Nonvolatile unipolar resistive switching in ultrathin films of graphene and carbon nanotubes

We report unipolar resistive switching in ultrathin films of chemically produced graphene (reduced graphene oxide) and multiwalled carbon nanotubes. The two-terminal devices with yield >99% are made at room temperature by forming continuous films of graphene of thickness similar to 20 nm on indium tin oxide coated glass electrode, followed by metal (Au or Al) deposition on the film. These memory devices are nonvolatile, rewritable with ON/OFF ratios up to similar to 10(5) and switching times up to 10 mu s. The devices made of MWNT films are rewritable with ON/OFF ratios up to similar to 400. The resistive switching mechanism is proposed to be nanogap formation and filamentary conduction paths. (C) 2011 Elsevier Ltd. All rights reserved.

V(2)O(5)-Anchored Carbon Nanotubes for Enhanced Electrochemical Energy Storage

Functionalized multiwalled carbon nanotubes (CNTs) are coated with a 4-5 nm thin layer of V(2)O(5) by controlled hydrolysis of vanadium alkoxide. The resulting V(2)O(5)/CNT composite has been investigated for electrochemical activity with lithium ion, and the capacity value shows both faradaic and capacitive (nonfaradaic) contributions. At high rate (1 C), the capacitive behavior dominates the intercalation as 2/3 of the overall capacity value out of 2700 C/g is capacitive, while the remaining is due to Li-ion intercalation. These numbers are in agreement with the Trasatti plots and are corroborated by X-ray photoelectron spectroscopy (XPS) studies on the V(2)O(5)/CNTs electrode, which show 85% of vanadium in the +4 oxidation state after the discharge at 1 C rate. The cumulative high-capacity value is attributed to the unique property of the nano V(2)O(5)/CNTs composite, which provides a short diffusion path for Lit-ions and an easy access to vanadium redox centers besides the high conductivity of CNTs. The composite architecture exhibits both high power density and high energy density, stressing the benefits of using carbon substrates to design high performance supercapacitor electrodes.

Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

1.5 V battery driven reduced graphene oxide-silver nanostructure coated carbon foam (rGO-Ag-CF) for the purification of drinking water

A porous carbon foam (CF) electrode modified with a reduced graphene oxide-Ag (rGO-Ag) nanocomposite has been fabricated to purify water. It can perform as an antibacterial device by killing pathogenic microbes with the aid of a 1.5 V battery, with very little power consumption. The device is recycled ten times with good performance for long term usage. It is shown that the device may be implemented as a fast water purifier to deactivate the pathogens in drinking water.

Carbonaceous nickel oxide nano-composites: as electrode materials in electrochemical capacitor applications

Carbonaceous nickel oxide powder samples have been synthesized from an adducted nickel beta-ketoester complex used as a ``single source precursor'' through a solution-based microwave-assisted chemical route. Comprehensive analysis of the resulting powder material has been carried out using various characterization techniques. These analysis reveal that, depending on the solvent used, either NiO/C or Ni/NiO/C composites are formed, wherein Ni and/or NiO nanocrystals are enveloped in amorphous carbon. As the components emerge from the same molecular source, the composites are homogeneous on a fine scale, making them promising electrode materials for supercapacitors. Electrochemical capacitive behavior of these oxide composites is studied in a three-electrode configuration. With a specific capacitance of 113 F g(-1), Ni/NiO/C is superior to NiO/C as capacitor electrode material, in 0.1 M Na2SO4 electrolyte. This is confirmed by impedance measurements, which show that charge-transfer resistance and equivalent series resistance are lower in Ni/NiO/C than in NiO/C, presumably because of the presence of metallic nickel in the former. The cyclic voltammograms are nearly rectangular and the electrodes display excellent cyclability in different electrolytes: Na2SO4, KOH and Ca(NO3)(2)center dot 4H(2)O. Specific capacitance as high as 143 F g(-1), is measured in Ca(NO3)(2)center dot 4H(2)O electrolyte.

Influence of binder solvent on carbon-layer structure in electrical-double-layer capacitors

Porous activated-carbons with a large surface-area have been the most common materials for electrical-double-layer capacitors (EDLCs). These carbons having a wide pore distribution ranges from micropores to macropores in conjunction with a random pore connection that facilitates the high specific-capacitance values. Pore distribution plays a central role in controlling the capacitance value of EDLCs, since electrolyte distribution inside the active material mainly depends on the pore distribution. This has a direct influence on the distribution of resistance and capacitance values within the electrode. As a result, preparation of electrodes remains a vital issue in realising high-performance EDLCs. Generally, carbon materials along with some binders are dispersed into a solvent and coated onto the current collectors. This study examines the role of binder solvents used for the carbon-ink preparation on the microstructure of the electrodes and the consequent performance of the EDLCs. It is observed that the physical properties of the binder solvent namely its dielectric constant, viscosity and boiling point have important role in determining the pore-size distribution as well as the microstructure of electrodes which influence their specific capacitance values.

