Effects of acid vapour mediated oxidization on the electrochemical performance of thermally exfoliated graphene

The surface modification of thermally exfoliated graphene (TEG) is an important technique for alteration of its hydrophobic nature and the resolution of its limited dispersibility. We have developed an easy acid-vapour-mediated method to functionalize the inert TEG surface with oxygen functional groups. The effects of oxygen functional groups on the capacitive performances of TEG were investigated with various reaction times. Ultraviolet–visible, Fourier transform infrared and Raman spectroscopy analyses demonstrated that the dispersibility of TEG was improved due to defect augmenting as the extent of oxidation progressed. Quantitative analyses of functional groups of the oxidized TEG samples (O-TEGs) were performed by thermogravimetric analysis and X-ray photoelectron spectroscopic studies. Physisorption surface analysis showed that the pore volumes of O-TEGs were greater than that of the pristine TEG, whereas the specific surface areas of O-TEGs were lower than that of pristine TEG. Electrochemical performances of the O-TEG samples were measured through cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy analysis. A maximum specific capacitance of 175.2 F g⁻¹ was recorded at a current density of 1 A g⁻¹ for the O-TEG oxidized for 2 h. Retention of specific capacitance for the sample was ∼97% after 5000 charge–discharge cycles.     

Microtubes made of carbon nanotubes

Microtubes made of multi-walled carbon nanotubes were prepared via infiltration of CNT-suspension through a microfiltration hollow fiber membrane. Shrinking of the entangled CNT network during the drying allows withdrawal of CNT-microtubes from the hollow fiber. Currently, microtubes have a length of ∼50 cm, outer diameter of ∼1.7 mm and scalable inner diameter by varying the infiltration time resulting in wall thicknesses of 130–320 μm. The BET surface area is 200 m²/g with a porosity of 48–67% and an electrical conductivity ∼20 S/cm. We propose to use such novel CNT-microtubes for the fabrication of tubular electrochemical cells and membrane filtration processes.     

Open cell geopolymer foams by a novel saponification/peroxide/gelcasting combined route

Using a novel saponification/peroxide/gelcasting combined route it was possible to produce geopolymer foams with a total porosity of ∼85 vol%, open porosity as high as ∼70 vol%, average cell size (D50) of 318 μm, and possessing a specific surface area of 50 m²/g. The in situ formation of surfactants by the saponification reaction of oil in the geopolymer alkaline environment led to increased total and open porosity in comparison to alternative methods for the fabrication of geopolymer foams.     

Cycle and rate performance of chemically modified super-aligned carbon nanotube electrodes for lithium ion batteries

Super-aligned multi-walled carbon nanotubes (MWCNTs), which had been produced in large-scale, were oxidized by H₂O₂ and HNO₃. The surface defects and oxygen-containing functional groups introduced during the oxidizing process were characterized by Raman spectroscopy and X-ray photoelectron spectroscopy. The surface modification of MWCNTs improved the electrochemical properties. As a result, H₂O₂-treated and HNO₃-treated MWCNTs displayed reversible capacities of 364 mA h/g and 391 mA h/g, respectively, after 80 galvanostatic cycles, corresponding to 143% and 154% improvements compared with pristine MWCNTs. The rate capability was also increased. At a current density of 3500 mA/g, H₂O₂-treated and HNO₃-treated MWCNTs exhibited reversible capacities of 66 mA h/g and 156 mA h/g, respectively. In contrast, pristine MWCNTs were only able to deliver 27 mA h/g at this current density.     

Mesoporous N-containing carbon nanosheets towards high-performance electrochemical capacitors

We developed a direct carbonization strategy to efficiently fabricate mesoporous N-containing carbon nanosheets (N-CNSs) by using polyaniline nanosheets as a carbon precursor. Physicochemical characterizations revealed that the as-synthesized N-CNSs with 5.9 wt.% N species possessed a well-developed mesoporous architecture with large specific surface area of 352 m² g⁻¹, high mesoporous volume of 0.32 cm³ g⁻¹, and average pore size of ∼5.2 nm. When further utilized as an electrode for electrochemical capacitors, the mesoporous N-CNSs delivered a large specific capacitance of 239 F g⁻¹ at 0.5 A g⁻¹, and even 197 F g⁻¹ at a high current load of 8 A g⁻¹, indicating its good rate behavior. Furthermore, the capacitance degradation of ∼4% over continuous 5000 charge–discharge cycles at 6 A g⁻¹ further verified its good electrochemical stability at high rates for long-term electrochemical capacitors application.     

