

Elucidating synthesis of noble metal nanoparticles/graphene oxide in free-scavenger γ-irradiation

Three representative noble metal (Ag, Au and Pt) nanoparticles decorated graphene oxide (NMNPs/GO) composites were fabricated via γ-irradiation without scavenger. The NMNPs/GO composites exhibited the pure and well-dispersed particles structure, which directly illustrated that the GO could be acted as scavenger to benefit reduction and growth of NMNPs. Compared with irradiated GO (IGO), the GO substrate of composites had the lower relative content of hydroxyl groups, meanwhile, the relative contents of carbonyl groups (Pt > Au > Ag) were increased with increasing valence of noble metal. Such results illustrated that the abundant hydroxyl groups could convert the hydrated electrons, hydroxyl and hydrogen radicals to promote the growth of NMNPs on the surface of GO. In addition, the Raman signals of Ag NPs/GO composites were significantly enhanced (6.18 fold more than pristine GO, respectively), exhibiting obvious surface-enhanced Raman scattering activity. Therefore, this paper revealed that the GO could convert the hydrated electrons and radicals to synthetizing NMNPs/GO composites during γ-ray irradiation.     

Tuning of electronic properties and dynamical stability of graphene oxide with different functional groups

The structural, electronic and vibrational properties of graphene oxide (GO) with varying proportion of epoxy and hydroxyl functional groups have been studied using density functional theory. The functional groups and oxygen density have an obvious influence on the electronic and vibrational properties. The dependence of band gap on associated functional groups and oxygen density shows a possibility of tuning the band gap of graphene by varying the functional groups as well as oxidation level. The absorption of high oxygen content in graphene leads to the gap opening and resulting in a transition from semimetal to semiconductor. Phonon dispersion curves show no imaginary frequency or no softening of any phonon mode throughout the Brillouin zone which confirms the dynamical stability of all considered GO models. Different groups and different oxygen density result into the varying characteristics of phonon modes. The computed results show good agreement with the experimental observations. Our results present interesting possibilities for engineering the electronic properties of graphene and GO and impact the fabrication of new electronics.     

基于芯-电子结合能偏移的碱金属中的表面、尺寸和热效应

还原氧化石墨烯是大规模生产石墨烯的前体;然而迄今为止,还原氧化石墨烯的电子结构还没有达成共识. 本文运用从头分子动力学方法研究羟基在石墨烯表面的吸附过程. 在吸附过程中,OH基团首先在位于两个碳原子桥位上方形成物理吸附络合物,然后翻越过渡态,最终被吸附在一个碳原子的顶位位点. 结果显示5×5石墨烯表面最多可以吸附6个羟基,表明石墨烯表面羟基的覆盖率约为12%. 计算结果还显示,负吸附能随着羟基吸附数目的增加而线性增加,带隙也随着羟基吸附数目的增加而线性增加.     

Ecofriendly Route for the Synthesis of Highly Conductive Graphene Using Extremophiles for Green Electronics and Bioscience

Highly conductive biocompatible graphene is synthesized using ecofriendly reduction of graphene oxide (GO). Two strains of non‐pathogenic extremophilic bacteria are used for reducing GO under both aerobic and anaerobic conditions. Degree of reduction and quality of bacterially reduced graphene oxide (BRGO) are monitored using UV–vis spectroscopy, X‐ray photoelectron spectroscopy, and Raman spectroscopy. Structural morphology and variation in thickness are characterized using electron microscopy and atomic force microscopy, respectively. Electrical measurements by three‐probe method reveal that the conductivity has increased by 10⁴–10⁵ fold from GO to BRGO. Biocompatibility assay using mouse fibroblast cell line shows that BRGO is non‐cytotoxic and has a tendency to support as well as enhance the cell growth under laboratory conditions. Hereby, a cost effective, non‐toxic bulk reduction of GO to biocompatible graphene for green electronics and bioscience application is achieved using halophilic extremophiles for the first time.     