Glassy dielectric response in Tb2NiMnO6 double perovskite with similarities to a Griffiths phase

Results of frequency-dependent and temperature-dependent dielectric measurements performed on the double-perovskite Tb2NiMnO6 are presented. The real (epsilon(1)(f,T)) and imaginary (epsilon(2)(f,T)) parts of dielectric permittivity show three plateaus suggesting dielectric relaxation originating from the bulk, grain boundaries and the sample-electrode interfaces, respectively. The epsilon(1)(f,T) and epsilon(2)(f,T) are successfully simulated by a RC circuit model. The complex plane of impedance, Z'-Z `', is simulated using a series network with a resistor R and a constant phase element. Through the analysis of epsilon(f,T) using the modified Debye model, two different relaxation time regimes separated by a characteristic temperature, T*, are identified. The temperature variation of R and C corresponding to the bulk and the parameter alpha from modified Debye fit lend support to this hypothesis. Interestingly, the T* compares with the Griffiths temperature for this compound observed in magnetic measurements. Though these results cannot be interpreted as magnetoelectric coupling, the relationship between lattice and magnetism is markedly clear. We assume that the observed features have their origin in the polar nanoregions which originate from the inherent cationic defect structure of double perovskites. Copyright (C) EPLA, 2013

Titania nanotube-modified screen printed carbon electrodes enhance the sensitivity in the electrochemical detection of proteins

The use of titania nanotubes (TiO2-NT) as the working electrode provides a substantial improvement in the electrochemical detection of proteins. A biosensor designed using this strategy provided a robust method to detect protein samples at very low concentrations (C-protein ca 1 ng/mu l). Reproducible measurements on protein samples at this concentration (I-p,I-a of 80 +/- 1.2 mu A) could be achieved using a sample volume of ca 30 mu l. We demonstrate the feasibility of this strategy for the accurate detection of penicillin binding protein, PBP2a, a marker for methicillin resistant Staphylococcus aureus (MRSA). The selectivity and efficiency of this sensor were also validated using other diverse protein preparations such as a recombinant protein tyrosine phosphatase (PTP10D) and bovine serum albumin (BSA). This electrochemical method also presents a substantial improvement in the time taken (few minutes) when compared to conventional enzyme-linked immunosorbent assay (ELISA) protocols. It is envisaged that this sensor could substantially aid in the rapid diagnosis of bacterial infections in resource strapped environments. (C) 2014 Elsevier B.V. All rights reserved.

Iminodiacetic acid functionalized polypyrrole modified electrode as Pb(II) sensor: Synthesis and DPASV studies

An electrochemical lead ion sensor has been developed by modification of carbon paste electrode (CPE) using polypyrrole functionalized with iminodiacetic acid (IDA-PPy) containing carboxyl group. The electrochemical response of Pb2+ ion on the IDA-PPy modified CPE has been evaluated and the controling parameters have been optimized using differential pulse anodic stripping voltammetry (DPASV). The IDA-PPy modified CPE shows a linear correlation for Pb2+ concentrations in the range of 1 x 10(-6) to 5 x 10(-9) M and the lower detection limit of Pb2+ has been found to be 9.6 x 10(-9) M concentration. Other tested metal ions, namely Cu2+, Cd2+, Co2+, Hg2+, Ni2+ and Zn2+, do not exhibit any voltammetric stripping response below 1 x 10(-7) M concentration. However, the Pb2+ response is affected in the presence of molar equivalents or higher concentrations of Cu2+, Cd2+ and Co2+ ions in binary systems with Pb2+, consequent to their ability to bind with iminodiacetic acid, while Hg2+, Ni2+ and Zn2+ do not interfere at all. A good correlation has been observed between the lead concentrations as analyzed by DPASV using IDA-PPy modified CPE and atomic absorption spectrophotometry for a lead containing industrial effluent sample. (C) 2014 Elsevier Ltd. All rights reserved.

Iron-carbon hybrid capacitor: A proof-of-concept study

In the present study, cost-intensive Ni electrode is replaced by high surface-area activated carbon (AC) cathode and the possibility of the Fe anode, used in Ni-Fe battery, to function as Fe-C hybrid capacitor has been examined. The electrochemical properties of Fe-C hybrid capacitor assembly are studied using cyclic voltammetry (CV) and galvanostatic charge-discharge cycles. Over 100 galvanostatic charge-discharge cycles for Fe-C hybrid capacitor are carried out and a maximum capacitance of 24 F g(-1) is observed.

