Selective Removal of Hydroxyl Groups from Graphene Oxide

Graphene has a wide range of potential applications, thus tremendous efforts have been put into ensuring that the most direct and effective methods for its large‐scale production are developed. The formation of graphene materials from graphene oxide through a chemical reduction method is still one of the most preferred routes. Numerous methods starting from various reducing agents have been developed to obtain near‐pristine graphene sheets. However, most of the reducing agents are not mechanistically supported by classical organic chemistry knowledge and of those that are supported, they are only theoretically capable of, at most, reducing oxygen‐containing groups on graphene oxide to hydroxyl groups. Herein, we present a mechanistically proven method for the selective defunctionalisation of hydroxyl groups from graphene oxide that is based on ethanethiol–aluminium chloride complexes and provides a graphene material with improved properties. The structural, morphological and electrochemical properties of the graphene materials have been fully characterised based on high‐resolution X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry techniques. Our analyses showed that the obtained graphene materials exhibited high heterogeneous electron‐transfer rates, low charge‐transfer resistance and high conductivity as compared to the parent graphene oxide. Moreover, the selective defunctionalisation of hydroxyl groups could potentially allow for the tailoring of graphene properties for various applications.     

A New Member of the Graphene Family: Graphene Acid

A new member of the family of graphene derivatives, namely, graphene acid with a composition close to C₁(COOH)₁, was prepared by oxidation of graphene oxide. The synthetic procedure is based on repeated oxidation of graphite with potassium permanganate in an acidic environment. The oxidation process was studied in detail after each step. The multiple oxidations led to oxidative removal of other oxygen functional groups formed in the first oxidation step. Detailed chemical analysis showed only a minor amount of other oxygen‐containing functional groups such as hydroxyl and the dominant presence of carboxyl groups in a concentration of about 30 wt %. Further oxidation led to complete decomposition of graphene acid. The obtained material exhibits unique sorption capacity towards metal ions and carbon dioxide. The highly hydrophilic nature of graphene acid allowed the assembly of ultrathin free‐standing membranes with high transparency.     

Covalent Functionalization of Strained Graphene

An enhancement of the chemical activity of graphene is evidenced by first‐principles modelling of the chemisorption of hydrogen, fluorine, oxygen and hydroxyl groups on strained graphene. For the case of negative strain or compression, chemisorption of the single hydrogen, fluorine or hydroxyl group is energetically more favourable than those of their pairs on different sublattices. This behaviour stabilizes the magnetism caused by the chemisorption being against its destruction by the pair formations. Initially flat, compressed graphene is shown to buckle spontaneously right after chemisorption of single adatoms. Unlike hydrogenation or fluorination, the oxidation process turns from the endothermic to exothermic for all types of the strain and depends on the direction of applied strains. Such properties will be useful in designing graphene devices utilizing functionalization as well as mechanical strains.     

Adsorption of epoxy and hydroxyl groups on zigzag graphene nanoribbons: Insights from density functional calculations

Density functional theory calculations have been used to investigate the adsorption of epoxy and hydroxyl groups on zigzag graphene nanoribbons. Our calculations show that the adsorbed epoxy groups and both the epoxy and hydroxyl groups on a ribbon surface can be transformed to a carbonyl pair and a carbonyl-hydroxyl pair. The energy barriers of these processes are 1.13 and 0.37 eV, respectively. In contrast to the reduced GO sheets, the stabilities of the carbonyl-hydroxyl pair and the carbonyl pair, with respect to the corresponding initial configuration, strongly depend on the adsorbed sites of groups. The vacancy defect improves the adsorptions of oxygen-containing groups on the surface. Because of the adsorption of new hydroxyl groups, the O-H bond belonging to the carbonyl-hydroxyl pair was highly dissociative and led to the formation of a highly stable carbonyl group with the release of water. The magnetic and electronic properties of the zigzag graphene nanoribbons were well tuned by different oxidized groups.     

Effects of hydroxyl group on H2 dissociation on graphene: A density functional theory study

Graphene-based materials are promising for hydrogen production and storage. In this work, using density functional theory calculations, we explored how a hydroxyl group influences H₂ dissociation on graphene. Presence of the hydroxyl group makes the binding of H atom with graphene stronger, as the binding energy of H atom with the hydroxyl-modified graphene is higher than that with the pristine graphene. The para-site is the most favorable site for H₂ dissociation on both the pristine and hydroxyl-modified graphene. The energy barrier of H₂ dissociation at para-site on the pristine graphene is 3.10 eV whereas that on the hydroxyl-modified graphene is 2.46 eV, indicating a more facile H₂ dissociation on the hydroxyl-modified graphene.     