Oxidation of arsenite in aqueous solutions by redox copolymer with N-bromosulfonamide functional groups

Macromolecular oxidant [P]-SO₂NBrNa (a macroporous styrene/divinylbenzene copolymer containing N-bromosulfonamide functional groups in the sodium form) was synthesized and used to oxidize arsenites to arsenates in dilute aqueous solutions. The oxidant, containing active bromine (1.65 mmol/g) in its functional groups, was obtained through the transformation of Amberlyst 15 (Rohm and Haas) commercial cation exchanger’s sulfonic functional groups. The batchwise method and the column method and NaAsO₂ solutions (375, 93 and 10 mg As(III)/dm³) in water alone and in 0.01 M NaOH were used in the investigations. Special potentiometric, reductometric measurements showed that the investigated oxidation reaction was favoured by a weak acidic to weak alkaline medium. The determined redox potential of the resin was 440 mV at pH = 6.3 and 130 mV at pH = 11.01. In the column process experiments, conducted using NaAsO₂ solutions with a concentration of 10 mg As(III)/dm³ at a flow rate of 6 BV/h, a breakthrough (defined as the exceedance of 0.01 mg As(III)/dm³ in the effluent) would occur after the solutions amounting to about 1700 bed volumes were passed though the column.     

Electrochemical cycling behaviour of lithium carbonate (Li2CO3) pre-treated graphite anodes – SEI formation and graphite damage mechanisms

Graphite electrode surfaces were treated using a simple process of sedimentation in aqueous solutions containing 0.5 and 1.0 wt.% Li₂CO₃ with particle sizes of ∼1–2 μm. During the first cycle of voltammetry tests (vs. Li/Li⁺), the graphite surface was subjected to electrochemical degradation as a result of fracture and removal of near-surface graphite particles. Surface degradation was accompanied by a 0.4% strain in the graphite lattice as determined by in situ Raman spectroscopy. Pre-treated electrodes experienced a capacity drop of 3% in the first cycle, compared to a 40% drop observed in case of untreated graphite electrodes. After testing for 100 cycles, a capacity of 0.54 mAh cm⁻² was recorded for the pre-treated electrodes as opposed to a significant drop to 0.11 mAh cm⁻² for the untreated graphite. Cross-sectional HR-TEM indicated that the SEI formed on the pre-treated electrodes primarily consisted of Li₂CO₃ crystals of 14.6 ± 6.9 nm in size distributed within an amorphous matrix. The results suggested that the Li₂CO₃ enriched SEI formed on the pre-treated electrodes reduced the intensity of solvent co-intercalation induced surface damage. It is proposed that the Li₂CO₃ enriched SEI facilitated Li⁺ diffusion and hence improved the capacity retention during long-term cycling.     

One-pot electrochemical synthesis of graphene by the exfoliation of graphite powder in sodium dodecyl sulfate and its decoration with platinum nanoparticles for methanol oxidation

We demonstrate a method which directly grows large areas of graphene on carbon paper and glassy carbon (GC) substrates from graphite powder and anionic surfactant, sodium dodecyl sulfate, assisted electrochemical exfoliation. The electrochemically reduced graphene has been carefully characterized by scanning electron microscopy (SEM) and electrochemical techniques. Particularly, SEM images show enhanced growth of graphene structures formed of ‘urchin’ objects. The CV spectra illustrate that a variety of the oxygen-containing functional groups has been thoroughly removed from the graphite plane via electrochemical reduction. Potential peak (Ep) of graphene electrode in [Fe(CN)₆]^3−/4− solution is as small as 212 mV which is 168 mV smaller than that of graphite electrode. This could be attributed to the high quality graphene accelerating the electron transfer rate in [Fe(CN)₆]^3−/4− electrochemistry. Finally, platinum was electro reduced onto the GC and graphene modified GC based electrodes for use in methanol oxidation. The catalytic activities of graphene-supported Pt nanoparticles and Pt-GC electrocatalysts for methanol oxidation were 1900 and 915.5 A g⁻¹ Pt, which can reveal the particular properties of the exfoliated graphene supports.     

