Synthesis of mono layer graphene oxide from sonicated graphite flakes and their Hall effect measurements

Graphene, a single atom thick sheet is considered a key candidate for the future nanotechnology, due to its unique extraordinary properties. Researchers are trying to synthesize bulk graphene via chemical route from graphene oxide precursor. In the present work, we investigated a safe and efficient way of monolayer graphene oxide synthesis. To get a high degree of oxidation, we sonicated the graphite flakes before oxidation. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) results confirmed graphene oxide formation and high degree of oxidation. Raman spectroscopy and atomic force microscopy (AFM) results revealed a monolayer of graphene oxide (GO) flakes. The sheet like morphology of the GO flakes was further confirmed by scanning electron microscopy (SEM). The Hall effect measurements were performed on the GO film on a silica substrate to investigate its electrical properties. The results obtained, revealed that the GO film is perfectly insulating, having electrical resistivity up to 8.4 × 10⁸ (Ω·cm) at room temperature.     

3D Graphene Hollow Nanospheres@Palladium‐Networks as an Efficient Electrocatalyst for Formic Acid Oxidation

Graphene has served widely as a support material for noble metal nanoparticle electrocatalysts in fuel cells. During the synthesis of electrocatalysts, however, the intense stacking and folding of graphene nanosheets decreases the utilization and activity of electrocatalysts, owing to the following aspects: i) the noble metal wrapped by the winding graphene cannot be fully utilized; ii) the structural destruction of graphene decreases the specific surface area and increases electrical resistance; and iii) the hydrophobicity and wrinkles of graphene greatly increase the mass transfer resistance of fuel molecules and electrolytes. In this work, 3D graphene oxide hollow nanospheres are designed to minimize wrinkles, maximize specific surface area, and realize the regular clipping of 2D graphene oxide. The 3D‐reduced graphene oxide hollow nanosphere supported Pd‐network nanohybrids (3D‐RGO/Pd‐NWs) are then obtained using 3D graphene oxide hollow nanospheres as a reaction precursor. The skeleton of 3D‐RGO not only acts as an exclusive inner conducting shell to promote electron and ion kinetics but is also crucial for enhancing the permeation of fuel molecules and electrolytes. Therefore, 3D‐RGO/Pd‐NWs exhibit enhanced electrocatalytic activity and durability for the formic oxidation reaction in an acidic medium compared to 2D graphene supported Pd nanoparticles and commercial Pd/C electrocatalysts.     

Self‐Assembly of Thiourea‐Crosslinked Graphene Oxide Framework Membranes toward Separation of Small Molecules

The poor mechanical strength of graphene oxide (GO) membranes, caused by the weak interlamellar interactions, poses a critical challenge for any practical application. In addition, intrinsic but large‐sized 2D channels of stacked GO membranes lead to low selectivity for small molecules. To address the mechanical strength and 2D channel size control, thiourea covalent‐linked graphene oxide framework (TU‐GOF) membranes on porous ceramics are developed through a facile hydrothermal self‐assembly synthesis. With this strategy, thiourea‐bridged GO laminates periodically through the dehydration condensation reactions via ? NH₂ and/or ? SH with ? O?C? OH as well as the nucleophilic addition reactions of ? NH₂ to C? O? C, leading to narrowed and structurally well‐defined 2D channels due to the small dimension of the covalent TU‐link and the deoxygenated processes. The resultant TU‐GOF/ceramic composite membranes feature excellent sieving capabilities for small species, leading to high hydrogen permselectivities and nearly complete rejections for methanol and small ions in gas, solvent, and saline water separations. Moreover, the covalent bonding formed at the GO/support and GO/GO interfaces endows the composite membrane with significantly enhanced stability.     

Electric Power Generation through the Direct Interaction of Pristine Graphene‐Oxide with Water Molecules

Converting ubiquitous environmental energy into electric power holds tremendous social and financial interests. Traditional energy harvesters and converters are limited by the specific materials and complex configuration of devices. Herein, it is presented that electric power can be directly produced from pristine graphene oxide (GO) without any pretreatment or additives once encountering the water vapor, which will generate an open‐circuit‐voltage of up to 0.4–0.7 V and a short‐circuit‐current‐density of 2–25 µA cm^?2 on a single piece of GO film. This phenomenon results from the directional movement of charged hydrogen ions through the GO film. The present work demonstrates and provides an extremely simple method for electric energy generation, which offers more applications of graphene‐based materials in green energy converting field.     

