Design of an aluminium ion battery with a graphyne host: lowest volume expansion, high stability and low diffusion barriers.

Commercialization of aluminium ion battery (AIB) requires limited volume expansion of the host cathode materials after AlCl4 intercalation, lower activation barrier, high theoretical specific capacity (TSC), cyclic durability and thermodynamic stability. Most of the carbon and non-carbon based cathode hosts explored so far failed to address the issue of volume expansion and there is a lack of clarity about thermodynamic stability. In this work, we employed multipronged first principles computational approaches on α- and γ-graphyne (GY) and showed that α-GY as a promising cathode host addresses each of the above concerns. Both α and γ-GYs provide ample space to accommodate more number of AlCl4 molecules leading to a high TSC of 186 mA h g-1 and open circuit voltages of 2.18 and 2.22 V, respectively. The absence of bond dissociation of AlCl4 and deformation of GY sheets at 300 and 600 K, as revealed by ab initio molecular dynamics (AIMD) simulation, indicates the stability of α- and γ-GY with adsorbed AlCl4. α-GY after intercalation shows a volume expansion of 186% which is the lowest among the cathode materials studied so far. The negligible expansion energy per unit surface area (∼0.003 eV Å-2) ensures the reversibility and hence cyclic durability of α-GY. Although the γ-GY shows a volume expansion of 249%, it is still promising. The NEB based diffusion study on monolayer and bilayer GY estimates the activation barriers to be (0.26, 0.06 eV) and (0.42, 0.16 eV) for α and γ phases, respectively. These values are either comparable to or lower than those of earlier reported cathode hosts.

A modified bulge test for in-situ study of ionic permeation properties of membranes under continuously tunable, uniform pressure.

The bulge test is a well-known material test to measure the mechanical properties of metal plates, thin films, and membranes. Also, two different experimental setups are needed to apply pressure and make a measurement. In this work, we describe a modified bulge test to both apply pressure and measure the electrical and ionic permeation properties of membranes in situ. A membrane, clamped at its periphery, with a circular window for measurement, is sandwiched between two liquids. The liquids serve dual purpose by facilitating the application of differential pressure and thus stress, by controlling the extent of immersion of the membrane in the liquid below the membrane, as well as enabling measurement of electrical and mass percolation properties. This was achieved with a stepper motor, a load cell, and a microcontroller. Relevant mathematical models are developed and discussed. Nafion was used to test and validate this approach, using electroimpedance spectroscopy in a 2-electrode configuration with gallium on both sides and in a 3-electrode configuration with electrolyte on one side and gallium on the other. Frequency-dependent response was modeled using equivalent circuits. The resistance of Nafion increases with the depth of immersion and therefore applied pressure. For Nafion in the 2-electrode configuration, conductivity was calculated to be ∼6.4 × 10-3 S/cm at the equilibrium position, where stress on the membrane is zero. This value matches well with existing literature values for partially hydrated Nafion. Also, it was observed that the response is symmetric about the equilibrium position.

Highly sensitive and selective non enzymatic electrochemical glucose sensors based on Graphene Oxide-Molecular Imprinted Polymer.

Graphene Oxide-Molecular Imprinted Polymer (GO-MIP) based electrochemical sensor was developed for the first time towards enzyme less determination of glucose. This GO-MIP was obtained from a series of fictionalization, polymerization and template molecule introduction/removal during the synthesizing process. The proposed GO-MIP based electrode showed excellent electrocatalytic activity towards glucose oxidation at optimized conditions and possessing detection limit of 0.1nM with a response time of ~2min. The current response of GO-MIP based glucose sensor was linearly related to the concentration of glucose. The results obtained from the real time usability of electrodes in human blood matches well with commercially available glucose monitors. Further, the reusability of the material is checked up to eight cycles and interference of glucose with ascorbic acid (AA), uric acid (UA) and dopamine (DA) were also studied. The obtained results endorse the promising application of GO-MIP towards superior glucose sensing with long term stability.

