Greatly enhanced corrosion/wear resistances of epoxy coating for Mg alloy through a synergistic effect between functionalized graphene and insulated blocking layer

The poor corrosion and wear resistances of Mg alloys seriously limit their potential applications in various industries.The conventional epoxy coating easily forms many intrinsic defects during the solidification process,which cannot provide sufficient protection.In the current study,we design a double-layer epoxy composite coating on Mg alloy with enhanced anti-corrosion/wear properties,via the spin-assisted assembly technique.The outer layer is functionalized graphene(FG)in waterborne epoxy resin(WEP)and the inner layer is Ce-based conversion(Ce)film.The FG sheets can be homogeneously dispersed within the epoxy matrix to fill the intrinsic defects and improve the barrier capability.The Ce film connects the outer layer with the substrate,showing the transition effect.The corrosion rate of Ce/WEP/FG composite coating is 2131 times lower than that of bare Mg alloy,and the wear rate is decreased by~90%.The improved corrosion resistance is attributed to the labyrinth effect(hindering the penetration of corrosive medium)and the obstruction of galvanic coupling behavior.The synergistic effect derived from the FG sheet and blocking layer exhibits great potential in realizing the improvement of multi-functional integration,which will open up a new avenue for the development of novel composite protection coatings of Mg alloys.

β-Cyclodextrin functionalized graphene oxide： an efficient and recyclable adsorbent for the removal of dye pollutants

A novel method for the preparation of β- cyclodextrin grafted graphene oxide （GO-β-CD） has been developed. The GO-β-CD was characterized by Fourier transform infrared spectroscopy, 13C NMR spectroscopy, Raman spectroscopy and thermogravimetric analysis. The ability of GO-β-CD to remove fuchsin acid from solution was also studied. The GO-β-CD had an excellent adsorption capacity for fuchsin acid and could be recycled and reused. The adsorption capacities of GO-β-CD for other dye pollutants such as methyl orange and methylene blue were also investigated. The absorption capacities for the three dyes are in the order： fuchsin acid 〉 methylene blue 〉 methyl orange.

Enhanced dispersibility and thermal stability of β-cyclodextrin functionalized graphene

A series of β-cyclodextrin （CDs） functionalized graphene nanohybrids have been successfully fabricated utilizing the classical covalent modification methods at different reaction temperatures. It is very interesting that although both CDs and graphene oxide （GO） could he easily decomposed, the effective combination of GO with CDs leads to significantly enhanced thermal stability of graphene derivatives （GO-CDs）. Moreover, the introduction of CDs could dramatically improve the dispersibility promotion of our products in both polar/protic and nonpolar/aprotic solvents, which will contribute to the preparation of polymer nanocomposites and increase of their thermal stability. The improved thermal degradation temperatures can be obtained for polyvinyl alcohol after filling with as little as 1 wt.% of the hybrid. The obtained products could be potentially used in heat-retardant or thermal-control materials.

Graphene effectively activating "dead" water molecules between manganese dioxide layers in potassium-ion battery

Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower specific capacity in aqueous electrolytes compared to organic systems and operates through a different reaction mechanism.The application of highly conductive graphene may effectively enhance the capacity of APIBs but could complicate the potassium storage environment.In this study,a MnO_(2) cathode pre-intercalated with K~+ions and grown on graphene(KMO@rGO) was developed using the microwave hydrothermal method for APIBs.KMO@rGO achieved a specific capacity of 90 mA h g^(-1) at a current density of 0.1 A g^(-1),maintaining a capacity retention rate of>90% after 5000 cycles at 5 A g^(-1).In-situ and exsitu characterization techniques revealed the energy-storage mechanism of KMO@rGO:layered MnO_(2)traps a large amount of "dead" water molecules during K~+ions removal.However,the introduction of graphene enables these water molecules to escape during K~+ ions insertion at the cathode.The galvanostatic intermittent titration technique and density functional theory confirmed that KMO@rGO has a higher K~+ions migration rate than MnO_(2).Therefore,the capacity of this cathode depends on the interaction between dead water and K~+ions during the energy-storage reaction.The optimal structural alignment between layered MnO_(2) and graphene allows electrons to easily flow into the external circuit.Rapid charge compensation forces numerous low-solvent K~+ions to displace interlayer dead water,enhancing the capacity.This unique reaction mechanism is unprecedented in other aqueous battery studies.