An Effective Method for Bulk Obtaining Graphene Oxide Solids

We report an effective method for bulk obtaining exfoliated graphene oxide (GO) solids from their aqueous solutions, which were prepared from nature graphite by an oxidation method. Tyndall effect proved that GO solution has a colloidal nature. Different flocculants were used to coagulate GO colloidal, and it was found that NaOH had the most obvious coagulation effect to GO. Transmission electron microscopy, X‐ray diffraction and atomic force microscopy analysis demonstrated that there were a large number of complete few‐layer GO sheets with thickness of about 0.8 nm, and the surfaces were very smooth, almost free of impurities. Liquid state ¹³C NMR and Fourier transformation infrared spectra showed the presence of abundant benzene carboxylic, hydroxyl and epoxide groups in the basal planes of GO. The graphene materials reduced from GO solids had good electrical conductivity. Our work explored a simple and effective route to extract GO from their solution, which is the most important to GO and graphene researches and applications.     

氮掺杂石墨烯与g-C3N4二维异质体对纳米Fe2O3光催化剂的复合改性

使用相分离的水解-溶剂热法制备了α-Fe₂O₃纳米粒子, 通过简单的湿化学法实现了质量分数为3%的石墨烯、 氮掺杂石墨烯和g-C₃N₄ 3种二维异质体对纳米α-Fe₂O₃的复合改性, 并比较了3种二维异质体对α-Fe₂O₃光催化活性的影响. 结果表明, 在光催化还原二氧化碳和降解液相苯酚过程中, 二维异质体的复合均提高了纳米α-Fe₂O₃的光催化活性, 氮掺杂石墨烯对α-Fe₂O₃的改性效果优于石墨烯, 其中g-C₃N₄对α-Fe₂O₃的改性效果最优. 通过表面光电压谱、 光电化学及羟基自由基等测试, 确认二维异质体的复合改性主要通过促进纳米α-Fe₂O₃的光生电荷分离和提高活性中间组分(羟基自由基)的含量提高纳米α-Fe₂O₃的光催化活性.     

π‐Conjugated Carbon Radicals at Graphene Oxide to Initiate Ultrastrong Chemiluminescence

Graphene oxide has widely been employed in various fields, but its structure and composition has still not been fully understood. Here we report that freshly prepared graphene oxide exhibits a large number of π‐conjugated carbon radicals at its π‐network plane, which result from the addition reaction of hydroxyl radicals from H₂O₂ onto the conjugated double bonds of graphene oxide. The π‐conjugated carbon radicals can directly initiate the long‐lasting visible chemiluminescence of luminol, which is even stronger than that obtained when horseradish peroxidase and H₂O₂ are used. Previously, graphene oxide was mainly reported to be a quencher of chemiluminescence instead. Remarkably, the reacted radicals can be regenerated, thereby enabling the repetitive initiation of chemiluminescence by re‐treatment of graphene oxide. The results reported here provide a new understanding of the structure, properties, and applications of graphene oxide.     

Density functional study of hydrogen adsorption and diffusion on Ni‐loaded graphene and graphene oxide

In this work, we performed density functional calculations to investigate the adsorption and diffusion of hydrogen on Ni‐loaded graphene and single layer graphene oxide (SLGO). We evaluated the feasibility of hydrogen spillover in the presence of Ni₄ cluster and the role of oxygen‐containing groups. Our calculations indicate that the hydrogen diffusion is difficult to take place on the Ni/graphene interface due to the stronger Ni? H bond strength. Further, the chemisorbed H atoms are also hard to diffuse freely on the graphene surface. For the SLGO surface, both hydroxyl and epoxide groups may not facilitate the hydrogen diffusion. Instead, they are readily attracted by the nearby Ni catalyst and hydrogenated to water molecules. © 2014 Wiley Periodicals, Inc.     

电化学法制备石墨烯及其复合材料

石墨烯是一种具有优异物理和化学性质的新型二维碳纳米材料,大规模低成本制备高品质石墨烯的方法是其能够得到广泛实际应用的重要前提. 电化学方法可以快捷、绿色无污染、批量制备高质量的石墨烯及其复合材料. 本综述在对石墨烯各种制备方法进行简要比较之后,对近年来石墨烯、石墨烯/无机纳米复合材料、石墨烯/聚合物复合材料以及类石墨烯材料的电化学法制备进展进行介绍并作了展望.     

Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications

Graphene oxide (GO)‐based materials offer great potential for biofunctionalization with applications ranging from biosensing to drug delivery. Such biofunctionalization utilizes specific functional groups, typically a carboxyl moiety, as anchoring points for biomolecule. However, due to the fact that the exact chemical structure of GO is still largely unknown and poorly defined (it was postulated to consist of various oxygen‐containing groups, such as epoxy, hydroxyl, carboxyl, carbonyl, and peroxy in varying ratios), it is challenging to fabricate highly biofunctionalized GO surfaces. The predominant anchoring sites (i.e., carboxyl groups) are mainly present as terminal groups on the edges of GO sheets and thus account for only a fraction of the oxygen‐containing groups on GO. Herein, we suggest a direct solution to the long‐standing problem of limited abundance of carboxyl groups on GO; GO was first reduced to graphene and consequently modified with only carboxyl groups grafted perpendicularly to its surface by a rational synthesis using free‐radical addition of isobutyronitrile with subsequent hydrolysis. Such grafted graphene oxide can contain a high amount of carboxyl groups for consequent biofunctionalization, at which the extent of grafting is limited only by the number of carbon atoms in the graphene plane; in contrast, the abundance of carboxyl groups on “classical” GO is limited by the amount of terminal carbon atoms. Such a graphene platform embedded with perpendicularly grafted carboxyl groups was characterized in detail by X‐ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy, and its application was exemplified with single‐nucleotide polymorphism detection. It was found that the removal of oxygen functionalities after the chemical reduction enhanced the electron‐transfer rate of the graphene. More importantly, the introduction of carboxyl groups promoted a more efficient immobilization of DNA probes on the electrode surface and improved the performance of graphene as a biosensor in comparison to GO. The proposed material can be used as a universal platform for biomolecule immobilization to facilitate rapid and sensitive detection of DNA or proteins for point‐of‐care investigations. Such reactive carboxyl groups grafted perpendicularly on GO holds promise for a highly efficient tailored biofunctionalization for applications in biosensing or drug delivery.     

The Route to Functional Graphene Oxide

We report on an easy‐to‐use, successful, and reproducible route to synthesize functionalized graphite oxide (GO) and its conversion to graphene‐like materials through chemical or thermal reduction of GO. Graphite oxide containing hydroxyl, epoxy, carbonyl, and carboxyl groups loses mainly hydroxyl and epoxy groups during reduction, whereas carboxyl species remain untouched. The interaction of functionalized graphene with fluorescent methylene blue (MB) is investigated and compared to graphite, fully oxidized GO, as well as thermally and chemically reduced GO. Optical absorption and emission spectra of the composites indicate a clear preference for MB interaction with the GO derivatives containing a large number of functional groups (GO and chemically reduced GO), whereas graphite and thermally reduced GO only incorporate a few MB molecules. These findings are consistent with thermogravimetric, X‐ray photoelectron spectroscopic, and Raman data recorded at every stage of preparation. The optical data also indicate concentration‐dependent aggregation of MB on the GO surface leading to stable MB dimers and trimers. The MB dimers are responsible for fluorescence quenching, which can be controlled by varying the pH value.     

Atomic Layer Deposition of Hafnium(IV) Oxide on Graphene Oxide: Probing Interfacial Chemistry and Nucleation by using X‐ray Absorption and Photoelectron Spectroscopies

Interfacing graphene with metal oxides is of considerable technological importance for modulating carrier density through electrostatic gating as well as for the design of earth‐abundant electrocatalysts. Herein, we probe the early stages of the atomic layer deposition (ALD) of HfO₂ on graphene oxide using a combination of C and O K‐edge near‐edge X‐ray absorption fine structure spectroscopies and X‐ray photoelectron spectroscopy. Dosing with water is observed to promote defunctionalization of graphene oxide as a result of the reaction between water and hydroxyl/epoxide species, which yields carbonyl groups that further react with migratory epoxide species to release CO₂. The carboxylates formed by the reaction of carbonyl and epoxide species facilitate binding of Hf precursors to graphene oxide surfaces. The ALD process is accompanied by recovery of the π‐conjugated framework of graphene. The delineation of binding modes provides a means to rationally assemble 2D heterostructures.     

