Synthesis and electrochemical properties of three-dimensional graphene/polyaniline composites for supercapacitor electrode materials

To improve the specific capacitance and rate capability of electrode material for supercapacitors, a three-dimensional graphene/polyaniline （3DGN/PANI） composite is prepared via in situ polymerization on GN hydrogel. PANI grows on the GN surface as a thin film, and its content in the composite is controlled by the concentration of the reaction monomer. The specific capacitance of the 3DGN/PANI composite containing 10 wt% PANI reaches 322.8 F.g-1 at a current density of 1 A.g-1, nearly twice as large as that of the pure 3DGN （162.8 F.g-1）. The capacitance of the composite is 307.9 F.g-1 at 30 A.g-1 （maintaining 95.4%）, and 89% retention after 500 cycles. This study demonstrates the exciting potential of 3DGN/PANI with high capacitance, excellent rate capability and long cycling life for supercapacitors.

A flexible solid-state supercapacitor based on graphene/polyaniline paper electrodes

The direct coating of graphene sheets obtained by electrochemical exfoliation on commercial paper renders the preparation of highly conductive flexible paper substrate for subsequent deposition of polyaniline (PANi) nanorods via electrochemical polymerization. The deposit ion of PANi can be well-controlled by adjusting the electrochemical polymerization time, leading to the formation of PANi coated graphene paper (PANi-GP). The as-prepared electrode exhibited high areal capacitance of 176 mF cm^-2 in three-electrode system at a current density of 0.2 mA cm^-2 which is around 10 times larger than that of pris-tine graphene paper due to the pseudocapacitive behavior of PANi. In-situ Raman test was used to determine the molecular changes during redox process of PANi. More importantly, all-solid-state symmetric capacitor assembled with two PANi-GP electrodes in a polymer electrolyte delivered an areal capacitanee of 123 mF cm^-2, corresponding to an areal energy density of 17.1 μWh cm^-2 and an areal power density of 0.25 mW cm^-2. The symmetric capacitor held a capacitive retention of 74.8% after 500 bending tests from 0 to 120°, suggesting the good flexibility and mechanical stability. These results showed the great promising application in flexible energy-storage devices.

Photoelectrocatalytic oxidation of methane into methanol and formic acid over ZnO/graphene/polyaniline catalyst

ZnO/graphene/polyaniline(PANI) composite is synthesized and used for photoelectrocatalytic oxidation of methane under simulated sun light illumination with ambient conditions. The photoelectrochemical(PEC) performance of pure ZnO, ZnO/graphene, ZnO/PANI, and ZnO/graphene/PANI photoanodes is investigated by cyclic voltammetry(CV),chronoamerometry(J–t) and electrochemical impedance spectroscopy(EIS). The yields of methane oxidation products,mainly methanol(CH_3OH) and formic acid(HCOOH), catalysed by the synthesized ZnO/graphene/PANI composite are 2.76 and 3.20 times those of pure ZnO, respectively. The mechanism of the photoelectrocatalytic process converting methane into methanol and formic acid is proposed on the basis of the experimental results. The enhanced photoelectrocatalytic activity of the ZnO/graphene/PANI composite can be attributed to the fact that graphene can efficiently transfer photo-generated electrons from the inner region to the surface reaction to form free radicals due to its superior electrical conductivity as an inter-media layer. Meanwhile, the introduction of PANI promotes solar energy harvesting by extending the visible light absorption and enhances charge separation efficiency due to its conducting polymer characteristics.In addition, the PANI can create a favorable π-conjunction structure together with graphene layers, which can achieve a more effective charge separation. This research demonstrates that the fabricated ZnO/graphene/PANI composite promises to implement the visible-light photoelectrocatalytic methane oxidation.

Synthesis and Characterisations of TiO₂Coated Multiwalled Carbon Nanotubes/Graphene/Polyaniline Nanocomposite for Supercapacitor Applications

Nowadays with ever increasing demand of energy, developing of alternative power sources is an important issue all over the world. In this respect we have prepared nanocomposites based on metal oxide (titanium oxide) coated multiwalled carbon nanotubes (MWCNTs)/polyaniline (PANI) with graphene and without graphene and studied their electrochemical performance. The formation of the polymer in the nanocomposites was confirmed by the Fourier Transform Infrared Spectroscopy (FTIR) study. The morphological characterisations were carried out by the Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). To characterize the prepared nanocomposites electrode, a cyclic voltammetry test for measuring specific capacitance, and an impedance test were conducted. The highest value of specific capacitance obtained for the TiO2 coated MWCNTs/PANI nanocomposite was 443.57 F/g at 2 mV/s scan rate. Upon addition of graphene nanosheet to the TiO2 coated MWCNTs in a weight ratio of (9:1) the specific capacitance value increased to 666.3 F/g at the same scan rate, also resulting in an increase in energy density and power density.