双酚A在氧化石墨烯表面吸附的分子动力学模拟

双酚A(bisphenol A,BPA)是一种内分泌干扰物,会对机体多方面产生不良影响,包括生殖系统、神经系统、胚胎发育等.因此,在水环境中如何检测和去除BPA显得尤为重要.实验研究表明,氧化石墨烯(graphene oxide,GO)对BPA具有优异的吸附去除性能,但在分子层面的吸附机制尚不清楚.分子动力学模拟,能提供BPA在GO表面的动态吸附过程以及吸附构象等详细信息,可以弥补实验的不足.本文利用GROMACS分子动力学模拟软件,系统模拟了BPA在含GO的水溶液中的吸附过程,并计算了吸附自由能.结果显示:所有的BPA均被吸附在GO两侧,通过分析BPA的吸附构象以及与GO的相互作用,发现π-π疏水作用对吸附起主导作用,且显示出很好的稳定性,而静电和氢键作用增加了GO的吸附能力.通过自由能计算,BPA在GO表面的结合能达30 k J/mol,远大于水分子的5 k J/mol.这些结果进一步证实GO对BPA具有很强的吸附能力以及GO作为吸附剂在水溶液中去除BPA的可行性.     

Hydrothermal method for the production of reduced graphene oxide

Reduced graphene oxide, RGO (also called chemically modified graphene, CMG) was synthesized by a simple hydrothermal method, with graphite oxide (GO), prepared by the modified Hummers method, served as the raw material. Structural and morphological studies indicate the degree of reduction is dependent on the temperature, which is also verified by Raman analysis. The variation in interlayer distance and the intensity ratio of the D to G Raman modes (I_D/I_G) indicates higher reaction temperature can accelerate the reduction of GO. The conductivity also varies with the degree of reduction, as verified by electrochemical analyzer. Moreover, the reaction process affects organic functional groups, the mechanism during the reaction process is discussed.     

Molecular responses of cells to 2-mercapto-1-methylimidazole gold nanoparticles (AuNPs)-mmi: investigations of histone methylation changes

Reduced graphene oxide (RGO) sheet was functionalized with nanocrystalline cellulose (NCC) via click coupling between azide-functionalized graphene oxide (GO-N₃) and terminal propargyl-functionalized nanocrystalline cellulose (PG-NCC). First, the reactive azide groups were introduced on the surface of GO with azidation of 2-chloroethyl isocyanate-treated graphene oxide (GO-Cl). Then, the resulted compounds were reacted with PG-NCC utilizing copper-catalyzed azide-alkyne cycloaddition. During the click reaction, GO was simultaneously reduced to graphene. The coupling was confirmed by Fourier transform infrared, Raman, DEPT135, and ¹³C NMR spectroscopy, and the complete exfoliation of graphene in the NCC matrix was confirmed with X-ray diffraction measurement. The degree of functionalization from the gradual mass loss of RGO-NCC suggests that around 23 mass % has been functionalized covalently. The size of both NCC and GO was found to be in nanometric range, which decreased after click reaction.     

水热法快速制备荧光氧化石墨烯量子点及其在细胞成像中的应用

作为一种新型荧光纳米材料,氧化石墨烯量子点(GO QDs)凭借其良好的水溶性和生物相容性得到广泛的关注。以氧化石墨烯为原料,过氧化氢为氧化剂,一步水热法在90 min内快速制备氧化石墨烯量子点,实现了快速、高效及绿色制备氧化石墨烯量子点。所制备得到的氧化石墨烯量子点分布均匀,透射电镜(TEM)图片表明氧化石墨烯量子点粒径分布在2.25～5.25 nm,傅里叶红外光谱(FTIR)和X射线电子能谱(XPS)显示氧化石墨烯量子点表面含有大量的羟基、羧基、羰基等含氧功能团,表明氧化石墨烯量子点具有很好的水溶性。荧光发射光谱(PL)表明氧化石墨烯量子点具有激发波长依赖性。基于其独特的纳米结构,良好的光学性能和生物相容性,氧化石墨烯量子点可替代传统荧光纳米材料应用于细胞成像。     

