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.

F-doped orthorhombic Nb_(2)O_(5) exposed with 97% (100) facet for fast reversible Liþ-Intercalation

Orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))is attractive for fast-charging Li-ion batteries,but it is still hard to realize rapid charge transfer kinetics for Li-ion storage.Herein,F-doped T-Nb_(2)O_(5) microflowers(F-Nb_(2)O_(5))are rationally synthesized through topotactic conversion.Specifically,F-Nb_(2)O_(5) are assembled by single-crystal nanoflakes with nearly 97%exposed(100)facet,which maximizes the exposure of the feasible Li^(+)transport pathways along loosely packed 4g atomic layers to the electrolytes,thus effectively enhancing the Li^(+)-intercalation performance.Besides,the band gap of F-Nb_(2)O_(5) is reduced to 2.87 eV due to the doping of F atoms,leading to enhanced electrical conductivity.The synergetic effects between tailored exposed crystal facets,F-doping,and ultrathin building blocks,speed up the Li^(+)/electron transfer kinetics and improve the pseudocapacitive properties of F-Nb_(2)O_(5).Therefore,F-Nb_(2)O_(5) exhibit superior rate capability(210.8 and 164.9 mAh g^(-1) at 1 and 10 C,respectively)and good long-term 10 C cycling performance(132.7 mAh g^(-1) after 1500 cycles).

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.

Exfoliation of poly(ethylene glycol)-intercalated graphite oxide composite in water without sonication

A novel method for exfoliating graphite oxide(GrO)was implemented through the mass water absorption of a GrO–poly(ethylene glycol)(GrO–PEG)composite.The GrO–PEG composite was prepared by intercalating PEG into the lamellae of GrO,and the variation of the basal spacing was measured by X-ray diffraction analysis.The yield of graphene was measured with an ultraviolet–visible spectrophotometer,and the properties of graphene oxide(GO)were characterized by atomic force microscopy,transmission electron microscopy(TEM),Raman spectrometry,and Fourier transform infrared spectroscopy.Increasing intercalation time was found to improve the yield of GO,whereas increasing the PEG molecular weight had the opposite effect.The GO sheets produced from the intercalation–absorption–exfoliation process were found to be a four-layer structure.TEM and Raman analyses indicate that the graphitized structure and oxygen groups of GO were preserved during the exfoliation process.Most importantly,the results show that good-quality GO could be prepared via a mild method involving water absorption of a GrO–PEG composite.

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.

Tungsten carbide-reduced graphene oxide intercalation compound as co-catalyst for methanol oxidation

Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.

Preparation and Properties of Phenolic Resin/Montmorillonite Intercalation Nanocomposites

Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.

Lithium intercalation/de-intercalation behavior of a composite Sn/C thin film fabricated by magnetron sputtering

A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, electron probe microanalyzer （EPMA）, X-ray photoelectron spectroscopy （XPS）, inductively coupled plasma atomic emission spectrometry （ICP）, cyclic voltammetry （CV）, and galvanostatic charge/discharge （GC） measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.

Influence of blasting on the properties of weak intercalation of a layered rock slope

A precondition for correctly analyzing the stability of a slope and designing its bracing structure is to study and determine the influence of excavation blasting on the properties of weak intercalation in the layered rock slope. On the basis of in-situ stratification-cracking blasting tests, the properties of weak intercalation were investigated using the LS-DYNA3D program. The displacement distribution and compactness of weak intercalation at different positions away from the charge center and their various laws are discussed. The critical displacement of stratification-cracking （0.1 mm） was obtained, and an approximate expression of compactness were deduced. Furthermore, through the simulation of a layered rock blasting under the same geological conditions, the stratification-cracking effect of deep-hole blasting on the properties of weak intercalation was compared with that of short-hole blasting, and the influencing differences, in addition to their causes, were analyzed. The results indicated that the blasting cavity of weak intercalation in short-hole blasting with a radius of 40 mm was nearly a circle, whose radius was about 28.7 cm; whereas in deep-hole blasting with a radius of 150 mm, the shape of the blasting cavity was different from that in short-hole blasting, the radius of the cavity behind the charge （89.1 cm） was further smaller than those of the other three （138.7 cm）, and there were sharp crinkles on the surface of weak intercalation. When the distance from the charge center （DCC） was less than 40 and 150 cm in short-hole and deep-hole blasting, respectively, the displacement of weak intercalation was reduced remarkably with the increase in DCC.

Preparation and Structural Investigation of CuCl_2 Graphite Intercalation Compounds

Superfine graphite powder was prepared by ball-milling exfoliated graphite containing anhydrous CuCl2 in planetary ball milling systems. Nano-scale CuCl2 graphite intercalation compounds were synthesized by heating a mixture of anhydrous CuCl2 and graphite nanosheets. Scanning electron microscopy, energy-dispersive X-ray spectroscopy and high-resolution transmission electron microscopy were performed to characterize the microstructures of stage-1 nano-scale CuCl2 graphite intercalation compounds. The structure and components of the domain wall and core in the nano-scale CuCl2 graphite intercalation compounds are described. The results show that the content of CuCl2 in the mixture plays a crucial role in the size of the nano-scale CuCl2 graphite intercalation compound.