Three-dimensional Porous Graphene/Polyaniline Hybrids for High Performance Supercapacitor Electrodes

Graphene-based composites took extensive attraction as electrodes for supercacitors these years.Three-dimensional cross-linking porous graphene(3D rGO-m)was obtained by KOH activation to graphene modified by 1,2,4-triaminobenzene.3D porous graphene/polyaniline hybrids(3D rGO-m/PANI)was prepared by the in-situ chemical oxidative polymerization.The rGO-m are reconstructed from 2D to 3D porous structure after KOH activation.The PANI nanorod arrays are successfully decorated on the surface of the 3D porous graphene sheets.The specific capacitance of the 3D rGO-m/PANI hybrids reach 985 F/g at 0.5 A/g.The capacitance retention of 3D rGO-m/PANI maintains 90%of its initial capacity after 1000 cycles,while rGO-m/PANI only keeps 83%of its initial capacity,the cycling stability of both hybrids are higher than that of pure PANI(69%).

Graphene/polyaniline composite sponge of three-dimensional porous network structure as supercapacitor electrode

As a supercapacitor electrode, the graphene/polyaniline （PANI） composite sponge with a three-dimensional （3D） porous network structure is synthesized by a simple three-step method. The three steps include an in situ polymerization, freeze-drying and reduction by hydrazine vapor. The prepared sponge has a large specific surface area and porous network structure, so it is in favor of spreading the electrolyte ion and increasing the charge transfer efficiency of the system. The process of preparation is simple, easy to operate and low cost. The composite sponge shows better electrochemical performance than the pure individual graphene sponge while PANI cannot keep the shape of a sponge. Such a composite sponge exhibits specific capacitances of 487 F.g-1 at 2 mV/s compared to pristine PANI of 397 F.g-1.

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.

N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

Radiative Blood-Based Hybrid Copper-Graphene Nanoliquid Flows along a Source-Heated Leaning Cylinder

Variant graphene,graphene oxides(GO),and graphene nanoplatelets(GNP)dispersed in blood-based copper(Cu)nanoliquids over a leaning permeable cylinder are the focus of this study.These forms of graphene are highly beneficial in the biological and medical fields for cancer therapy,anti-infection measures,and drug delivery.The non-Newtonian Sutterby(blood-based)hybrid nanoliquid flows are generalized within the context of the Tiwari-Das model to simulate the effects of radiation and heating sources.The governing partial differential equations are reformulated into a nonlinear set of ordinary differential equations using similar transformational expressions.These equations are then transformed into boundary value problems through a shooting technique,followed by the implementation of the bvp4c tool in MATLAB.The influences of various parameters on the model’s nondimensional velocity and temperature profiles,reduced skin friction,and reduced Nusselt number are presented for detailed discussions.The results indicated that Cu-GNP/blood and Cu-GO/blood hybrid nanofluids exhibit the lowest and highest velocity distributions,respectively,for increased nanoparticles volume fraction,curvature parameter,Sutterby fluid parameter,Hartmann number,and wall permeability parameter.Conversely,opposite trends are observed for the temperature distribution for all considered parameters,except the mixed convection parameter.Increases in the reduced skin friction magnitude and the reduced Nusselt number with higher values of graphene/GO/GNP nanoparticle volume fraction are also reported.Finally,GNP is identified as the superior heat conductor,with an average increase of approximately 5%and a peak of 7.8%in the reduced Nusselt number compared to graphene and GO nanoparticles in the Cu/blood nanofluids.

Aggregation-regulated bioreduction process of graphene oxide by Shewanella bacteria

The bioreduction of graphene oxide(GO)using environmentally functional bacteria such as Shewanella represents a green approach to produce reduced graphene oxide(rGO).This process differs from the chemical reduction that involves instantaneous molecular reactions.In bioreduction,the contact of bacterial cells and GO is considered the rate-limiting step.To reveal how the bacteria-GO integration regulates rGO production,the comparative experiments of GO and three Shewanella strains were carried out.Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,Raman spectroscopy,and atomic force microscopy were used to characterize the reduction degree and the aggregation degree.The results showed that a spontaneous aggregation of GO and Shewanella into the condensed entity occurred within 36 h.A positive linear correlation was established,linking three indexes of the aggregation potential,the bacterial reduction ability,and the reduction degree(ID/IG)comprehensively.