High-Performance Anion Exchange Membrane Fuel Cells Enabled by Nitrogen Configuration Optimization in Graphene-Coated Nickel for Enhanced Hydrogen Oxidation

Anion exchange membrane fuel cell(AEMFC)technology is attracting intensive attention,due to its great potential by using non-precious-metal catalysts(NPMCs)in the cathode and cheap bipolar plate materials in alkaline media.However,in such case,the kinetics of hydrogen oxidation reaction(HOR)in the anode is two orders of magnitude sluggish than that of acidic electrolytes,which is recognized as the grand challenge in this field.Herein,we report the rationally designed Ni nanoparticles encapsulated by N-doped graphene layers(Ni@NG)using a facile pyrolysis strategy.Based on the density functional theory calculations and electrochemical performance analysis,it is witnessed that the rich Pyridinic-N within the graphene shell optimizes the binding energy of the intermediates,thus enabling the fundamentally enhanced activity for HOR with robust stability.As a proof of concept,the resultant Ni@NG sample as the anode with a low loading(1.8 mg cm^(-2))in AEMFCs delivers a high peak power density of 500 mW cm^(-2),outperforming all of those of NPMC-based analogs ever reported.

Torsional postbuckling characteristics of functionally graded graphene enhanced laminated truncated conical shell with temperature dependent material properties

Buckling and postbuckling characteristics of laminated graphene-enhanced composite(GEC)truncated conical shells exposed to torsion under temperature conditions using finite element method(FEM)simulation are presented in this study.In the thickness direction,the GEC layers of the conical shell are ordered in a piece-wise arrangement of functionally graded(FG)distribution,with each layer containing a variable volume fraction for graphene reinforcement.To calculate the properties of temperaturedependent material of GEC layers,the extended Halpin-Tsai micromechanical framework is used.The FEM model is verified via comparing the current results obtained with the theoretical estimates for homogeneous,laminated cylindrical,and conical shells,the FEM model is validated.The computational results show that a piece-wise FG graphene volume fraction distribution can improve the torque of critical buckling and torsional postbuckling strength.Also,the geometric parameters have a critical impact on the stability of the conical shell.However,a temperature rise can reduce the crucial torsional buckling torque as well as the GEC laminated truncated conical shell’s postbuckling strength.

States of graphene oxide and surface functional groups amid adsorption of dyes and heavy metal ions

Water pollution regarding dyes and heavy metal ions is crucial facing the world.How to effectively separate these contaminants from water has been a key issue.Graphene oxide(GO)promises the greenwater world as a long-lasting spotlight adsorbent material and therefore,harnessing GO has been the research hotspot for over a decade.The state of GO as well as its surface functional groups plays an important role in adsorption.And the way of preparation and structural modification matters to the performance of GO.In this review,the significance of the state of existence of stock GO and surface functional groups is explored in terms of preparation,structural modification,and adsorption.Besides,various adsorbates for GO adsorption are also involved,the discussion of which is rarely established elsewhere.

Non-covalently Functionalized Graphene Oxide-Based Coating to Enhance Thermal Stability and Flame Retardancy of PVA Film

The synergistic effect of conventional flame-retardant elements and graphene has received extensive attention in the development of a new class of flame retardants. Compared to covalent modification, the noncovalent strategy is simpler and expeditious and entirely preserves the original quality of graphene. Thus, non-covalently functionalized graphene oxide(FGO) with a phosphorus–nitrogen compound was successfully prepared via a one-pot process in this study. Polyethyleneimine and FGO were alternatively deposited on the surface of a poly(vinyl alcohol)(PVA) film via layer-by-layer assembly driven by electrostatic interaction, imparting excellent flame retardancy to the coated PVA film. The multilayer FGO-based coating formed a protective shield encapsulating the PVA matrix, effectively blocking the transfer of heat and mass during combustion. The coated PVA has a higher initial decomposition temperature of about 260 °C and a nearly 60% reduction in total heat release than neat PVA does. Our results may have a promising prospect for flame-retardant polymers.

