Two-dimensional polyaniline nanosheets via liquid-phase exfoliation

Two-dimensional（2D） organic nanomaterials are fascinating because of their unique properties and pentential applications in future optoelectronic devices.Polyaniline（PANI） has attracted much attention for its high conductivity,good environmental stability and unusual doping chemistry.We report on liquid-phase exfoliation of layered PANI films grown by electrochemical polymerization.Atomic force microscopy images demonstrate that few-or even mono-layer PANI nanosheets can be fabricated.The PANI nanosheets can be transferred onto a variety of surfaces,providing a promising route to their incorporation into a variety of devices for further studies and various applications.

Liquid-phase exfoliation of violet phosphorus for electronic applications

Large-scale production of two-dimensional(2D)materials still is a crucial point toward its practical applications.Violet phosphorus(VP)with a wide bandgap accelerates and broadens the potential applications of elemental phosphorus in optoelectronics.Here,we demonstrate the scalable production of solution-processable violet phosphorus flakes stably dispersed in several solvents.The exfoliated VP flakes exhibit thickness-dependent visible photoluminescence characteristics,which covers the shortcoming of black phosphorus.Meanwhile,the VP-based field-effect transistor reveals relatively competitive electrical properties to other liquid-phase exfoliated 2D materials.Our study paves the way for a wide range of applications of optical devices,energy storage,catalysis,and sodium batteries based on large-scale VP flakes.

Solvothermal-assisted liquid-phase exfoliation of large size and high quality black phosphorus

Black phosphorus(BP),especially for BP nanosheets,with unique layered structure among two dimensional(2D)materials has attracted much attention due to its outstanding physical properties,such as ultra-high mobility,in-plane anisotropic properties.However,the small horizontal-size of reported BP limits its applications in the integrated circuit or some functional devices.In this work,a solvothermalassisted liquid-phase exfoliation technique is firstly employed for preparing large size and high-quality BP nanosheets.In the high-polar acetonitrile solvent,solvothermal treatment weakens the Van der Waals forces of block BP.Together with the subsequently ultrasonic processing,effective exfoliation of large size and high-quality BP nanosheets are realized.The TEM,AFM and Raman results indicate that the prepared BP nanosheets are high quality with an average thickness of about 2 nm,and the horizontalsize is up to 10μm.This facile and effective method for exfoliated BP nanosheets provides a promising strategy for the exfoliation of other 2D materials.

One-Step Scalable Fabrication of Nitrogen and Chlorine Co-doped Graphene by Electrochemical Exfoliation for High-Performance Supercapacitors

The stacking and aggregation of graphene nanosheets have been obstacles to their application as electrode materials for microelectronic devices.This study deploys a one-step,scalable,facile electrochemical exfoliation technique to fabricate nitrogen(N)and chlorine(Cl)co-doped graphene nanosheets(i.e.,N-Cl-G)via the application of constant voltage on graphite in a mixture of 0.1 mol/L H_(2)SO_(4)and 0.1 mol/L NH_(4)Cl without using dangerous and exhaustive operation.The introduction of Cl(with its large radius)and N,both with high electrical negativity,facilitates the modulation of the electronic structure of graphene and creation of rich structural defects in it.Consequently,in the as-constructed supercapacitors,N-Cl-G exhibits a high specific capacitance of 77 F/g at 0.2 A/g and remarkable cycling stability with 91.7%retention of initial capacitance after 20,000 cycles at 10 A/g.Furthermore,a symmetrical supercapacitor assembled with N-Cl-G as the positive and negative electrodes(denoted as N-Cl-G//N-Cl-G)exhibits an energy density of 3.38 Wh/kg at a power density of 600 W/kg and superior cycling stability with almost no capacitance loss after 5000 cycles at 5 A/g.This study provides a scalable protocol for the facile fabrication of high-performance co-doped graphene as an electrode material candidate for supercapacitors.

Impact of cooling rate on exfoliation corrosion resistance of a Li-containing 7xxx aluminum alloy

The impact of cooling rate after solution heat treatment on exfoliation corrosion resistance of a Li-containing 7xxx aluminum alloy was investigated by accelerated immersion and electrochemical impedance spectroscopy test,optical microscope,electron backscatter diffraction and scanning transmission electron microscope.With the decrease of cooling rate from 1700℃/s to 4℃/s,exfoliation corrosion resistance of the aged specimens decreases with rating changing from EA to EC and the maximum corrosion depth increasing from about 169.4μm to 632.1μm.Exfoliation corrosion tends to develop along grain boundaries in the specimens with cooling rates higher than about 31℃/s and along both grain boundaries and sub-grain boundaries in the specimens with lower cooling rates.The reason has been discussed based on the changes of the microstructure and microchemistry at grain boundaries and sub-grain boundaries due to slow cooling.