Valley-dependent transport in a mescoscopic twisted bilayer graphene device

We study the valley-dependent electron transport in a four-terminal mesoscopic device of the two monolayer graphene nanoribbons vertically stacked together, where the intersection forms a bilayer graphene lattice with a controllable twist angle. Using a tight-binding lattice model, we show that the longitudinal and transverse conductances exhibit significant valley polarization in the low energy regime for small twist angles. As the twist angle increases, the valley polarization shifts to the high energy regime. This arises from the regrouping effect of the electron band in the twisted bilayer graphene region. But for relatively large twist angles, no significant valley polarization is observed. These results are consistent with the spectral densities of the twisted bilayer graphene.

对二维Graphene/VS_(2)/BN范德华多层异质结构作为LIBs的阳极材料的相关研究

通过范德华尔斯作用将单层石墨烯(Graphene)、单层二硫化钒(VS2)和单层氮化硼(BN)构建成Graphene/VS2/BN范德华三层异质结构,并将其与不同数量的锂结合,研究了其作为锂离子电池(Li-Ion Batterys,LIBs)中阳极电极材料的可行性.Graphene/VS_(2)/BN范德华三层异质结构具有-0.33 e V/A2的形成能,具有较强的稳定性,理论上可实现合成.同时,计算了Graphene/VS_(2)/BN范德华异质结构的平面内刚度,得出的杨氏模量(Y)为886.88 N/m,高于单层VS_(2)的Y(82.5 N/m),具有较好的力学性能.Graphene/VS_(2)/BN范德华三层异质结构表面和界面上吸附Li的吸附能(-5~-2 e V)远大于相应单层的吸附能,表明其对Li具有较好的吸附性能.Li在Graphene/VS_(2)/BN范德华三层异质结构的不同表面和界面处迁移时的扩散势垒非常小(0.3~0.6 e V),对电池速率性能极为有利.Graphene/VS_(2)/BN范德华三层异质结构在LIBs的阳极电极材料方面的应用具有广泛的前景.

La内嵌graphene/MoS_(2)层的储氢性能研究

运用密度泛函理论研究了La内嵌graphene/MoS_(2)层的储氢性能.由于La的内嵌graphene/MoS_(2)异质结的层间距被拉大.详细研究了氢气分子在La内嵌的graphene/MoS_(2)结构上的吸附行为.结果表明,一个La原子最多可以吸附六个氢气分子,采用GGA/PBE泛函计算得到氢气分子的平均吸附能为0.198 eV.合适的吸附能使得设计材料能够在温和条件下实现可逆存储.重要的是,La原子能够分散地内嵌在graphene/MoS_(2)异质结中,这将为氢气分子提供更多吸附位.研究表明理论上预测La内嵌graphene/MoS_(2)材料是一种潜在的储氢材料.

Valley filtering and valley-polarized collective modes in bulk graphene monolayers

The presence of two sublattices in hexagonal graphene brings two energetically degenerate extremes in the conduction and valence bands, which are identified by the valley quantum number. Recently, this valley degree of freedom has been suggested to encode and process information, which develops a new carbon-based electronics named graphene valleytronics. In this topical review, we present and discuss valley-related transport properties in bulk graphene monolayers,which are due to strain-induced pseudomagnetic fields and associated vector potential, sublattice-stagger potential, and the valley-Zeeman effect. These valley-related interactions can be utilized to obtain valley filtering, valley spatial separation, valley-resolved guiding modes, and valley-polarized collective modes such as edge or surface plasmons. The present challenges and the perspectives on graphene valleytronics are also provided in this review.

Carbon nanocages bridged with graphene enable fast kinetics for dual-carbon lithium-ion capacitors

Lithium-ion capacitors(LICs) combining the advantages of lithium-ion batteries and supercapacitors are considered a promising nextgeneration energy storage device. However, the sluggish kinetics of battery-type anode cannot match the capacitor-type cathode, restricting the development of LICs. Herein, hierarchical carbon framework(HCF) anode material composed of 0D carbon nanocage bridged with 2D graphene network are developed via a template-confined synthesis process. The HCF with nanocage structure reduces the Li^(+) transport path and benefits the rapid Li^(+) migration, while 2D graphene network can promote the electron interconnecting of carbon nanocages. In addition, the doped N atoms in HCF facilitate to the adsorption of ions and enhance the pseudo contribution, thus accelerate the kinetics of the anode. The HCF anode delivers high specific capacity, remarkable rate capability. The LIC pouch-cell based on HCF anode and active HCF(a-HCF) cathode can provide a high energy density of 162 Wh kg^(-1) and a superior power density of 15.8 kW kg^(-1), as well as a long cycling life exceeding 15,000cycles. This study demonstrates that the well-defined design of hierarchical carbon framework by incorporating 0D carbon nanocages and 2D graphene network is an effective strategy to promote LIC anode kinetics and hence boost the LIC electrochemical performance.