Discovery of effective solvents for platelet-type graphite nanofibers

The dispersibility of platelet-type graphite nanofibers (PGNFs), an archetype of carbon material with a surface dominated by graphitic edge planes, has been measured in 28 solvents and rationalized on the basis of solvent surface tension and Hansen solubility parameters. Successful solvents possess surface tensions of ∼25–35 mJ m⁻² and substantial values of the hydrogen-bonding Hansen parameter (δ_H ∼ 14–16 MPa^1/2), and many of them are alcohols, such as 1-butanol, ethanol or cyclohexanol. Such result is mainly attributed to the fact that the PGNF edge planes are decorated with oxygen functional groups. The dispersion behavior of the nanofibers could be changed to that typically exhibited by carbon nanotubes and graphene by means of a high temperature annealing that converted their surface edge planes to curved basal planes.     

Corrosion behavior study of AZ91 magnesium alloy coated with methyltriethoxysilane doped with cerium ions

The present work aims to investigate the corrosion behavior of AZ91 magnesium alloy treated with a 4% (v/v) methyltriethoxysilane (MTES) alcohol solution, with and without an alkaline pretreatment. The corrosion resistance was assessed by electrochemical impedance spectroscopy (EIS) and current densities were monitored by potentiodynamic polarization curves during immersion in a 0.1 M Na₂SO₄ solution. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to perform a surface analysis. The electrochemical results showed an improvement of anticorrosion properties of AZ91. Furthermore, alkaline pretreatment enhances adhesion between silane film and substrate surface. This can be attributed to a surface enrichment in hydroxyl groups after the alkaline step, which increases formation of Si–O–Mg covalent bonds. The addition of Ce(NO₃)₃ to the MTES bath was evaluated, and it was found that the electrochemical response depends on the cerium ions concentration used. It was shown that the addition of 6.0 × 10⁻⁵ M of Ce(NO₃)₃ to a MTES bath improves corrosion resistance. Higher concentration of cerium ions lead to destabilizing the siloxane network, decreasing the efficiency of the silane coatings.     

Self-assembly hydrothermal assisted synthesis of mesoporous anatase in the presence of ethylene glycol

Mesoporous nanocrystalline anatase was prepared hydrothermally employing P123 as structure-directing agent. Ethylene glycol was used as a key synthesis parameter to fine tune the morphology, crystal size and pore size of the resultant mesophases. The incorporation of EG in the synthesis gel resulted in the formation of 1–2 μm sphere-like shapes and led to an increase in the specific surface area from ∼95 to ∼170 m²/g, decrease in the average pore size from ∼11 to ∼4.8 nm, and decrease in the average crystallite size from ∼17 to ∼12 nm. These mesophases were used as photocatalysts for the UV degradation of methylene blue and methyl orange. The mesoporous anatase phases photodegraded MB ∼1.5–3× faster than commercially available P25 and showed limited photocatalytic behavior for methyl orange.     

Electrochemical generation of oxygen-containing groups in an ordered microporous zeolite-templated carbon

Zeolite templated carbon (ZTC) was electrochemically oxidized under various conditions, and its chemistry and structural evolution were compared to those produced by conventional chemical oxidation. In both oxidation methods, a general loss of the original structure regularity and high surface area was observed with increasing amount of oxidation. However, the electrochemical method showed much better controllability and enabled the generation of a large number of oxygen functional groups while retaining the original structure of the ZTC. Unlike chemical treatments, highly microporous carbons with an ordered 3-D structure, high surface area (ranging between 1900 and 3500 m²/g) and a large number of oxygen groups (O = 11,000–3300 μmol/g), have been prepared by the electrochemical method. Some insights into the electrooxidation mechanism of carbon materials are proposed from the obtained polarization curves, using ZTC as a model carbon material.     

Removal of aqueous rare earth elements (REEs) using nano-iron based materials

The uptake of REEs was investigated using nano-zero valent iron (nZVI) and alumina-supported nZVI (Al-nZVI). The results indicated fast uptake, with saturation approached within 10 min of contact between solutions and solids. Upon using nZVI, the uptake of REEs seemed to be quantitative over the studied range of concentration; 1.0–100.0 mg L^?1. When Al-nZVI was used, complete removal was achieved within the range of 1.0–10.0 mg L^?1. The solids demonstrated stable performance beyond pH of 2.0, up to neutral pH conditions. Fractionation of REEs on Al-nZVI was observed. The REE ions seem to be fixed to oxide and oxyhydroxide surface groups.     

