Cathodic corrosion of Cu substrates as a route to nanostructured Cu/M (M = Ag, Au, Pd) surfaces

The electrochemical formation of nanostructured materials is generally achieved by reduction of a metal salt onto a substrate that does not influence the composition of the deposit. In this work we report that Ag, Au and Pd electrodeposited onto Cu under conditions where galvanic replacement is not viable and hydrogen gas is evolved results in the formation of nanostructured surfaces that unexpectedly incorporate a high concentration of Cu in the final material. Under cathodic polarization conditions the electrodissolution/corrosion of Cu occurs which provides a source of ionic copper that is reduced at the surface-electrolyte interface. The nanostructured Cu/M (M = Ag, Au and Pd) surfaces are investigated for their catalytic activity for the reduction of 4 nitrophenol by NaBH4 where Cu/Ag was found to be extremely active. This work indicates that a substrate electrode can be utilized in an interesting manner t make bimetallic nanostructures with enhanced catalytic activity.

Electropolymerisation of catalytically active PEDOT from an ionic liquid on a flexible carbon cloth using a sandwich cell configuration

We report the electropolymerization of poly(3,4-ethylenedioxythiopene) (PEDOT) from an ionic liquid, butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (C4mpyrTFSI) onto flexible carbon cloth electrodes. A continuous, homogeneous and well adhered coating of the individual cloth fibres is achieved by employing a sandwich cell arrangement where the carbon cloth which is soaked with electrolyte is placed between two indium tin oxide electrodes isolated from each other by a battery separator. The resultant PEDOT modified carbon cloth electrode demonstrates excellent activity for the oxygen reduction reaction which is due to the doping level, conductivity and morphology of the PEDOT layer and is also tolerant to the presence of methanol in the electrolyte. This simple approach therefore offers a route to fabricate flexible polymer electrodes that could be used in various electronic applications.

Storing energy in plastics : a review on conducting polymers & their role in electrochemical energy storage

Conducting polymers have become the focus of research due to their interesting properties, such as a wide range of conductivity, facile production, mechanical stability, light weight and low cost and due to the ease with which conducting polymers can be nanostructured to meet the specific application. They have become valuable materials for many applications, such as energy storage and generation. Recently, conducting polymers have been studied to be used in supercapacitors, battery electrode and fuel cells. This article is to briefly discuss the background & theory behind their conductivity as well as to highlight the recent contributions of conducting polymers to the field of energy and their significance. Furthermore, the methods of production of the conducting polymers in addition to the different ways utilised to nano-engineer special morphologies are discussed.

Mechanistic details of the membrane perforation and passive translocation of TAT peptides

The trans-activator of transcription (TAT) peptide is regarded as the “gold standard” for cell-penetrating peptides, capable of traversing a mammalian membrane passively into the cytosolic space. This characteristic has been exploited through conjugation of TAT for applications such as drug delivery. However, the process by which TAT achieves membrane penetration remains ambiguous and unresolved. Mechanistic details of TAT peptide action are revealed herein by using three complementary methods: quartz crystal microbalance with dissipation (QCM-D), scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM). When combined, these three scales of measurement define that the membrane uptake of the TAT peptide is by trans-membrane insertion using a “worm-hole” pore that leads to ion permeability across the membrane layer. AFM data provided nanometre-scale visualisation of TAT punctuation using a mammalian-mimetic membrane bilayer. The TAT peptide does not show the same specificity towards a bacterial mimetic membrane and QCM-D and SECM showed that the TAT peptide demonstrates a disruptive action towards these membranes. This investigation supports the energy-independent uptake of the cationic TAT peptide and provides empirical data that clarify the mechanism by which the TAT peptide achieves its membrane activity. The novel use of these three biophysical techniques provides valuable insight into the mechanism for TAT peptide translocation, which is essential for improvements in the cellular delivery of TAT-conjugated cargoes including therapeutic agents required to target specific intracellular locations.

Liquid metal/metal oxide frameworks with incorporated Ga2O3 for photocatalysis

Solvothermally synthesized Ga2O3 nanoparticles are incorporated into liquid metal/metal oxide (LM/MO) frameworks in order to form enhanced photocatalytic systems. The LM/MO frameworks, both with and without incorporated Ga2O3 nanoparticles, show photocatalytic activitydue to a plasmonic effect where performance is related to the loading of Ga2O3 nanoparticles. Optimum photocatalytic efficiency is obtained with 1 wt% incorporation of Ga2O3 nanoparticles. This can be attributed to the sub-bandgap states of LM/MO frameworks, contributing to pseudo-ohmic contacts which reduce the free carrier injection barrier to Ga2O3.

Nanoparticle–electrode collisions as a dynamic seeding route for the growth of metallic nanostructures

The collisions between colloidal metal nanoparticles and a carbon electrode were explored as a dynamic method for the electrodeposition of a diverse range of electrocatalytically active Ag and Au nanostructures whose morphology is dominated by the electrostatic interaction between the charge of the nanoparticle and metal salt.

A simple approach to improve the electrocatalytic properties of commercial Pt/C

Here we demonstrate that commercial carbon supported Pt nanoparticles react with [AuCl4]- ions at room temperature to produce a highly active Au/Pt/C material with an ultralow coverage of elemental Au on the Pt nanoparticles that exhibits significantly enhanced activity for ethanol oxidation when compared to Pt/C.