Synthesis of Blue‐, Green‐, Yellow‐, and Red‐Emitting Graphene‐Quantum‐Dot‐Based Nanomaterials with Excitation‐Independent Emission

A one‐pot method is described for the preparation of graphene quantum dots/graphene oxide (GQDs/GO) hybrid composites with emission in the visible region, through heteroatom doping and hydroxyl‐radical‐induced decomposition of GO. The NH₄OH‐ and thiourea‐mediated dissociation of H₂O₂ produces hydroxyl radicals. Treatment of GO with hydroxyl radicals results in the production of small‐sized GO sheets and GQDs, which self‐assemble to form GQDs/GO through strong π–π interactions. For example, the reaction of GO with a mixture of NH₄OH and H₂O₂ for 40, 120, and 270 min generates yellow‐emitting GQDs/GO (Y‐GQDs/GO), green‐emitting GQDs/GO, and blue‐emitting GQDs, while red‐emitting GQDs/GO (R‐GQDs/GO) are prepared by incubating GO with a mixture of thiourea and H₂O₂. From the analysis of these four GQD‐based nanomaterials by transmission electron microscopy, atomic force microscopy, and fluorescence lifetime spectroscopy, it is found that this tunable fluorescence wavelength results from the differences in particle size. All four GQD‐based nanomaterials exhibit moderate quantum yields (1–10%), nanosecond fluorescence lifetimes, and excitation‐independent emissions. Except for R‐GQDs/GO, the other three GQD‐based nanomaterials are stable in a high‐concentration salt solution (e.g., 1.6 m NaCl) and under high‐power irradiation, enabling the sensitive (high‐temperature resolution and large activation energy) and reversible detection of temperature change. It is further demonstrated that Y‐GQD/GO can be used to image HeLa cells.     

Dye-sensitized solar cells with 3D flower-like α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-decorated reduced graphenes oxide as photoanodes

For the first time, we report a one-step fabrication of an environment-friendly approach to synthesize flower-like α-Fe₂O₃ hierarchical nanoparticles (NPs)/reduced graphene oxide (RGO) hybrids by combining the graphene oxide (GO) with the growth of α-Fe₂O₃ NPs. The GO sheet which possesses the functional group, such as hydroxyl (–OH) and carbonyl groups (–OOH), can be easily incorporated with the petal of the flower-like α-Fe₂O₃ in ethanol and water solution through a solvothermal process, during which GO is reduced to RGO without the addition of any strong reducing agent or requiring any post-high-temperature annealing process. The as-prepared samples are loose and porous with flower-like structure, and the RGO hybrids were wrapped up uniformly on the sheet of α-Fe₂O₃ NPs. To demonstrate the potential applications, we have fabricated dye-sensitized solar cells (DSSCs) from the as-synthesized hierarchical flower-like α-Fe₂O₃/RGO and investigated it for the photoanode of DSSCs. Results show that the hierarchical α-Fe₂O₃/RGO solar cell exhibits improved performances in comparison with the free α-Fe₂O₃ NPs. The enhancement of photovoltaic properties is attributed to the unique porous nature and good conductivity which allow more efficient diffusion of I^? ions and facilitate the transfer of electron in the network.     

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.     

Direct synthesis of graphene nanosheets support Pd nanodendrites for electrocatalytic formic acid oxidation

We report a solvothermal method preparation of dendritic Pd nanoparticles(DPNs) and spherical Pd nanoparticles(SPNs) supported on reduced graphene oxide(RGO). Drastically different morphologies of Pd NPs with nanodendritic structures or spherical structures were observed on graphene by controlling the reduction degree of graphene oxide(GO) under mild conditions. In addition to being a commonplace substrate, GO plays a more important role that relies on its surface groups, which serves as a shape-directing agent to direct the dendritic growth. As a result, the obtained DPNs/RGO catalyst exhibits a significantly enhanced electro-catalytic behavior for the oxidation of formic acid compared to the SPNs/RGO catalyst.     