Application of Few-Layered Reduced Graphene Oxide Nanofluid as a Working Fluid for Direct Absorption Solar Collectors.

Direct absorption solar collectors (DASC) convert solar energy into heat energy and transfer this heat energy to a carrier fluid. Numerical and experimental studies have shown that replacing the absorber medium with nanofluids in DASC increases the efficiency of solar collector significantly. Present work investigates the dispersion stability, optical and thermal properties of reduced few-layered graphene oxide (rGO) dispersed nanofluids for DASC. The synthesis of rGO was carried out by hydrogen exfoliation of graphene oxide at 200 °C. As-synthesized rGO was suitably functionalized to impart the hydrophilic nature. Different characterization techniques were employed to analyze the surface morphology of the sample. Nanofluids were prepared by dispersing calculated amount of functionalized rGO in DI water and ethylene glycol. Optical properties study reveals that the nanofluids exhibit good absorption ability over base fluids. The extinction coefficient of nanofluids showed significant improvement even at low concentration. Furthermore, the temperature dependent thermal conductivity study with different volume fractions, carried out for DI water and ethylene glycol-based nanofluids, shows considerable enhancement.

Tri-iodide reduction activity of ultra-small size PtFe nanoparticles supported nitrogen-doped graphene as counter electrode for dye-sensitized solar cell.

Efficient and cost effective counter electrode (CE) is pre-requisite for the commercialization of dye-sensitized solar cell (DSSC). Present work investigates ultra small size platinum-iron alloy nanoparticles dispersed over nitrogen-doped graphene (PtFe/NG) as an effective counter electrode for DSSC. Hereby we achieve low loading of Pt by alloying with Fe accompanied by superior electrocatalytic activity towards the iodide-triiodide (I-/I3-) mechanism. Enhancement in electrocatalytic performance of PtFe/NG has been shown by cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization analysis. PtFe/NG counter electrode exhibits higher power conversion efficiency (∼6.12%) with lower charge transfer resistance, which helps in faster diffusion of I-/I3- ions as compared to NG and Pt/NG counter electrodes. The increased electrocatalytic activity of PtFe/NG is due to the collective effect of intrinsic electronic effects by alloying, uniform dispersion of small PtFe alloy nanoparticles over nitrogen doped graphene, and additional catalytic sites offered by nitrogen-doped graphene.

pH Responsive Release of Doxorubicin to the Cancer Cells by Functionalized Multi-Walled Carbon Nanotubes.

The main aim of the current study is to formulate the Doxorubicin loaded functionalized carbon nanotubes to deliver the drug only to the cancer cells by using pH difference. Multi walled Carbon Nanotubes (MWNTs) have been identified as an efficient drug carrier through π-π linkage, because this covalent bond is sensitive to tumor microenvironments. This bond is acid cleavable, thereby providing a strong pH-responsive drug release, which may facilitate effective release near the acidic tumor microenvironment and thus reduces its overall systemic toxicity. Doxorubicin was released at low pH and taken up by tumor cells via adenosine triphosphate (ATP)-dependent endocytosis. By varying the Concentration of MWNTs with the Doxorubicin, it forms a conjugate. It is due to supra molecular interactions between the drug and MWNTs, so it shows high loading, prolonged release and improved cytotoxicity against cancer cells. This study shows the phenomenal pH responsive drug release to the cancerous microenvironment and prolonged release. This study suggests that MWNTs have a great potential as a drug carrier; the efficient formulation strategy requires further study.

Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine.

The fabrication of a novel amperometric biosensor based on selective determination of dopamine (DA) using nafion coated cerium oxide nanoparticles (NPs) decorated graphene nanosheets (CeO2-HEG-nafion) as a transducer candidate is reported. Graphene was synthesized by hydrogen exfoliation technique. Decoration of CeO2NPs over graphene nanosheets was done by chemical reduction method. The electrochemical impedance spectroscopy (EIS) study shows the enhanced electron transfer kinetics of the composite compared to HEG modified and bare glassy carbon electrode (GCE). The response of the composite towards dopamine displays a lower oxidation potential of 0.23 V and a high oxidation current. The sensor exhibits linearity from 10 µM to 780 µM with a detection limit of 1 µM. In the presence of nafion, it shows excellent selectivity for coexisting interference species like Ascorbic acid (AA) and Uric acid (UA). The excellent performance of the biosensor can be attributed to large active surface area, enhanced electron transfer kinetics and high catalytic activity of the composite.