Microwave-Assisted Confining Growth and Liquid Exfoliation of sp^(3)-Hybrid Carbon Nitride Nano/Micro-Crystals

As one promising carbon-based material,sp^(3)-hybrid carbon nitride has been predicted with various novel physicochemical properties.However,the synthesis of sp^(3)-hybrid carbon nitride is still limited by the nanaoscale,low crystallinity,complex source,and expensive instruments.Herein,we have presented a facile approach to the sp^(3)-hybrid carbon nitride nano/micro-crystals with microwave-assisted confining growth and liquid exfoliation.Actually,the carbon nitride nano/micro-crystals can spontaneously emerge and grow in the microwave-assisted polymerization of citric acid and urea,and the liquid exfoliation can break the bulk disorder polymer to retrieve the highly crystalline carbon nitride nano/micro-crystals.The obtained carbon nitride nano/micro-crystals present superior blue light absorption strength and surprising photoluminescence quantum yields of 57.96% in ethanol and 18.05%in solid state.The experimental characterizations and density functional theory calculations reveal that the interface-trapped localized exciton may contribute to the excellent intrinsic light emission capability of carbon nitride nano/micro-crystals and the interparticle staggered stacking will prevent the aggregation-caused-quenching partially.Finally,the carbon nitride nano/micro-crystals are demonstrated to be potentially useful as the phosphor medium in light-emitting-diode for interrupting blue light-induced eye damage.This work paves new light on the synthesis strategy of sp^(3)-hybrid carbon nitride materials and thus may push forward the development of multiple carbon nitride research.

Influence of dual retrogression and re-aging temper on microstructure,strength and exfoliation corrosion behavior of Al-Zn-Mg-Cu alloy

Influence of dual retrogression and re-aging（dual-RRA） temper on microstructure,strength and exfoliation corrosion（EC） behavior of Al-Zn-Mg-Cu alloy was investigated by hardness measurements,tensile properties tests,exfoliation corrosion tests,transmission electron microscopy（TEM） and scanning electron microscopy（SEM） observation combined energy dispersive X-ray detector（EDX） analysis.Dual-RRA temper maintains the matrix precipitates（MPs） similar to RRA temper,meanwhile obtains coarser and sparser grain boundary precipitates（GBPs） as well as higher Cu and lower Zn content compared with T76 temper.Therefore,dual-RRA temper not only keeps strength equivalent to the RRA temper but also obtains higher EC resistance than T76 temper.

Exfoliation corrosion behavior of 7050-T6 aluminum alloy treated with various quench transfer time

The exfoliation corrosion （EFC） behavior of 7050-T6 aluminum alloy treated with various quench transfer time after solution heat treatment was investigated by standard EFC immersion tests, strength loss measurements after EFC tests and electrochemical impedance spectroscope （EIS） technique. The results showed that EFC resistance of the alloy decreased with increasing quench transfer time. Backscattered electron scanning electron microscope （SEM） together with transmission electron microscope （TEM） observations revealed that the coverage ratio and microstructure of precipitates at grain boundary area are the most important factors which influence the EFC susceptibility of the alloy, while precipitate-free zone （PFZ） near grain boundary has no or only a minor effect on it. In addition, galvanostatic measurements of the alloy present a good correlation between EFC resistance and transients in potential. The cumulated number of transients in potential can be used to evaluate EFC resistance of the alloy.

Pt nanoparticles entrapped in ordered mesoporous carbons:An efficient catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives

Pt nanoparticles entrapped in ordered mesoporous CMK-3 carbons with p6mm symmetry were prepared using a facile impregnation method, and the resulting materials were characterized using X-ray diffraction spectroscopy, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The Pt nanoparticles were highly dispersed in the CMK-3 with 43.7% dispersion. The Pt/CMK-3 catalyst was an effective catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives under the experimental conditions studied here. The Pt/CMK-3 catalyst was more active than commercial Pt/C catalyst in most cases. A highest turnover frequency of 43.8 s-1 was measured when the Pt/CMK-3 catalyst was applied for the hydrogenation of 2-methyl-nitrobenzene in ethanol under optimal conditions. It is worthy of note that the Pt/CMK-3 catalyst could be recycled easily, and could be reused at least fourteen times without any loss in activity or selectivity for the hydrogenation of nitrobenzene in ethanol.