Controllable Bipolar Doping of Graphene with 2D Molecular Dopants

The fine control of graphene doping levels over a wide energy range remains a challenging issue for the electronic applications of graphene. Here, the controllable doping of chemical vapor deposited graphene, which provides a wide range of energy levels (shifts up to ± 0.5 eV), is demonstrated through physical contact with chemically versatile graphene oxide (GO) sheets, a 2D dopant that can be solution‐processed. GO sheets are a p‐type dopant due to their abundance of electron‐withdrawing functional groups. To expand the energy window of GO‐doped graphene, the GO surface is chemically modified with electron‐donating ethylene diamine molecules. The amine‐functionalized GO sheets exhibit strong n‐type doping behaviors. In addition, the particular physicochemical characteristics of the GO sheets, namely their sheet sizes, number of layers, and degree of oxidation and amine functionality, are systematically varied to finely tune their energy levels. Finally, the tailor‐made GO sheet dopants are applied into graphene‐based electronic devices, which are found to exhibit improved device performances. These results demonstrate the potential of GO sheet dopants in many graphene‐based electronics applications.     

Nanomanufacturing of RGO‐CNT Hybrid Film for Flexible Aqueous Al‐Ion Batteries

A highly electrically conductive film‐type current collector is an essential part of batteries. Apart from the metal‐based current collectors, lightweight and highly conductive carbon materials such as reduced graphene oxide (RGO) and carbon nanotubes (CNTs) show great potential as current collectors. However, traditional RGO manufacturing usually requires a long time and high energy, which decreases the product yielding rate and manufacturing efficiency. Moreover, the performance of the manufactured RGO needs to be further improved. In this work, CNT and GO are evenly mixed into GO‐CNT, which can be directly reduced into RGO‐CNT by Joule heating at 2936 K within less than 1 min. The fabricated RGO‐CNT achieves a high electrical conductivity of 2750 S cm^?1, and realizes a 10⁶‐fold increase. The assembled flexible aqueous Al‐ion battery with RGO‐CNT as the current collector exhibits impressive electrochemical performance in terms of superior cycling stability and exceptional rate capability, and excellent mechanical ability regarding the tolerance to mechanical damage such as bending, folding, piercing, and cutting without detrimental consequences.     

Graphene Oxide as an Optical Biosensing Platform

Since graphene exhibits innovative mechanical, electrical, thermal, and optical properties, this 2D material is increasingly attracting attention and is under active research. Among the various graphene forms with lattice‐like nanostructure, graphene oxide (GO) displays advantageous characteristics as a biosensing platform due to its excellent capabilities for direct wiring with biomolecules, a heterogeneous chemical and electronic structure, the possibility to be processed in solution and the ability to be tuned as insulator, semiconductor or semi‐metal. Moreover, GO photoluminescences with energy transfer donor/acceptor molecules exposed in a planar surface and is even proposed as a universal highly efficient long‐range quencher, which is opening the way to several unprecedented biosensing strategies. Here, the rationale behind the use of GO in optical biosensing applications is discussed by describing different potentially exploitable properties of GO, and an overview of the current approaches are presented along with future perspectives and challenges.     

Graphene–Graphene Oxide Floating Gate Transistor Memory

A novel transparent, flexible, graphene channel floating‐gate transistor memory (FGTM) device is fabricated using a graphene oxide (GO) charge trapping layer on a plastic substrate. The GO layer, which bears ammonium groups (NH₃⁺), is prepared at the interface between the crosslinked PVP (cPVP) tunneling dielectric and the Al₂O₃ blocking dielectric layers. Important design rules are proposed for a high‐performance graphene memory device: i) precise doping of the graphene channel, and ii) chemical functionalization of the GO charge trapping layer. How to control memory characteristics by graphene doping is systematically explained, and the optimal conditions for the best performance of the memory devices are found. Note that precise control over the doping of the graphene channel maximizes the conductance difference at a zero gate voltage, which reduces the device power consumption. The proposed optimization via graphene doping can be applied to any graphene channel transistor‐type memory device. Additionally, the positively charged GO (GO–NH₃⁺) interacts electrostatically with hydroxyl groups of both UV‐treated Al₂O₃ and PVP layers, which enhances the interfacial adhesion, and thus the mechanical stability of the device during bending. The resulting graphene–graphene oxide FGTMs exhibit excellent memory characteristics, including a large memory window (11.7 V), fast switching speed (1 μs), cyclic endurance (200 cycles), stable retention (10⁵ s), and good mechanical stability (1000 cycles).     