Design of Wood/Montmorillonite (MMT) Intercalation Nanocomposite

Studying new wood composites through nano science and technology (NSC) will develop new compounding theory of wood, and accelerate the combination of new technology, wood science, material science and other disciplines. The compounding of wood and inorganic MMT on nanoscale molecular level has high potential to greatly improve the mechanical properties, fire retardance, abrasion resistance, decay resistance, dimensional stability and other properties of wood. Based on the great achievements of polymer/montmorillonite (MMT) nanocomposites, this paper reviewed nano intercalation compounding methods (i.e. in-situ intercalative polymerization and direct polymer intercalation), and discussed the structure, properties and modification of montmorillonite (MMT). According to the main chemical components and particular structure of wood, the authors discussed the liquefaction and plasticization of wood, compared the dissolvability and meltability between wood and polymer, and then systematically put forward the basic idea, technological processes and schematic diagram to prepare wood/MMT nanocomposites (WMNC). The key technology to prepare WMNC is either to introduce delaminated MMT nanolayers into wood with the help of some intermediate polymers, or to obtain liquefied wood or plasticized wood from the complicated natural composite. It is applicable and effective to realize wood/MMT nanoscale compounding with the help of proper intercalation agent and medium polymer through the proposed 搊ne-step?or 搕wo-step?impregnating processes.

Intercalation Assembly Method and Intercalation Process Control of Layered Intercalated Functional Materials

Layered intercalated functional materials of layered double hydroxide type are an important class of functional materials developed in recent years. Based on long term studies on these materials in the State Key Laboratory of Chemical Resource Engineering in Beiiing University of Chemical Technology, the orinciole for the design of controlled intercalation processes in the light of tuture production processing requirements has been developed. Intercalation assembly methods and technologies have been invented to control the intercalation process for preparing layered intercalated materials with various structures and functions.

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.

Preparation and Photochemical Behavior of a Cationic Azobenzene Dye-Montmorillonite Intercalation Compound

Montmorillonite/cationic azobenzene dye（p-（δ-triethylammoniobutoxy）-p＇-methyl- azobenzene bromide） intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure cationic azo-dye, the thermal stability of the intercalated dye was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated dye shifted towards longer wave length by 38 nm. This could be ascribed to the strong conjugation of cationic azo-dye supramolecular order structure（J cluster） confined in a nanoscale space of montmorillonite interlayer gallery. UV/vis spectra data show that the intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and daylight cis-to-trans back reaction. FTIR indicates the successful intercalation of cationic azo-dye into the montmorillonite interlayer.

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.

Preintercalation of Layered γ-Zirconium Phosphate for Preparation of Immobilized Hemoglobin

Layeredγ-Zirconium phosphate (γ-ZrP) preintercalated with butylamine, tetra (n-butylammonium)hydroxide, dimethylamine respectively, or only ultrasonificated, for preparation of immobilized hemoglobin were investigated in this report.

Melting Intercalation Method to Prepare Lauric Acid/Organophilic Montmorillonite Shape-stabilized Phase Change Material

A kind of novel shape-stabilized phase change material （SSPCM） was prepared by using a melting intercalation technique. This kind of SSPCM was made of lauric acid （LA） as a phase change material and organophilic montmorillonite （OMMT） as a support material. And the thermal properties and morphology of the SSPCM were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, scanning electronic microscope （SEM）, scanning calorimeter （DSC）, and differential thermal cravimetry （TG）. The DSC result shows that the phase change temperature of the SSPCM is close to that of LA, and its latent heat is equivalent to that of the calculated value based on the mass ratio of LA measured by TG. The XRD, SEM and TEM results demonstrate that the LA intercalates into the silicate layers of the OMMT, thus forming a typically intercalted hybrid, which can restrict the molecular chain of the LA within the structure of OMMT at high temperature. And consequently SSPCM can keep its solid state during its solid-liquid phase change processing.

STUDY ON INTERCALATION MECHANISM OF GELATIN/MMT NANOCOMPOSITE

A gelatin/MMT nanocomposite was prepared in an aqueous solution and investigated by XRD,FTIR and 13 C NMR,and then the intercalation mechanism was discussed.The result of XRD indicated that the gelatin molecule had already inserted into the interlayer of MMT,and the intercalation or exfoliation structure had been achieved.The result of 13 C NMR demonstrated that the ions interaction between gelatin and MMT was attributed to the driving force for intercalation.In order to confirm the role of -COO - of gelatin in the combination with MMT,lauric sodium was brought in as a model to react with MMT,and was characterized by XRD and FTIR,the result proved that there existed a kind of strong interaction between -COO - and ions of MMT.