Electrochemical exfoliation of two-dimensional layered black phosphorus and applications

With the discovery of graphene,black phosphorus(BP)has been rediscovered as a two-dimensional(2 D)layered material.Since its first preparation in 2014,2 D BP has elicited immense interest,and has exhibited excellent properties,such as distinct pleated structures in layers,adjustable direct bandgap,high carrier mobility,moderate on/off ratio,large specific surface area,and various interesting in-layer anisotropies.However,the realization of these excellent properties depends on the preparation of highquality 2 D BP sheets.Electrochemical exfoliation methods are typically performed under mild conditions,thus,these methods are convenient,controllable,and can produce high-quality 2 D BP sheets.This review summarizes research progress in BP sheets preparation through anodic,cathodic,and electrolyte exfoliation in recent years.Different exfoliating methods affect the quality of 2 D BP sheets.Moreover,possible exfoliating mechanisms and the potential applications of different exfoliating methods are summarized and discussed in detail.Lastly,the shortcomings of existing research on electrochemical exfoliation are presented,and suggestions and prospects for future research on the electrochemical exfoliation of 2 D BP are proposed.

The Effect of Thermal Exfoliation Temperature on the Structure and Supercapacitive Performance of Graphene Nanosheets

Graphene nanosheets(GSs) were prepared from graphite oxide by thermal exfoliation method. The effect of thermal exfoliation temperature on the structure and supercapacitive performance of GSs has been investigated. The results show that the GSs with pore sizes center around 4.0 nm. With an increase of thermal reduction temperature, the number of stacking layers and the structure disorder degree increase, while the oxygen-containing groups content, BET surface area,and electrical resistivity of GSs decrease. The results indicate that 673 K is the preferable thermal exfoliation temperature to acquire good supercapacitive performance. In this case, the GSs have the best supercapacitive performance(233.1 F g-1) in a 6 mol L-1KOH electrolyte. The prepared GSs at the preferable thermal exfoliation temperature have good rate performance and cycle stability.

Influences of the [Co^2＋]/[Co^3＋] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air

Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2.4H2O as catalyst.The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance.The results showed that [Co3+] reached the maximum at about 25-30min.[Co3+] increased with increasing Co catalyst amount at total Co concentration<150 mg.L-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+] max.A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.

Electron microscopic investigation of anterior lens capsule in an individual with true exfoliation

AIMTo determine the changes which occur in the anterior capsule in true exfoliation which is a very rare condition.

Kinetics of Liquid-Phase Hydrogenation of Toluene Catalyzed by Hydrogen Storage Alloy MlNi_5

The kinetics of liquid-phase hydrogenation of toluene catalyzed by MlNi_5 was studied by investigating the influences of the reaction temperature and pressure on the mass transfer-reaction processes inside the slurry. The results show that the reaction rate accelerates when the reaction temperature increases, and reaches its maximum at about 490 K, but if temperature is higher than 510 K, the reaction rate decreases rapidly. The whole reaction process is controlled by the reaction at the surface of the catalyst particles. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particle can be neglected. The apparent reaction rate is zero order for toluene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model is obtained. The kinetic model fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MlNi_5-toluene slurry system is 41.01 kJ·mol^(-1).

The role of electrolyte acid concentration in the electrochemical exfoliation of graphite:Mechanism and synthesis of electrochemical graphene oxide

Electrochemistry has emerged as a major route for graphene and graphene oxide synthesis from graphite.Anodic graphite oxidation is commonly used with dilute mineral acid or aqueous salt electrolytes.In this system,the electrolyte acid concentration appears to be a critical parameter.However,the effect of the acid concentration,particularly at low concentrations,is still not fully understood.To address this issue,we used a packed bed electrochemical reactor to synthesize seven different electrochemical graphite oxide(EGO)products in 2–16M sulfuric acid.Detailed XRD,XPS,Raman,conductivity and optical microscopy analysis of the products was carried out.We found dilute acid(<10 M)graphite oxides were less crystalline and less oxidized than those produced in stronger acids.The oxygen evolution reaction at the graphite surface appears to affect the structural changes,oxidation mechanism,and electrochemical corrosion of the anode.EGO conductivity is also strongly affected by the electrolyte’s acidity.We show that well oxidized,yet reasonably conductive,single layer graphene oxide can be produced from 7.1M acid.These results broaden our understanding of graphite electrochemistry and will serve to inform future electrochemical graphene synthesis efforts.

On the liquid-phase technology of carbon fiber/aluminum matrix composites

The main problems with the liquid-phase technology of carbon fiber/aluminum matrix composites include poor wetting of the fiber with liquid aluminum and formation of aluminum carbide on the fibers’surface.This paper aims to solve these problems.The theoretical and experimental dependence of porosity on the applied pressure were determined.The possibility of obtaining a carbon fiber/aluminum matrix composite wire with a strength value of about 1500 MPa was shown.The correlation among the strength of the carbon fiber reinforced aluminum matrix composite,the fracture surface,and the degradation of the carbon fiber surface was discussed.