Pillar effect induced by ultrahigh phosphorous/nitrogen doping enables graphene/MXene film with excellent cycling stability for alkali metal ion storage

Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.

Surface Morphology and Thermo-Electrical Energy Analysis of Polyaniline (PANI) Incorporated Cotton Fabric

With the exponential development in wearable electronics,a significant paradigm shift is observed from rigid electronics to flexible wearable devices.Polyaniline(PANI)is considered as a dominant material in this sector,as it is endowed with the optical properties of both metal and semiconductors.However,its widespread application got delineated because of its irregular rigid form,level of conductivity,and precise choice of solvents.Incorporating PANI in textile materials can generate promising functionality for wearable applications.This research work employed a straightforward in-situ chemical oxidative polymerization to synthesize PANI on Cotton fabric surfaces with varying dopant(HCl)concentrations.Pre-treatment using NaOH is implemented to improve the conductivity of the fabric surface by increasing the monomer absorption.This research explores the morphological and structural analysis employing SEM,FTIR and EDX.The surface resistivity was measured using a digital multimeter,and thermal stability is measured using TGA.Upon successful polymerization,a homogenous coating layer is observed.It is revealed that the simple pre-treatment technique significantly reduces the surface resistivity of Cotton fabric to 1.27 kΩ/cm with increasing acid concentration and thermal stability.The electro-thermal energy can also reach up to 38.2°C within 50 s with a deployed voltage of 15 V.The modified fabric is anticipated to be used in thermal regulation,supercapacitor,sensor,UV shielding,antimicrobial and other prospective functional applications.

A green cross-linking method for the preparation of renewable threedimensional graphene sponges for efficient adsorption of Congo red dye

Graphene-based materials possess significant potential for the treatment of dye wastewater due to their exceptional adsorption properties toward stubborn pollutants.However,their utilization is hindered by high preparation costs,low yields,environmental pollution during synthesis,and challenges in regenerating the adsorbent.This study proposes a novel approach to address these limitations by developing nitrogen-doped three-dimensional(3D)polyvinyl alcohol(PVA)crosslinked graphene sponges(N-PGA)using a cross-linking method with ammonium carbonate.This method offers a relatively mild,environmentally friendly approach.Ammonium carbonate serves as both a reducing and modifying agent,facilitating the formation of the intrinsic structure of N-PGA and acting as a nitrogen source.Meanwhile,PVA is utilized as the cross-linking agent.The results demonstrate that N-PGA exhibits a favorable internal 3D hierarchical porous structure and possesses robust mechanical properties.The measured specific surface area(BET)of N-PGA was as high as406.538 m^(2)·g^(-1),which was favorable for its efficient adsorption of Congo red(CR)dye molecules.At an initial concentration of 50 mg·L^(-1),N-PGA achieved an impressive removal rate of 89.6%and an adsorption capacity of 112 mg·g^(-1)for CR dye.Furthermore,it retained 79%of its initial adsorption capacity after 10 cycles,demonstrating excellent regeneration performance.In summary,the synthesized N-PGA displays remarkable efficacy in the adsorption of CR dye in wastewater,opening up new possibilities for utilizing 3D porous graphene nanomaterials as efficient adsorbents in wastewater treatment.

Bimodal growth of Fe islands on graphene

Magnetic metals deposited on graphene hold the key to applications in spintronics. Here, we present the results of Fe islands grown on graphene/Si C(0001) by molecular beam epitaxy, which are investigated by scanning tunneling microscopy. The two types of islands distinguished by flat or round tops are revealed, indicating bimodal growth of Fe. The atomic structures on the top surfaces of flat islands are also clearly resolved. Our results may improve the understanding of the mechanisms of metals deposited on graphene and pave the way for future spintronic applications of Fe/graphene systems.

Progress on the application of graphene-based composites toward energetic materials:A review

Carbon material is an important additive in energetic materials.Graphene is a monolayer carbon material in which carbon atoms are arranged in two-dimensional honeycomb structure,who has special optical,electrical,and mechanical properties.Recently,the application of graphene-based composites in energetic materials has received extensive attention.This review mainly summarizes the applications of graphene and graphene-based nanomaterials in energetic materials.The effects of these materials on the thermal stability,sensitivity,mechanical property,ignition and combustion of energetic materials were discussed.Furthermore,the progress of functionalized modification of graphene has been summarized,including covalent bonding modification and doping modification.These studies show that graphenebased materials exhibit excellent performances and might emerge as promising candidate for energetic materials.