Nitrogen-Doped Graphene for Ionic Liquid Based Supercapacitors.

Graphene is a promising electrode material for supercapacitor applications due to its unique properties. Interaction of electrolyte ions with graphene lattice sites is a crucial factor in ionic liquid electrolyte based supercapacitors. In an effort to increase the interaction of high viscous electrolyte with electrode material, here, we here report the results of a systematic study carried out on a supercapacitor with nitrogen doped graphene as electrode material and [BMIM][TFSI] as electrolyte. In this study, nitrogen doped hydrogen exfoliated graphene (N-HEG) is prepared by radio frequency (R.F) magnetron sputtering and employed as electrode material for [BMIM][TFSI] electrolyte based high performance supercapacitor. N-HEG shows a high specific capacitance of 170.1 F/g compared to that of electrolyte modified graphene (124.5 F/g), at a specific current of 2 A/g. The improved performance of N-HEG based supercapacitor is attributed to the presence of nitrogen atoms in the graphene lattice which in turn increases the lattice-ion interaction and the electrical conductivity. In addition, the presence of wrinkles on the graphene surface provides a shortest directional path to access pores and surface. The device shows high charge storage capacity (72.37 Wh/kg) along with wide operating voltage (3.5 V) and high cyclic stability.

Enhanced electrochemical performance by unfolding a few wings of graphene nanoribbons of multiwalled carbon nanotubes as an anode material for Li ion battery applications.

The present work provides an incredible route towards achieving the ideal Li ion battery anode material with high specific capacity and rate capability as a result of unraveling a few upper layers of multiwalled carbon nanotubes (MWNTs) as graphene nanoribbons attached to the core MWNT. These partially exfoliated nanotubes when used as an anode material show an 880 mA h g(-1) capacity at a 100 mA g(-1) current density and high rate capability by delivering a stable 157 mA h g(-1) capacity at a current density of 10 A g(-1). The enhanced performance of this anode material can be attributed to the synergistic effect of the homogeneous distribution of the hybrid carbon nanostructure of 1-D multiwalled carbon nanotubes and 2-D graphene nanoribbons. This configuration provides a large available surface area, high electrical conductivity and a high number of defect sites, leading to improved Li intercalation with a better transfer rate compared to only graphene, multiwalled carbon nanotubes or other reported combinations of the two.

Hydrogen storage in platinum decorated hydrogen exfoliated graphene sheets by spillover mechanism.

Development of lightweight materials with high hydrogen storage capacities is a great challenge for the hydrogen economy. Here, we report high pressure hydrogen adsorption-desorption studies of platinum-decorated hydrogen-exfoliated graphene sheets (Pt-HEG). Pt-HEG shows a maximum hydrogen uptake capacity of 1.4 wt% at 25 °C and 3 MPa. Analysis of the isosteric heat of adsorption provides evidence of spillover mechanism.

Synthesis and characterization of gold graphene composite with dyes as model substrates for decolorization: a surfactant free laser ablation approach.

A facile surfactant free laser ablation mediated synthesis (LAMS) of gold-graphene composite is reported here. The material was characterized using transmission electron microscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, powdered X-ray diffraction, Raman spectroscopy, Zeta potential measurements and UV-Visible spectroscopic techniques. The as-synthesized gold-graphene composite was effectively utilized as catalyst for decolorization of 4 important textile and laser dyes. The integration of gold nanoparticles (AuNPs) with high surface area graphene has enhanced the catalytic activity of AuNPs. This enhanced activity is attributed to the synergistic interplay of pristine gold's electronic relay and π-π stacking of graphene with the dyes. This is evident when the Rhodamine B (RB) reduction rate of the composite is nearly twice faster than that of commercial citrate capped AuNPs of similar size. In case of Methylene blue (MB) the rate of reduction is 17,000 times faster than uncatalyzed reaction. This synthetic method opens door to laser ablation based fabrication of metal catalysts on graphene for improved performance without the aid of linkers and surfactants.