Pre-treatment of adsorbents for waste water treatment using adsorption coupled-with electrochemical regeneration

With the aim to address waste water treatment problems, a novel and economic water treatment technology was introduced at the University of Manchester. It comprised of a unique combination of adsorption and electrochemical regeneration in a single unit. This process successfully eliminated a number of organic pollutants by using an electrically conducting adsorbent material called Nyex? which was a modified form of synthetic graphite. To expand the scope of other graphite types in waste water treatment applications, natural vein and recycled vein graphite materials were selected for electrochemical surface treatment (pre-treatment) in order to evaluate their adsorptive and electrical properties. New graphite based adsorbents were developed and characterized using a laser diffraction particle size analyser, BET surface area, SEM analysis, X-ray (EDS) elemental analysis, X-ray powder diffraction, Boehm surface titration, Zeta potential electrical bed conductivity and bulk density measurements. Boehm surface titration and EDS (X-ray) elemental analysis showed a significant increase in oxygen containing surface functional groups. Although, no significant improvement in bed electrical conductivity was found to occur after electrochemical surface treatment, however, natural vein and recycled vein graphite materials presented highest bed electrical conductivity amongst competing graphite materials. Aqueous solution of acid violet 17 as a standard pollutant was used to evaluate the comparative performance of these adsorbents. The investigations revealed that electrochemical surface treatment contributed to an increase in the adsorption capacity by a factor of two only for natural vein graphite. Un-treated recycled vein graphite adsorbent delivered the same adsorptive capacity (3.0 mg g^?1) to that of electrochemically treated natural vein graphite. The electrochemical regeneration efficiency at around 100% was obtained using a treatment time of 60 and 30 min, current density of 14 mA cm^?2, charge passed of 36 and 18 C g^?1 for synthetic graphite, natural and recycled vein graphite materials respectively. Relatively a small consumption of electrical energy, 24 J g^?1 for regenerating natural vein graphite adsorbent versus 36 J g^?1 for synthetic graphite adsorbent, was found to be required for destruction/oxidation of adsorbed acid violet 17. Multiple adsorption/regeneration cycles presented no loss in adsorptive capacity over 5 adsorption/regeneration cycles. The use of natural and recycled vein graphite adsorbents offered some advantages over graphite intercalation based adsorbents with reduced electrical energy consumption during regeneration and simpler separation of particulate adsorbent.     

Single step preparation of meso-porous and reduced graphene oxide by gamma-ray irradiation in gaseous phase

A facile and highly efficient route to produce simultaneously porous and reduced graphene oxide by gamma ray irradiation in hydrogen is here demonstrated. Narrowly distributed nano-scale pores (average size of ∼3 nm and surface density >44,900 pore μm⁻²) were generated across 10 μm thick graphene oxide bucky-papers at a total irradiation dose of 500 kGy. The graphene oxide sheet reduction was confirmed to occur homogeneously across the structures by Fourier transform infrared spectroscopy and Raman analysis. This one-step, catalyst-free, high penetration and through-put technique, offers great promises potential for the mass production of reduced graphene oxide from cheap graphene oxide.     

Carbon nanotubes growth in AlPO4-5 zeolites: Evidence for density dependent field emission characteristics

We report on the correlation between the concentration of Fe-catalyst, doped in the aluminum phosphate (AlPO₄-5) zeolite and the resulting density of carbon nanotubes (CNTs) to obtain the optimum electron field emission conditions from the CNTs. Initially, AlPO₄-5 crystallites were impregnated, for a period of ∼ 10–60 min, in the Fe-catalyst solution and subjected to Electron Spectroscopy for Chemical Analysis (E.S.C.A.). The analysis revealed that the concentration of Fe-catalyst, C_Fe, was increased from ∼ 1.7% to ∼ 8.6%, respectively, with increase in impregnation time, I_T. The HRTEM results showed that Fe nano-clusters, with diameter ∼ 7–10 nm, were formed in the surface region of the crystallites. These crystallites were sprayed on the conducting substrates, under identical spraying conditions. SEM study revealed that the coverage of the crystallites on the substrates was ∼ 10³–10⁴ crystallites/cm². These substrates were subjected to direct current plasma enhanced chemical vapor deposition (dc-PECVD) process, to grow CNTs. The SEM micrographs were recorded for the CNT-grown substrates and the average areal density of CNTs, (σ_T)_av, on the crystallites (t/cm²) was estimated. The analysis indicated that (σ_T)_av increased from ∼ 6.24 ± 0.19 × 10¹⁰ to 2.04 ± 0.61 × 10¹¹ t/cm² with gradual increase in C_Fe. The field emission study of the samples revealed that the optimum values of the turn-on electric field, ∼ 3.69 V/μm and the field emission current density, ρ_d, ∼ 1.78 × 10³ μA/cm² were achieved for (σ_T)_av, ∼ 6.24 ± 0.19 × 10¹⁰ t/cm², at a concentration of Fe, C_Fe, ∼ 3.0%, encapsulated in the AlPO₄-5 crystallites.     