Functionalized graphene oxide-reinforced electrospun carbon nanofibers as ultrathin supercapacitor electrode

Graphene oxide has been used widely as a starting precursor for applications that cater to the needs of tunable graphene. However, the hydrophilic characteristic limits their application, especially in a hydrophobic condition. Herein, a novel non-covalent surface modification approach towards graphene oxide was conducted via a UV-induced photo-polymerization technique that involves two major routes; a UV-sensitive initiator embedded via pi-pi interactions on the graphene planar rings, and the polymerization of hydrophobic polymeric chains along the surface. The functionalized graphene oxide successfully achieved the desired hydrophobicity as it displayed the characteristic of being readily dissolved in organic solvent. Upon its addition into a polymeric solution and subjected to an electrospinning process,non-woven random nanofibers embedded with graphene oxide sheets were obtained. The prepared polymeric nanofibers were subjected to two-step thermal treatments that eventually converted the polymeric chains into a carbon-rich conductive structure. A unique morphology was observed upon the addition of the functionalized graphene oxide, whereby the sheets were embedded and intercalated within the carbon nanofibers and formed a continuous structure. This reinforcement effectively enhanced the electrochemical performance of the carbon nanofibers by recording a specific capacitance of up to 140.10 F/g at the current density of 1 A/g, which was approximately three folds more than that of pristine nanofibers.It also retained the capacitance up to 96.2% after 1000 vigorous charge/discharge cycles. This functionalization technique opens up a new pathway in tuning the solubility nature of graphene oxide towards the synthesis of a graphene oxide-reinforced polymeric structure.

Self-standing rationally functionalized graphene as high-performance electrode materials for supercapacitors

Supercapacitors（SCs） have attracted much attention as one of the alternative energy devices due to their high power performance,long cycle life,and low maintenance cost.Graphene is considered as an innovative and promising material due to its large theoretical specific surface area,high electrical conductivity,good mechanical properties and chemical stability.Herein,we report an effective strategy for elaborately constructing rationally functionalized self-standing graphene（SG） obtained from giant graphene oxide（GGO） paper followed by an ultrarapid thermal-processing.This treatment results in both the exfoliation of graphene sheets and the reduction of GGO by elimination of oxygencontaining groups.The as-prepared SG electrode materials without additive and conducting agent provide an excellent combination of the electrical double layer capacitor（EDLC） and pseudocapacitor（PC） functions and exhibit superior electrochemical performance,including high specific capacitance,good rate capability and excellent cycling stability when investigated in three-electrode electrochemical cells.

Preparation of Functionalized Graphene Nano-platelets and Use for Adsorption of Pb2+ from Solution

Functionalized graphene nano-platelets(FGN) were obtained via treating graphene nanoplatelets(GN) with HNO3, and served as adsorbent for the removal of Pb2+from solutions. We investigated the FGN adsorption capacity for Pb2+at different initial concentrations, varying pH, contact time and temperature. The characterization results of scanning electron microscopy(SEM), thermal analysis(TG/DTG), Fourier transform infrared spectroscopy(FT-IR) and Brunauer-Emmett-Teller(BET) method indicated that FGN layers were thin and possess large specific area with oxygen-containing functional groups grafted onto their surface. Meanwhile, the determined equilibrium adsorption capacity of FGN for Pb2+was 57.765 mg/g and adsorption isotherms well confirmed to Langmuir isotherms models. The results reveals that the FGN has better effect of water treatment.

Functionalized Exfoliated Graphene Oxide as Supercapacitor Electrodes

Functionalized exfoliated graphene oxide (EGO) for supercapacitor electrodes have been synthesized by simple chemical methods from the exfoliated graphite (EG) as precursor. Structural and morphological characterizations of EGO have been carried out using X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), FTIR and Raman spectroscopy. Electrochemical performance of these electrodes has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The fabricated supercapacitor gave a specific capacitance of 146 Fg-1 and energy density of 20 Wh·kg-1 for a highly oxidized sample with more functional groups compared to pure, lower level oxidized and reduced samples. The single and multi layered graphene oxide sheets produced by this method have a lower degree of agglomeration. We found that the graphene oxide with functional oxygen groups of quinine type enhances the capacitance compared to other oxygen functional groups.