Variations in magnetic properties of nanostructured nickel.

The magnetic properties of carbon nanotube encapsulated nickel nanowires (C.E. nanowires of diameter to approximately 10 nm), and its comparison to other forms of Ni are carried out in this work. The saturation magnetization (Ms) and coercivity (Hc) for C.E. nanowires are 1.0 emu/g and 230 Oe. The temperature dependence of coercivity follows T0.77 dependence indicating a superparamagnetic behavior. The field-cooled and zero-field-cooled plots indicate that the blocking temperature (T(B)) to approximately 300 K. These altered magnetic properties of C.E. nanowires are mainly due to the nanoscale confinement effect from carbon nanotube encapsulation. The shape and magnetic environment enhance the total magnetic anisotropy of C.E. nanowires by a factor of four.

Platinum-TM (TM = Fe, Co) alloy nanoparticles dispersed nitrogen doped (reduced graphene oxide-multiwalled carbon nanotube) hybrid structure cathode electrocatalysts for high performance PEMFC applications.

The efforts to push proton exchange membrane fuel cells (PEMFC) for commercial applications are being undertaken globally. In PEMFC, the sluggish kinetics of oxygen reduction reactions (ORR) at the cathode can be improved by the alloying of platinum with 3d-transition metals (TM = Fe, Co, etc.) and with nitrogen doping, and in the present work we have combined both of these aspects. We describe a facile method for the synthesis of a nitrogen doped (reduced graphene oxide (rGO)-multiwalled carbon nanotubes (MWNTs)) hybrid structure (N-(G-MWNTs)) by the uniform coating of a nitrogen containing polymer over the surface of the hybrid structure (positively surface charged rGO-negatively surface charged MWNTs) followed by the pyrolysis of these (rGO-MWNTs) hybrid structure-polymer composites. The N-(G-MWNTs) hybrid structure is used as a catalyst support for the dispersion of platinum (Pt), platinum-iron (Pt3Fe) and platinum-cobalt (Pt3Co) alloy nanoparticles. The PEMFC performances of Pt-TM alloy nanoparticle dispersed N-(G-MWNTs) hybrid structure electrocatalysts are 5.0 times higher than that of commercial Pt-C electrocatalysts along with very good stability under acidic environment conditions. This work demonstrates a considerable improvement in performance compared to existing cathode electrocatalysts being used in PEMFC and can be extended to the synthesis of metal, metal oxides or metal alloy nanoparticle decorated nitrogen doped carbon nanostructures for various electrochemical energy applications.

Hydrogen storage studies of palladium decorated nitrogen doped graphene nanoplatelets.

Hydrogen storage in materials is of significant importance in the present scenario of depleting conventional energy sources. Porous solids such as activated carbon or nanostructured carbon materials have promising future as hydrogen storage media. The hydrogen storage capacity in nanostructured carbon materials can be further enhanced by atomic hydrogen spillover from a supported catalyst. In the present work, the hydrogen storage properties of nitrogen doped graphene nanoplatelets (N-GNP) and palladium decorated nitrogen doped graphene nanoplatelets (Pd/N-GNP) have been investigated. The results show that hydrogen uptake capacity of nitrogen doped graphene nanoplatelets and palladium decorated nitrogen doped graphene nanoplatelets at pressure 32 bar and temperature 25 degrees C is 0.42 wt% and 1.25 wt% respectively. The dispersion of palladium nanoparticles increases the hydrogen storage capacity of nitrogen doped graphene nanoplatelets by 0.83 wt%. This may be due to high dispersion of palladium nanoparticles and strong adhesion between metal and graphene nanoplatelets over the surface of N-GNP, which enhances the spillover mechanism. Thus, an increase in the hydrogen spillover effect and the binding energy between metal nanoparticles and supporting material achieved by nitrogen doping has been observed to result in a higher hydrogen storage capacity of pristine GNP.