Oxidative exfoliation of spent cathode carbon:A two-in-one strategy for its decontamination and high-valued application

Spent cathode carbon(SCC)from aluminum electrolysis is a potential graphite resource.However,full use of the SCC remains a challenge,since it contains many hazardous substances(e.g.,fluoride salts,cyanides),encapsulated within the thick carbon layers and thus posing serious environmental concerns.This work presents a chemical oxidative exfoliation route to achieve the recycling of SCC and the decontaminated SCC with high-valued graphene oxide(GO)-like carbon structures(SCC-GO)is applied as an excellent adsorbent for organic pollutants.Specifically,after the oxidative exfoliation,the embedded hazardous constituents are fully exposed,facilitating their subsequent removal by aqueous leaching.Moreover,benefiting from the enhanced specific surface areas along with abundant O-containing functional groups,the as-produced SCC-GO,shows an adsorption capacity as high as 347 mg·g^(-1)when considering methylene blue as a pollutant model,which exceeds most of the recently reported carbon-based adsorbents.Our study provides a feasible solution for the efficient recycling of hazardous carbonaceous wastes.

Effect of Scandium and Zirconium on Mechanical and Exfoliation Corrosion Properties of Al-Mg-Mn Alloys

To quest for the best combination of mechanical properties and exfoliation corrosion resisting property of Al-Mg-Mn base alloys, and to seek after the effect of Sc and Zr on mechanical and exfoliation corrosion properties of Al-Mg-Mn alloys, comparative research technique was used, the mechanical properties of Al-Mg-Mn alloys with and without minor Sc and Zr treated by different annealing were measured, the degrees of exfoliation corrosion for these alloys through accelerated exfoliation corrosion test were evaluated, and polarization curves of these alloys were measured, too. The micro-morphologies of corrosion specimens were observed by SEM and the corrosion product was analyzed using EDS. Optical microscope and TEM were used, the relationship between their microstruc-tures and mechanical properties, exfoliation corrosion resisting property was investigated, and the results show that the addition of minor Sc and Zr can enhance the strength greatly and also improve the combination of strength and plasticity. Moreover, the addition of minor Sc, Zr does not cause appreciable decrease of exfoliation corrosion resisting property, the Al-Mg-Mn-Sc-Zr alloy annealed at 350 ℃ for 1 h has excellent combination of mechanical properties and exfoliation corrosion resisting property, the satisfied combination of mechanical properties nad exfoliation corrosion resisting property can be obtained by means of adding minor Sc and Zr, decreasing the content of Mn, and adopting reasonable annealing practice.

Synthesis of graphene materials by electrochemical exfoliation: Recent progress and future potential

Synthesis of structurally controlled graphene materials is critical for realizing their practical applications.The electrochemical exfoliation of graphite has emerged as a simple method to produce graphene materials.This review examines research progress in the last 5 years,from 2015 to 2019.Graphene material synthesis methods generally have a trade‐off between increasing production yield and achieving better material property control.The synthesis conditions for synthesizing pristine graphene,graphene oxide(GO),and graphene composites are significantly different.Thus,in this review,we first discuss synthesis methods for graphene materials with high C/O ratios from four aspects:graphite electrodes,equipment engineering,electrolytes,and additional reduction methods.Next,we survey synthesis methods for GO and examine how the pretreatment of the graphite electrodes,electrolytes,and operation parameters,such as applied voltages,electrolyte temperatures,and mechanical forces,affect the quality of GO.Further,we summarize electrochemical exfoliation methods used to dope graphene materials,introduce covalent functional groups,incorporate various nanoparticles,and assembly of graphene architectures.For all synthesis methods,we compare the properties of resulting graphene materials such as C/O ratios,lateral size,layer numbers,and quality characterized by Raman spectroscopy.Lastly,we propose our perspectives on further research.We hope this review stimulates more studies to realize the on‐demand production of graphene materials with desired properties using electrochemical exfoliation methods.

Self-Exfoliation of Flake Graphite for Bioinspired Compositing with Aramid Nanofiber toward Integration of Mechanical and Thermoconductive Properties

Flexible yet highly thermoconductive materials are essential for the development of next-generation flexible electronic devices.Herein,we report a bioinspired nanostructured film with the integration of large ductility and high thermal conductivity based on self-exfoliated pristine graphene and three-dimensional aramid nanofiber network.A self-grinding strategy to directly exfoliate flake graphite into few-layer and few-defect pristine graphene is successfully developed through mutual shear friction between graphite particles,generating largely enhanced yield and productivity in comparison to normal liquid-based exfoliation strategies,such as ultrasonication,high-shear mixing and ball milling.Inspired by nacre,a new bioinspired layered structural design model containing three-dimensional nanofiber network is proposed and implemented with an interconnected aramid nanofiber network and high-loading graphene nanosheets by a developed continuous assembly strategy of sol-gel-film transformation.It is revealed that the bioinspired film not only exhibits nacre-like ductile deformation behavior by releasing the hidden length of curved aramid nanofibers,but also possesses good thermal transport ability by directionally conducting heat along pristine graphene nanosheets.