三维多孔结构聚苯胺/石墨烯复合材料的制备及电化学性能

以自制聚苯胺水凝胶和氧化石墨烯为原料采用原位聚合法和溶液灌注法制备三维多孔结构的聚苯胺/氧化石墨烯复合材料,然后在氢碘酸的还原下制备聚苯胺/石墨烯复合材料。采用红外光谱法、场发射扫描电子显微镜和热重分析法对制备的复合材料的结构、形貌和组成进行表征,并采用三电极测试方式对其电化学性能进行测试。结果表明,氧化石墨烯的掺入能有效防止聚苯胺和氧化石墨烯的团聚和堆叠问题,获得了具有良好三维多孔结构的聚苯胺/氧化石墨烯复合物;聚苯胺/氧化石墨烯复合材料被氢碘酸还原后,得到的聚苯胺/石墨烯复合材料的热稳定性有所降低,但其比电容和导电性等有了很大的提高,在电流密度为0.5 A/g时,PANI/GO和PANI/r GO的比电容分别为240.38 F/g和321.91F/g。     

Silver Nanoflower Decorated Graphene Oxide Sponges for Highly Sensitive Variable Stiffness Stress Sensors

Soft conductive materials should enable large deformation while keeping high electrical conductivity and elasticity. The graphene oxide (GO)‐based sponge is a potential candidate to endow large deformation. However, it typically exhibits low conductivity and elasticity. Here, the highly conductive and elastic sponge composed of GO, flower‐shaped silver nanoparticles (AgNFs), and polyimide (GO‐AgNF‐PI sponge) are demonstrated. The average pore size and porosity are 114 µm and 94.7%, respectively. Ag NFs have thin petals (8–20 nm) protruding out of the surface of a spherical bud (300–350 nm) significantly enhancing the specific surface area (2.83 m² g^?1). The electrical conductivity (0.306 S m^?1 at 0% strain) of the GO‐AgNF‐PI sponge is increased by more than an order of magnitude with the addition of Ag NFs. A nearly perfect elasticity is obtained over a wide compressive strain range (0–90%). The strain‐dependent, nonlinear variation of Young's modulus of the sponge provides a unique opportunity as a variable stiffness stress sensor that operates over a wide stress range (0–10 kPa) with a high maximum sensitivity (0.572 kPa^?1). It allows grasping of a soft rose and a hard bottle, with the minimal object deformation, when attached on the finger of a robot gripper.     

A Force‐Engineered Lint Roller for Superclean Graphene

Contamination is a major concern in surface and interface technologies. Given that graphene is a 2D monolayer material with an extremely large surface area, surface contamination may seriously degrade its intrinsic properties and strongly hinder its applicability in surface and interfacial regions. However, large‐scale and facile treatment methods for producing clean graphene films that preserve its excellent properties have not yet been achieved. Herein, an efficient postgrowth treatment method for selectively removing surface contamination to achieve a large‐area superclean graphene surface is reported. The as‐obtained superclean graphene, with surface cleanness exceeding 99%, can be transferred to dielectric substrates with significantly reduced polymer residues, yielding ultrahigh carrier mobility of 500 000 cm² V^?1 s^?1 and low contact resistance of 118 Ω µm. The successful removal of contamination is enabled by the strong adhesive force of the activated‐carbon‐based lint roller on graphene contaminants.     

Photocatalytic Reduction of Graphene Oxide–TiO2 Nanocomposites for Improving Resistive‐Switching Memory Behaviors

Graphene oxide (GO)‐based resistive‐switching (RS) memories offer the promise of low‐temperature solution‐processability and high mechanical flexibility, making them ideally suited for future flexible electronic devices. The RS of GO can be recognized as electric‐field‐induced connection/disconnection of nanoscale reduced graphene oxide (RGO) conducting filaments (CFs). Instead of operating an electrical FORMING process, which generally results in high randomness of RGO CFs due to current overshoot, a TiO₂‐assisted photocatalytic reduction method is used to generate RGO‐domains locally through controlling the UV irradiation time and TiO₂ concentration. The elimination of the FORMING process successfully suppresses the RGO overgrowth and improved RS memory characteristics are achieved in graphene oxide–TiO₂ (Go‐TiO₂) nanocomposites, including reduced SET voltage, improved switching variability, and increased switching speed. Furthermore, the room‐temperature process of this method is compatible with flexible plastic substrates and the memory cells exhibit excellent flexibility. Experimental results evidence that the combined advantages of reducing the oxygen‐migration barrier and enhancing the local‐electric‐field with RGO‐manipulation are responsible for the improved RS behaviors. These results offer valuable insight into the role of RGO‐domains in GO memory devices, and also, this mild photoreduction method can be extended to the development of carbon‐based flexible electronics.     