Theoretical design and experimental synthesis of counter electrode for dye-sensitized solar cells: Amino-functionalized graphene

For some specific catalytic reaction, how to construct active sites on two dimensional materials is of great scientific significance. Dye-sensitized solar cells（DSCs） can be viewed as one representative photovoltaics because in which liquid electrolyte with triiodide/iodide（I;/I;） as redox couples are involved. In this study, amino-functionalized graphene（AFG） has been designed according to theoretically analyzing iodine reduction reaction（IRR） processes and rationally screening the volcanic plot. Then, such AFG has been successfully synthesized by a simple hydrothermal method and shows high electrocatalytic activity towards IRR when serving as counter electrode in DSCs. Finally, a high conversion efficiency of 7.39% by AFG-based DSCs was obtained, which is close to that using Pt as counter electrode.

Effects of Surface Charges on the Seawater Desalination Using Functionalized Graphene

In this paper, we investigate the selection rule for desalinating seawater using functionalized graphene sheet as a semi-permissible membrane. Both the applied mathematical modeling and MD simulations will be used to determine the acceptance conditions for water molecule or sodium ion permeating into the functionalized graphene. Both the Lennard-Jones potential and Coulomb forces are considered by taking into accounts the major molecular and ionic interactions between molecules, ions and functionalized graphene sheet. The continuous approximation will then be used to coarse grain most significant molecular and ionic interactions so that the multi-body problems could be simplified into several two-body problems and the 3D motions are reduced into degenerated 1D motion. Our mathematical model and simulations show that the negatively charged graphene always accepts sodium ions and water;however the permeability of water molecules and sodium ions becomes very sensitive to the presence of positive charges on the graphene.

Thermal Nonlinearity of Functionalized Graphene Enhanced by Gold Nanorods

The nonlinearity of functionalized and nonfunctionlaized graphene as well as gold nanorods were investigated using the Z-scan system with an Ar＋ laser beam tuned at a wavelength of 514 nm in a CW （continuous wave） regime that was in resonance with AuNRs （gold nanorods）. Z-scan experimental study indicated that functionalized graphene had a negative nonlinear refraction with self-defocusing performance. The result concluded that gold nanorods （average length was 36 ± 3 nm, and the average diameter was 12 ± 2 nm） enhance the thermal nonlinear properties of graphene oxide materials. Gold nanorods were proved to enhance the nonlinear absorption by 50%, and there was a large enhancement on the thermal nonlinear refraction and the thermo-optical coefficient （dn/dT）. It was observed that the AuFG （functionalized graphene film with gold nanorods） presented a large thermal nonlinear refraction. The value of the nonlinear refraction （nl＇） of FG and AuFG samples was shifted from -0.533 x 10.7 cm2/W to -2.92 x 10-7 cm2/W. There was a large enhancement in thermal refraction value that was about five factors larger than the nonlinear refraction of the host material （FG） and much larger （4 orders of magnitude） than that for AuNRs.

Improved nitrogen reduction electroactivity by unique MoS_(2)‐SnS_(2) heterogeneous nanoplates supported on poly(zwitterionic liquids)functionalized polypyrrole/graphene oxide

Unique MoS_(2)‐SnS_(2)heterogeneous nanoplates have successfully in‐situ grown on poly(3‐(1‐vinylimidazolium‐3‐yl)propane‐1‐sulfonate)functionalized polypyrrole/graphene oxide(PVIPS/PPy/GO).PVIPS can attract heptamolybdate ion(Mo7O246−)and Sn^(4+)as the precursors by the ion‐exchange,resulting in the simultaneous growth of 1T’‐MoS2 and the berndtite‐2T‐type hexagonal SnS_(2)by the interfacial induced effect of PVIPS.The obtained MoS_(2)‐SnS_(2)/PVIPS/PPy/GO can serve as electrocatalysts,exhibiting good NRR performance by the synergistic effect.The semi‐conducting SnS_(2)would limit the surface electron accessibility for suppressing HER process of 1T’‐MoS_(2),while metallic 1T’‐MoS_(2)might efficiently improve the NRR electroactivity of SnS_(2)by the creation of Mo‐Sn‐Sn trimer catalytic sites.Otherwise,the irreversible crystal phase transition has taken place during the NRR process.Partial 1T’‐MoS_(2)and SnS_(2)have electrochemically reacted with N_(2),and irreversibly converted into Mo^(2)N and SnxNz due to the formation of Mo−N and Sn−N bonding,meanwhile,partial SnS_(2) has been irreversibly evolved into SnS due to the reduction by the power source in the electrochemical system.It would put forward a new design idea for optimizing the preparation method and electrocatalytic activity of transition metal dichalcogenides.