Vertical electric field induced bacterial growth inactivation on amorphous carbon electrodes

The objective of the present work is to understand the vertical electric field stimulation of the bacterial cells, when grown on amorphous carbon substrates in vitro. In particular, the antibacterial activity against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli are studied using MTTassay, live/dead assay and inner membrane permeabilization assays. In our experiments, the carbon substrate acts as one electrode and the counter electrode is positioned outside the culture medium, thus suppressing the current, electrokinetic motions and chemical reactions. Guided by similar experiments conducted in our group on neuroblastoma cells, the present experimental results further establish the interdependence of field strength and exposure duration towards bacterial growth inactivation in vitro. Importantly, significant reduction in bacterial viability was recorded at the 2.5 V/cm electric field stimulation conditions, which does not reduce the neural cell viability to any significant extent on an identical substrate. Following electrical stimulation, the bacterial growth is significantly inhibited for S. aureus bacterial strain in an exposure time dependent manner. In summary, our experiments establish the effectiveness of the vertical electric field towards bacterial growth inactivation on amorphous carbon substrates, which is a cell type dependent phenomenon (Gram-positive vs. Gram-negative). (C) 2014 Elsevier Ltd. All rights reserved.

Si-mediated fabrication of reduced graphene oxide and its hybrids for electrode materials

Here, we demonstrate a Si-mediated environmentally friendly reduction of graphene oxide (GO) and the fabrication of its hybrids with multiwall carbon nanotubes and nanofibers. The reduction of GO is facilitated by nascent hydrogen generated by the reaction between Si and KOH at similar to 60 degrees C. The overall process takes 5 to 7 minutes and 10 to 15 mu m of Si is consumed each time. We show that Si can be used multiple times and the rGO based hybrids can be used for electrode materials.

Electrospun SnSb Crystalline Nanoparticles inside Porous Carbon Fibers as a High Stability and Rate Capability Anode for Rechargeable Batteries

In an electrochemical alloying reaction, the electroactive particles become mechanically unstable owing to large volume changes occurring as a result of high amounts of lithium intake. This is detrimental for long-term battery performance. Herein, a novel synthesis approach to minimize such mechanical instabilities in tin particles is presented. An optimal one-dimensional assembly of crystalline single-phase tin-antimony (SnSb) alloy nanoparticles inside porous carbon fibers (abbreviated SnSb-C) is synthesized for the first time by using the electrospinning technique (employing non-oxide precursors) in combination with a sintering protocol. The ability of antimony to alloy independently with lithium is beneficial as it buffers the unfavorable volume changes occurring during successive alloying/dealloying cycles in Sn. The SnSb-C assembly provides nontortuous (tortuosity coefficient, =1) fast conducting pathways for both electrons and ions. The presence of carbon in SnSb-C completely nullifies the conventional requirement of other carbon forms during cell electrode assembly. The SnSb-C exhibited remarkably high electrochemical lithium stability and high specific capacities over a wide range of currents (0.2-5Ag(-1)). In addition to lithium-ion batteries, it is envisaged that SnSb-C also has potential as a noncarbonaceous anode for other battery chemistries, such as sodium-ion batteries.

Synthesis of cadmium oxide and carbon nanotube based nanocomposites and their use as a sensing interface for xanthine detection

Xanthine oxidase (XOD) extracted from bovine milk was immobilized covalently via N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) chemistry onto cadmium oxide nanoparticles (CdO)/carboxylated multiwalled carbon nanotube (c-MWCNT) composite film electrodeposited on the surface of an Au electrode. The nanocomposite modified Au electrode was characterized by Fourier transform infrared (FTIR), cyclic voltammetry (CV), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) before and after immobilization of XOD. Under optimal operation conditions (25 degrees C, + 0.2 V vs. Ag/AgCl, sodium phosphate buffer, pH 7.5), the following characteristics are attributed to the biosensor: linearity of response up to xanthine concentrations of 120 mu M, detection limit of 0.05 mu M (S/N = 3) and a response time of at most 4 s. After being used 100 times over a period of 120 days, only 50% loss of the initial activity of the biosensor was evaluated when stored at 4 degrees C. The fabricated biosensor was successfully employed for the determination of xanthine in fish meat.

Achieving Highly Efficient, Selective, and Stable CO2 Reduction on Nitrogen-Doped Carbon Nanotubes

The challenge in the electrosynthesis of fuels from CO2 is to achieve durable and active performance with cost-effective catalysts. Here, we report that carbon nanotubes (CNTs), doped with nitrogen to form resident electron-rich defects, can act as highly efficient and, more importantly, stable catalysts for the conversion of CO2 to CO. The unprecedented overpotential (-0.18 V) and selectivity (80%) observed on nitrogen-doped CNTs (NCNTs) are attributed to their unique features to facilitate the reaction, including (i) high electrical conductivity, (ii) preferable catalytic sites (pyridinic N defects), and (iii) low free energy for CO2 activation and high barrier for hydrogen evolution. Indeed, DFT calculations show a low free energy barrier for the potential-limiting step to form key intermediate COOH as well as strong binding energy of adsorbed CON and weak binding energy for the adsorbed CO. The highest selective site toward CO production is pyridinic N, and the NCNT-based electrodes exhibit no degradation over 10 h of continuous operation, suggesting the structural stability of the electrode.