Surface Energy Engineering in the Solvothermal Deoxidation of Graphene Oxide

A route to achieving high yields of monodisperse, deeply deoxidized graphene oxide (GO) in solution is presented. It overcomes many of the problems of dispersibility and inefficient reduction of GO in solvothermal deoxidation that are usually observed, despite the previous use of strong reducing agents (e.g. Fe²⁺, S or hydrazine). It is shown that the incomplete deoxidation is most likely due to agglomeration/self‐assembly of partially reduced GO, which also creates poor dispersibility. GO deoxidation is found to be highly sensitive to the solvent surface energy and, through experiments and empirical calculations, tuning the solvent surface energy to around 85.6 mJ/m² (at 100 °C) leads to fully deoxidized GO. These calculations also allow appropriate solvent surface energies to be calculated for other temperatures for deep deoxidation of GO. This approach makes solvothermal deoxidation of GO a potential route to large scale, economic production of highly disperse monolayered graphene.     

Chemical Preparation of Graphene‐Based Nanomaterials and Their Applications in Chemical and Biological Sensors

Graphene is a flat monolayer of carbon atoms packed tightly into a 2D honeycomb lattice that shows many intriguing properties meeting the key requirements for the implementation of highly excellent sensors, and all kinds of proof‐of‐concept sensors have been devised. To realize the potential sensor applications, the key is to synthesize graphene in a controlled way to achieve enhanced solution‐processing capabilities, and at the same time to maintain or even improve the intrinsic properties of graphene. Several production techniques for graphene‐based nanomaterials have been developed, ranging from the mechanical cleavage and chemical exfoliation of high‐quality graphene to direct growth onto different substrates and the chemical routes using graphite oxide as a precusor to the newly developed bottom‐up approach at the molecular level. The current review critically explores the recent progress on the chemical preparation of graphene‐based nanomaterials and their applications in sensors.     

Synthetic Multifunctional Graphene Composites with Reshaping and Self‐Healing Features via a Facile Biomineralization‐Inspired Process

Since graphene is a type of 2D carbon material with excellent mechanical, electrical, thermal, and optical properties, the efficient preparation of graphene macroscopic assemblies is significant in the potentially large‐scale application of graphene sheets. Conventional preparation methods of graphene macroscopic assemblies need strict conditions, and, once formed, the assemblies cannot be edited, reshaped, or recycled. Herein, inspired by the biomineralization process, a feasible approach of shapeable, multimanipulatable, and recyclable gel‐like composite consisting of graphene oxide/poly(acrylic acid)/amorphous calcium carbonate (GO‐PAA‐ACC) is designed. This GO‐PAA‐ACC material can be facilely synthesized at room temperature with a cross‐linking network structure formed during the preparation process. Remarkably, it is stretchable, malleable, self‐healable, and easy to process in the wet state, but tough and rigid in the dried state. In addition, these two states can be readily switched by adjusting the water content, which shows recyclability and can be used for 3D printing to form varied architectures. Furthermore, GO‐PAA‐ACC can be functionalized or processed to meet a variety of specific application requirements (e.g., energy‐storage, actuators). The preparation method of GO‐PAA‐ACC composite in this work also provides a novel strategy for the versatile macroscopic assembly of other materials, which is low‐cost, efficient, and convenient for broad application.     

Design of 3D Graphene‐Oxide Spheres and Their Derived Hierarchical Porous Structures for High Performance Supercapacitors

Graphene‐oxide (GO) based porous structures are highly desirable for supercapacitors, as the charge storage and transfer can be enhanced by advancement in the synthesis. An effective route is presented of, first, synthesis of three‐dimensional (3D) assembly of GO sheets in a spherical architecture (GOS) by flash‐freezing of GO dispersion, and then development of hierarchical porous graphene (HPG) networks by facile thermal‐shock reduction of GOS. This leads to a superior gravimetric specific capacitance of ≈306 F g⁻¹ at 1.0 A g⁻¹, with a capacitance retention of 93% after 10 000 cycles. The values represent a significant capacitance enhancement by 30–50% compared with the GO powder equivalent, and are among the highest reported for GO‐based structures from different chemical reduction routes. Furthermore, a solid‐state flexible supercapacitor is fabricated by constructing the HPG with polymer gel electrolyte, exhibiting an excellent areal specific capacitance of ≈220 mF cm⁻² at 1.0 mA cm⁻² with exceptional cyclic stability. The work reveals a facile but efficient synthesis approach of GO‐based materials to enhance the capacitive energy storage.     