Interactions of Anionic and Neutral Serine with Pure and Metal-doped Graphene Studied by Density Functional Theory

We present a theoretical study of interactions of anionic and neutral serine （Ser） on pure or metal-doped graphene surfaces using density functional theory calculations. Interactions of both types of Ser with the pure graphene surface show weak non-covalent interactions due to the formation of-COOH…π, -COO^-…π, and -OH…π interactions. On metal- doped graphene, covalent interactions to the surface dominate, due to the formation of strong metal-O and O-metal-O interactions. Furthermore, the doped Fe, Cr, Mn, A1, or Ti enhances the ability of graphene to attract both types of Ser by a combination of the adsorption energy, the density of states, the Mulliken atomic charges, and differences of electron density. At the same time, the interaction strengths of anionic Ser on various graphene surfaces are stronger than those of neutral Ser. These results provide useful insights for the rational design and development of graphene-based sensors for the two forms of Ser by introducing appropriate doped atoms. Ti and Fe are suggested to be the best choices among all doped atoms for the anionic Ser and neutral Ser, respectively.

Reduced graphene oxide-embedded nerve conduits loaded with bone marrow mesenchymal stem cell-derived extracellular vesicles promote peripheral nerve regeneration

We previously combined reduced graphene oxide(rGO)with gelatin-methacryloyl(GelMA)and polycaprolactone(PCL)to create an rGO-GelMA-PCL nerve conduit and found that the conductivity and biocompatibility were improved.However,the rGO-GelMA-PCL nerve conduits differed greatly from autologous nerve transplants in their ability to promote the regeneration of injured peripheral nerves and axonal sprouting.Extracellular vesicles derived from bone marrow mesenchymal stem cells(BMSCs)can be loaded into rGO-GelMA-PCL nerve conduits for repair of rat sciatic nerve injury because they can promote angiogenesis at the injured site.In this study,12 weeks after surgery,sciatic nerve function was measured by electrophysiology and sciatic nerve function index,and myelin sheath and axon regeneration were observed by electron microscopy,immunohistochemistry,and immunofluorescence.The regeneration of microvessel was observed by immunofluorescence.Our results showed that rGO-GelMA-PCL nerve conduits loaded with BMSC-derived extracellular vesicles were superior to rGO-GelMA-PCL conduits alone in their ability to increase the number of newly formed vessels and axonal sprouts at the injury site as well as the recovery of neurological function.These findings indicate that rGO-GelMA-PCL nerve conduits loaded with BMSC-derived extracellular vesicles can promote peripheral nerve regeneration and neurological function recovery,and provide a new direction for the curation of peripheral nerve defect in the clinic.

The Prospective Two-Dimensional Graphene Nanosheets: Preparation, Functionalization, and Applications

Graphene, as an intermediate phase between fullerene and carbon nanotube, has aroused much interests among the scientific community due to its outstanding electronic, mechanical, and thermal properties.With excellent electrical conductivity of 6000 S/cm, which is independent on chirality, graphene is a promising material for high-performance nanoelectronics, transparent conductor, as well as polymer composites. On account of its Young's Modulus of 1 TPa and ultimate strength of 130 GPa, isolated graphene sheet is considered to be among the strongest materials ever measured. Comparable with the single-walled carbon nanotube bundle,graphene has a thermal conductivity of 5000 W/(m·K), which suggests a potential application of graphene in polymer matrix for improving thermal properties of the graphene/polymer composite. Furthermore, graphene exhibits a very high surface area, up to a value of 2630 m^2/g. All of these outstanding properties suggest a wide application for this nanometer-thick, two-dimensional carbon material. This review article presents an overview of the significant advancement in graphene research: preparation, functionalization as well as the properties of graphene will be discussed. In addition, the feasibility and potential applications of graphene in areas, such as sensors, nanoelectronics and nanocomposites materials, will also be reviewed.