Studies on structural,morphological, electrical and electrochemical properties of activated carbon prepared from sugarcane bagasse

Activated carbon composite was prepared from sugarcane bagasse. The X-ray diffraction revealed the evolution of crystallites of carbon and silica during activation at higher temperature. FTIR spectrum shows the presence of functional groups and silica in the carbon composite. The morphology of the carbon sample was determined by SEM. The surface area, pore volume and pore size distribution of carbon composites were measured. The dc conductivity was determined and conductivity at room temperature was found to increase from 10.22 × 10^?3 to 25.131 × 10^?3 S cm^?1. The samples show good electrochemical property and the specific capacitance in the range of 92–340 F g^?1.     

Tribological study of amorphous BC4N coatings

Amorphous BC₄N thin films with a thickness of ∼ 2 μm have been deposited by Ion Beam Assisted Deposition (IBAD) on hard steels substrates, in order to study the wear behavior under high loads and the applicability as protective coatings. The bonding structure of the a-BC₄N film was assessed by X-ray Absorption Near Edge Spectroscopy (XANES) and Infrared Spectroscopy, indicating atomic mixing of B–C–N atoms, with a proportion of ∼ 70% sp² hybrids and ∼ 30% sp³ hybrids. Nanoindentation shows a hardness of ∼ 18 GPa and an elastic modulus of ∼ 170 GPa. A detailed tribological study is performed by pin-on-disk tests, combined with spectromicroscopy of the wear track at the coating and wear scar at pin. The tests were performed at ambient conditions, against WC/Co counterface balls under loads up to 30 N, with the sample rotating at 375 rpm. The coatings suffer a continuous wear, at a constant rate of 2 × 10^− 7 mm³/Nm, without catastrophic failure due to film spallation, and show a coefficient of friction of ∼ 0.2.     

Direct electrochemical reduction of titanium dioxide in molten lithium chloride

The electrochemical reduction of TiO₂ has been carried out in a molten LiCl salt at 650 °C. The direct reduction mechanism of TiO₂ in the molten LiCl was suggested by the CV experiment and the constant voltage electrolysis. TiO₂ was electrochemically converted to the metallic titanium via various reaction intermediates such as LiTiO₂, TiO, and Ti₂O. The interrupted voltage electrolysis was demonstrated to be effective for the direct electrochemical reduction of TiO₂ to achieve a high current efficiency. The surface morphology of the produced metal was investigated by SEM and TEM.     

High-surface area carbons from renewable sources with a bimodal micro-mesoporosity for high-performance ionic liquid-based supercapacitors

Highly porous materials with a bimodal pore size distribution in the micro-mesopore range have been produced from biomass by adding melamine to the hydrochar/KOH mixture used in the activation process. These carbons are characterized by BET surface areas in excess of ∼3300 m² g⁻¹ and a porosity equally distributed between micropores and mesopores. The use of melamine in the synthesis process not only extends the pore size distribution into the mesopore region, but leads to the incorporation of a certain amount of nitrogen atoms into the carbon framework. These materials combine high ion adsorption capacities (micropores) and enhanced ion-transport kinetics (mesopores) leading to an outstanding capacitive performance in ionic liquid-based supercapacitors. Thus, they have specific capacitances >160 F g⁻¹ at 1 A g⁻¹ and >140 F g⁻¹ at 60 A g⁻¹ in both pure ionic liquid and in acetonitrile-diluted ionic liquid, enabling these materials to store up to a maximum of ca. 60 W h kg⁻¹ in both kinds of electrolytes and deliver ca. 20 W h kg⁻¹ at ∼42 kW kg⁻¹ (discharge time ca. 2 s) in pure ionic liquid and ∼25–30 W h kg⁻¹ at ∼97–100 kW kg⁻¹ (discharge time ∼1 s) in acetonitrile-diluted ionic liquid.