Synthesis and thermal transport studies of nanofluids based on metal decorated photochemically oxidized multiwalled carbon nanotubes.

Nanoparticle fluid suspensions were prepared using photochemically functionalized multiwalled carbon nanotubes in polar base fluids. Multiwalled carbon nanotubes prepared by catalytic chemical vapour deposition technique have been functionalized by irradiating with ultraviolet light of wavelength 254 nm. The photochemical oxidation of multiwalled carbon nanotubes under UV irradiation introduces oxygen containing functional groups onto the surface of the nanotubes, generating new defects on their structure. Silver nanoparticles have been deposited over multiwalled carbon nanotubes by chemical method. The enhancement in thermal conductivity of the prepared nanofluids using functionalized multiwalled carbon nanotubes and Ag nanoparticles deposited functionalized multiwalled carbon nanotubes with volume fraction, temperature and aspect ratio has been demonstrated. Silver deposited functionalized multiwalled carbon nanotubes based nanofluids in DI water with 0.02% volume fraction exhibit a thermal conductivity enhancement of 9.9% and 47% at room temperature and at 50 degrees C respectively.

Graphite nanoplatelets/multiwalled carbon nanotubes hybrid nanostructure for electrochemical capacitor.

Recently, the focus on carbon based nanostructures for various applications has been due to their novel properties such as high electrical conductivity, high mechanical strength and high surface area. In the present work, we have investigated the charge storage capacity of modified graphite nanoplatelets and hybrid structure of graphite nanoplatelets-multiwalled carbon nanotubes (MWNTs). These MWNTs can be used as spacers to reduce the possibility of restacking of graphite nanoplatelets and hence increases the surface area of the hybrid carbon nanostructure thereby high degree of metal oxide decoration is achieved over the hybrid structure. MWNTs were prepared by catalytic chemical vapor deposition technique and further purified with air oxidation and acid treatment. Graphite was treated with conc. nitric acid and sulphuric acid in the volumetric ratio of 1:3 for 3 days and these modified graphite nanoplatelets were further stirred with MWNTs in equal weight ratio to form hybrid nanostructure. Further, ruthenium oxide (RuO2) nanoparticles were decorated on this hybrid structure using chemical route followed by calcination. RuO2 decorated hybrid carbon nanostructure was characterized by using X-ray diffraction, Electron microscopy and Raman spectroscopy. The performance of the hybrid structure based nanocomposite as electrochemical capacitor electrodes was analyzed by studing its capacitive and charge-discharge behaviours using cyclic voltammetry and chronopotentiometry techniques and the results have been discussed.

Cerium oxide dispersed multi walled carbon nanotubes as cathode material for flexible field emitters.

Nanomaterials based electron sources are omnipresent in modern flat panel displays. Multi walled carbon nanotubes (MWNT) are the well studied electron emitter among the carbon materials. Since the surface modification of MWNT with low work function materials would have a positive impact on the field emission property of MWNT, cerium oxide (CeO2) nanoparticles dispersed multi walled carbon nanotubes (CeO2/MWNT) were synthesized by catalytic chemical vapour deposition followed by chemical reduction and its field emission property was investigated. The high-purity MWNT as well as CeO2/MWNT showed crystalline structure conformed by X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Further characterisation was done with Raman spectroscopy, UV-Visible absorption spectra and Fourier transform IR spectroscopy (FT-IR). The morphology and structural details of CeO2/MWNT composite was probed by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX). The direct evidence of the formation of CeO2/MWNT composites was given by transmission electron microscopy (TEM). The synthesized sample was coated over a flexible carbon paper using spin coating technique. The experiment was performed under a vacuum of 1 x 10(-6) Torr and Fowler-Nordheim equation was used to analyse the data. The turn-on voltage for the cerium oxide dispersed MWNT was found for a current density of 10 microA/cm2. The emission current density from the CeO2 nanoparticles dispersed MWNT reached 0.2 mA/cm2 at a reasonable bias field of 2.58 V/microm. The results were compared with those of pure MWNT and pure CeO2 nanoparticles with literature values.