不同尺度的蛋白质在纯石墨烯及氧化石墨烯表面的吸附比较

Using all-atom molecular dynamics (MD) simulations, we have investigated the adsorption stability and conformation change of different proteins on the surface of pristine graphene (PG) and graphene oxide (GO). We find that: (i) with the cooperation of the electrostatic interactions between proteins and oxygen-containing groups, GO shows better adsorption stability than PG; (ii) the peptide loses its secondary structure on both PG and GO surface, and the a-helix structure of the protein fragment is partially broken on PG surface, but is well preserved on GO surface, while the secondary structure of globular protein has no distinct change on both PG and GO surface. In general, GO presents better biocompatibility than PG. Our results are of significant importance to understand the interactions between proteins and PG/GO and the applications of PG/GO in biotechnology and biomedicine.     

Synthesis of RGO/Cu8S5/PPy Composite Nanosheets with Enhanced Peroxidase‐Like Activity for Sensitive Colorimetric Detection of H2O2 and Phenol

In this paper, a novel strategy for the fabrication of reduced graphene oxide (rGO)/Cu₈S₅/polypyrrole (PPy) composite nanosheets with Cu₈S₅ nanoparticles and PPy layer anchored on the surface of rGO as peroxidase‐like nanocatalyst is reported. During the synthesis, graphene oxide (GO)/CuO composite nanosheets are prepared first and used as templates, then the sulfuration of CuO and polymerization of pyrrole are accompanied with the reduction of GO, resulting in ternary rGO/Cu₈S₅/PPy composite nanosheets. The synthesized Cu₈S₅ nanoparticles with a diameter in the range from tens to hundreds of nanometers are dispersed within PPy decorated rGO nanosheets. The resultant ternary rGO/Cu₈S₅/PPy composite nanosheets exhibit a higher peroxidase‐like catalytic activity toward the oxidation of 3,3′,5,5′‐tetramethylbenzidine in the presence of H₂O₂ than GO/CuO and rGO/CuS composite nanosheets, revealing a synergistic effect on their activity. The as‐prepared rGO/Cu₈S₅/PPy platform provides a simple colorimetric approach for the detection of H₂O₂ and phenol with a high sensitivity. This work offers a new way for the fabrication of rGO‐based nanocomposite with superior enzyme‐like activity, which displays great potential applications in biocatalysis and environmental monitoring.     

Synthesis of graphene oxide sheets decorated by silver nanoparticles in organic phase and their catalytic activity

The graphene oxide(GO) sheets decorated by Ag nanoparticles were prepared using a liquid–liquid two-phase method at the room temperature. The synthesized samples existed in the organic phase and were characterized by X-ray diffraction, transmission electron microscopy, UV–vis spectroscopy and Raman spectra. The results demonstrate that these silver-nanoparticles with diameter of about 10 nm assembled on graphene oxide sheets are flexible and can form stable suspensions in organic phase. Raman signals of graphene oxide sheets are increased by the attached silver nanoparticles, displaying higher surface-enhanced Raman scattering activity. Furthermore, Ag/GO are found to serve as effective catalysts to activate the reduction of 4-nitrophenol (4NP) in the presence of NaBH₄.     

Influence of Mechanical Stretching on Adsorption Properties of Nitrogen-Doped Graphene

This paper presents the results of quantum chemical modeling of chemisorption of atomic hydrogen and epoxy, carboxyl, and hydroxyl functional groups on nitrogen-doped graphene. It is shown that the substitutional nitrogen atom does not bind to adsorbing groups directly, but significantly increases the adsorption activity of neighboring carbon atoms. Mechanical stretching of doped graphene reduces the adsorption energy of all the aforementioned radicals. This reduction is significantly greater for the epoxy group than for the other functional groups. The results obtained confirm that, upon a sufficient stretching of a nitrogen-doped graphene sheet, the dissociation of molecular hydrogen and oxygen with subsequent precipitation of the resulting radicals onto graphene can be energetically favorable.