An Increase in Membrane Cholesterol by Graphene Oxide Disrupts Calcium Homeostasis in Primary Astrocytes

The use of graphene nanomaterials (GNMs) for biomedical applications targeted to the central nervous system is exponentially increasing, although precise information on their effects on brain cells is lacking. In this work, the molecular changes induced in cortical astrocytes by few‐layer graphene (FLG) and graphene oxide (GO) flakes are addressed. The results show that exposure to FLG/GO does not affect cell viability or proliferation. However, proteomic and lipidomic analyses unveil alterations in several cellular processes, including intracellular Ca²⁺ ([Ca²⁺]_i) homeostasis and cholesterol metabolism, which are particularly intense in cells exposed to GO. Indeed, GO exposure impairs spontaneous and evoked astrocyte [Ca²⁺]_i signals and induces a marked increase in membrane cholesterol levels. Importantly, cholesterol depletion fully rescues [Ca²⁺]_i dynamics in GO‐treated cells, indicating a causal relationship between these GO‐mediated effects. The results indicate that exposure to GNMs alters intracellular signaling in astrocytes and may impact astrocyte–neuron interactions.     

Sulfur and Nitrogen Co‐Doped Graphene for Metal‐Free Catalytic Oxidation Reactions

Sulfur and nitrogen co‐doped reduced graphene oxide (rGO) is synthesized by a facile method and demonstrated remarkably enhanced activities in metal‐free activation of peroxymonosulfate (PMS) for catalytic oxidation of phenol. Based on first‐order kinetic model, S–N co‐doped rGO (SNG) presents an apparent reaction rate constant of 0.043 ± 0.002 min^?1, which is 86.6, 22.8, 19.7, and 4.5‐fold as high as that over graphene oxide (GO), rGO, S‐doped rGO (S‐rGO), and N‐doped rGO (N‐rGO), respectively. A variety of characterization techniques and density functional theory calculations are employed to investigate the synergistic effect of sulfur and nitrogen co‐doping. Co‐doping of rGO at an optimal sulfur loading can effectively break the inertness of carbon systems, activate the sp²‐hybridized carbon lattice and facilitate the electron transfer from covalent graphene sheets for PMS activation. Moreover, both electron paramagnetic resonance (EPR) spectroscopy and classical quenching tests are employed to investigate the generation and evolution of reactive radicals on the SNG sample for phenol catalytic oxidation. This study presents a novel metal‐free catalyst for green remediation of organic pollutants in water.     

From Graphite to Graphene Oxide and Graphene Oxide Quantum Dots

Many methods have been reported for synthesizing graphene oxide (GO) and graphene oxide quantum dots (GOQDs) where a tedious operational procedure and long reaction time are generally required. Herein, a facile one‐pot solvothermal method that allows selective synthesis of pure GO and pure GOQDs, respectively is demonstrated. What is more, the final product of either GO or differently sized GOQDs can be easily controlled by adjusting the reaction temperatures or reactant ratios, which is also feasible when enlarged to gram scale. The 2.5 nm GOQDs show excellent photoluminescence that can be utilized for bioimaging or distinctive detection of Eu³⁺ and Tb³⁺ from their respective mixtures with other rare earth and/or transition metal ions, at sub‐ppm level.     

Spectroscopic studies of large sheets of graphene oxide and reduced graphene oxide monolayers prepared by Langmuir-Blodgett technique

Graphene oxide (GO) sheets prepared by chemical exfoliation were spread at the air-water interface and transferred to silicon substrates by Langmuir-Blodgett technique as closely spaced monolayers of 20-40 μm size. Hydrazine exposure followed by annealing in vacuum and argon ambient results in the formation of reduced graphene oxide (RGO) monolayers, without significantly affecting the overall morphology of the sheets. The monolayer character of both GO and RGO sheets was ascertained by atomic force microscopy. X-ray photoelectron spectroscopy supported by Fourier transform infrared spectroscopy revealed that the reduction process results in a significant decrease in oxygen functionalities, accompanied by a substantial decrease in the ratio of non-graphitic to graphitic (sp² bonded) carbon in the monolayers from 1.2 to 0.35. Raman spectra of GO and RGO monolayers have shown that during the reduction process, the G-band shifts by 8-12 cm^− 1 and the ratio of the intensities of D-band to G-band, I(D)/I(G) decreases from 1.3 ± 0.3 to 0.8 ± 0.2, which is in tune with the smaller non-graphitic carbon content of RGO monolayers. The significant decrease in I(D)/I(G) has been explained by assuming that substantial order is present in precursor GO monolayers as well as RGO monolayers obtained by solid state reduction.