Effect of nitrogen doping on hydrogen storage capacity of palladium decorated graphene.

A high hydrogen storage capacity for palladium decorated nitrogen-doped hydrogen exfoliated graphene nanocomposite is demonstrated under moderate temperature and pressure conditions. The nitrogen doping of hydrogen exfoliated graphene is done by nitrogen plasma treatment, and palladium nanoparticles are decorated over nitrogen-doped graphene by a modified polyol reduction technique. An increase of 66% is achieved by nitrogen doping in the hydrogen uptake capacity of hydrogen exfoliated graphene at room temperature and 2 MPa pressure. A further enhancement by 124% is attained in the hydrogen uptake capacity by palladium nanoparticle (Pd NP) decoration over nitrogen-doped graphene. The high dispersion of Pd NP over nitrogen-doped graphene sheets and strengthened interaction between the nitrogen-doped graphene sheets and Pd NP catalyze the dissociation of hydrogen molecules and subsequent migration of hydrogen atoms on the doped graphene sheets. The results of a systematic study on graphene, nitrogen-doped graphene, and palladium decorated nitrogen-doped graphene nanocomposites are discussed. A nexus between the catalyst support and catalyst particles is believed to yield the high hydrogen uptake capacities obtained.

Non-enzymatic amperometric glucose biosensor from zinc oxide nanoparticles decorated multi-walled carbon nanotubes.

The present work describes the development of novel ZnO dispersed multi-walled carbon nanotubes (MWNT) based non-enzymatic glucose biosensor with 1 M NaOH solution as the supporting electrolyte. For a comparison, the same material has been used for the fabrication of enzymatic biosensor and studied its electrochemical activity with phosphate buffer solution as the electrolyte. MWNT have been synthesized by catalytic chemical vapor decomposition (CCVD) and a simple sol-gel method was used for decorating crystalline ZnO nanoparticles on MWNT. Cyclic voltammetry and chronoamperometry were used to study and optimize the electrochemical performance of the resulting enzymatic and non-enzymatic ZnO/MWNT biosensors. The non enzymatic Nafion/ZnO/MWNT/GC electrode shows linearity in the range 700 nM to 31 mM with the detection limit of 500 nM. Similarly enzymatic biosensor fabricated using Nafion/GOD/ZnO/MWNT on glassy carbon electrode (GCE) shows a linearity from 1 microM to 22 mM. This excellent performance of non enzymatic Nafion/ZnO/MWNT/GC is due to high surface area, good electron transfer rate of ZnO/MWNT and the high electrochemical catalytic activity of ZnO in NaOH solution.

Correlated conformation and charge transport in multiwall carbon nanotube-conducting polymer nanocomposites.

The strikingly different charge transport behaviours in nanocomposites of multiwall carbon nanotubes (MWNTs) and conducting polymer polyethylenedioxythiophene-polystyrene-sulfonic-acid (PEDOT-PSS) at low temperatures are explained by probing their conformational properties using small-angle x-ray scattering (SAXS). The SAXS studies indicate the assembly of elongated PEDOT-PSS globules on the walls of nanotubes, coating them partially, thereby limiting the interaction between the nanotubes in the polymer matrix. This results in a charge transport governed mainly by small polarons in the conducting polymer despite the presence of metallic MWNTs. At T > 4 K, hopping of the charge carriers following one-dimensional variable range hopping is evident which also gives rise to a positive magnetoresistance (MR) with an enhanced localization length (∼5 nm) due to the presence of MWNTs. However, at T < 4 K, the observation of an unconventional positive temperature coefficient of resistivity is attributed to small polaron tunnelling. The exceptionally large negative MR observed in this temperature regime is conjectured to be due to the presence of quasi-1D MWNTs that can aid in lowering the tunnelling barrier across the nanotube-polymer boundary resulting in large delocalization.