Selective Nitrogen Functionalization of Graphene by Bucherer‐Type Reaction

Nitrogen functionalization of graphene offers new hybrid materials with improved performance for important technological applications. Despite studies highlighting the dependence of the performance of nitrogen‐functionalized graphene on the types of nitrogen functional groups that are present, precise synthetic control over their ratio is challenging. Herein, the synthesis of nitrogen‐functionalized graphene rich in amino groups by a Bucherer‐type reaction under hydrothermal conditions is reported. The efficiency of the synthetic method under two hydrothermal conditions was examined for graphite oxide produced by Hummers and Hofmann oxidation routes. The morphological and structural properties of the amino‐functionalized graphene were fully characterized. The use of a synthetic method with a well‐known mechanism for derivatization of graphene will open new avenues for highly reproducible functionalization of graphene materials.     

Controlled Chemistry Approach to the Oxo‐Functionalization of Graphene

Graphene is the best‐studied 2D material available. However, its production is still challenging and the quality depends on the preparation procedure. Now, more than a decade after the outstanding experiments conducted on graphene, the most successful wet‐chemical approach to graphene and functionalized graphene is based on the oxidation of graphite. Graphene oxide has been known for more than a century; however, the structure bears variable large amounts of lattice defects that render the development of a controlled chemistry impossible. The controlled oxo‐functionalization of graphene avoids the formation of defects within the σ‐framework of carbon atoms, making the synthesis of specific molecular architectures possible. The scope of this review is to introduce the field of oxo‐functionalizing graphene. In particular, the differences between GO and oxo‐functionalized graphene are described in detail. Moreover analytical methods that allow determining lattice defects and functional groups are introduced followed by summarizing the current state of controlled oxo‐functionalization of graphene.     

Covalent 2D Patterning,Local Electronic Structure and Polarization Switching of Graphene at the Nanometer Level

A very facile and efficient protocol for the covalent patterning and properties tuning of graphene is reported. Highly reactive fluorine radicals were added to confined regions of graphene directed by laser writing on graphene coated with 1-fluoro-3,3-dimethylbenziodoxole. This process allows for the realization of exquisite patterns on graphene with resolutions down to 200 nm. The degree of functionalization, ranging from the unfunctionalized graphene to extremely high functionalized graphene, can be precisely tuned by controlling the laser irradiation time. Subsequent substitution of the initially patterned fluorine atoms afforded an unprecedented graphene nanostructure bearing thiophene groups. This substitution led to a complete switch of both the electronic structure and the polarization within the patterned graphene regions. This approach paves the way towards the precise modulation of the structure and properties of nanostructured graphene.     

Two-dimensional nanocomposites based on chemically modified graphene

The multiple functional groups and unique two-dimensional (2D) morphology make chemically modified graphene (CMG) an ideal template for the construction of 2D nanocomposites with various organic/inorganic components. Additionally, the recovered electrical conductivity of CMG may provide a fast-electron-transport channel and can thus promote the application of the resultant nanocomposites in optoelectronic and electrochemical devices. This Concept article summarizes the different strategies for the bottom-up fabrication of CMG-based 2D nanocomposites with small organic molecules, polymers, and inorganic nanoparticles, which represent the new directions in the development of graphene-based materials.     

大尺寸石墨烯量子点组装体的制备及电化学发光性能

对氧化石墨烯纳米材料进行HNO₃氧化处理, 制备了水溶性好且具有强电化学发光(ECL)活性的大尺寸石墨烯量子点组装体(Large-sized graphene quantum dot assemblies, LSGQD-NAs). 利用透射电子显微镜(TEM)、 原子力显微镜(AFM)、 傅里叶变换红外光谱(FTIR)和拉曼光谱(Raman)等方法对其进行了表征, 结果表明, 石墨烯量子点组装体的平均高度为20 nm, 且富含大量的羟基和羧基. 电化学测试结果显示, 在共反应物K₂S₂O₈存在下, LSGQD-NAs在阴极产生很强的ECL(峰值约在685 nm); 并推测了其ECL反应机理, 发现LSGQD-NAs容易通过中心未氧化的石墨烯π-π作用于GC电极表面进行组装修饰. 本研究为基于石墨烯量子点ECL传感器的研究提供了新方法.     

氧化石墨烯和石墨烯在催化领域中的应用研究进展

石墨烯具有独特的二维平面结构,其导电性能好,比表面积大,耐酸碱,耐高温.基于石墨烯的优异特性,本文作者从材料的合成和结构等方面对石墨烯基催化剂的研制及其催化性能进行了评述.介绍了石墨烯催化体系的类型和机理,对石墨烯催化中存在的问题进行了简单分析,并对石墨烯在催化领域的应用前景进行了展望.