Electrochemical restructuring of copper surfaces using organic additives and its effect on the electrocatalytic reduction of nitrate ions

This work describes the fabrication of nanostructured copper electrodes using a simple potential cycling protocol that involves oxidation and reduction of the surface in an alkaline solution. It was found that the inclusion of additives, such as benzyl alcohol and phenylacetic acid, has a profound effect on the surface oxidation process and the subsequent reduction of these oxides. This results in not only a morphology change, but also affects the electrocatalytic performance of the electrode for the reduction of nitrate ions. In all cases, the electrocatalytic performance of the restructured electrodes was significantly enhanced compared with the unmodified electrode. The most promising material was formed when phenylacetic acid was used as the additive. In addition, the reduction of residual oxides on the surface after the modification procedure to expose freshly active reaction sites on the surface before nitrate reduction was found to be a significant factor in dictating the overall electrocatalytic activity. It is envisaged that this approach offers an interesting way to fabricate other nanostructured electrode surfaces.

Synergistic fusion of vertical graphene nanosheets and carbon nanotubes for high-performance supercapacitor electrodes

Graphene and carbon nanotubes (CNTs) are attractive electrode materials for supercapacitors. However, challenges such as the substrate-limited growth of CNTs, nanotube bundling in liquid electrolytes, under-utilized basal planes, and stacking of graphene sheets have so far impeded their widespread application. Here we present a hybrid structure formed by the direct growth of CNTs onto vertical graphene nanosheets (VGNS). VGNS are fabricated by a green plasma-assisted method to break down and reconstruct a natural precursor into an ordered graphitic structure. The synergistic combination of CNTs and VGNS overcomes the challenges intrinsic to both materials. The resulting VGNS/CNTs hybrids show a high specific capacitance with good cycling stability. The charge storage is based mainly on the non-Faradaic mechanism. In addition, a series of optimization experiments were conducted to reveal the critical factors that are required to achieve the demonstrated high supercapacitor performance.

Direct electrochemical formation of nanostructured amorphous Co(OH)2 on gold electrodes with enhanced activity for the oxygen evolution reaction.

The oxides of cobalt have recently been shown to be highly effective electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. In general species such as Co3O4 and CoOOH have been investigated that often require an elevated temperature step during their synthesis to create crystalline materials. In this work we investigate the rapid and direct electrochemical formation of amorphous nanostructured Co(OH)2 on gold electrodes under room temperture conditions which is a highly active precursor for the OER. During the OER some conversion to crystalline Co3O4 occurs at the surface, but the bulk of the material remains amorphous. It is found that the underlying gold electrode is crucial to the materials enhanced performance and provides higher current density than can be achieved using carbon, palladium or copper support electrodes. This catalyst exhibits excellent activity with a current density of 10 mA cm-2 at an overpotential of 360 mV with a high turnover frequency of 2.1 s-1 in 1 M NaOH. A Tafel slope of 56 mV dec-1 at low overpotentials and a slope of 122 mV dec-1 at high overpotentials is consistent with the dual barrier model for the electrocatalytic evolution of oxygen. Significantly, the catalyst maintains excellent activity for up to 24 hr of continuous operation and this approach offers a facile way to create a highly effective and stable material.

Robust nanostructured silver and copper fabrics with localized surface plasmon resonance property for effective visible light induced reductive catalysis

Inspired by high porosity, absorbency, wettability and hierarchical ordering on the micrometer and nanometer scale of cotton fabrics, a facile strategy is developed to coat visible light active metal nanostructures of copper and silver on cotton fabric substrates. The fabrication of nanostructured Ag and Cu onto interwoven threads of a cotton fabric by electroless deposition creates metal nanostructures that show a localized surface plasmon resonance (LSPR) effect. The micro/nanoscale hierarchical ordering of the cotton fabrics allows access to catalytically active sites to participate in heterogeneous catalysis with high efficiency. The ability of metals to absorb visible light through LSPR further enhances the catalytic reaction rates under photoexcitation conditions. Understanding the mode of electron transfer during visible light illumination in Ag@Cotton and Cu@Cotton through electrochemical measurements provides mechanistic evidence on the influence of light in promoting electron transfer during heterogeneous catalysis for the first time. The outcomes presented in this work will be helpful in designing new multifunctional fabrics with the ability to absorb visible light and thereby enhance light-activated catalytic processes.

Synthesis and applications of carbon nanomaterials for energy generation and storage

The world is facing an energy crisis due to exponential population growth and limited availability of fossil fuels. Over the last 20 years, carbon, one of the most abundant materials found on earth, and its allotrope forms such as fullerenes, carbon nanotubes and graphene have been proposed as sources of energy generation and storage because of their extraordinary properties and ease of production. Various approaches for the synthesis and incorporation of carbon nanomaterials in organic photovoltaics and supercapacitors have been reviewed and discussed in this work, highlighting their benefits as compared to other materials commonly used in these devices. The use of fullerenes, carbon nanotubes and graphene in organic photovoltaics and supercapacitors is described in detail, explaining how their remarkable properties can enhance the efficiency of solar cells and energy storage in supercapacitors. Fullerenes, carbon nanotubes and graphene have all been included in solar cells with interesting results, although a number of problems are still to be overcome in order to achieve high efficiency and stability. However, the flexibility and the low cost of these materials provide the opportunity for many applications such as wearable and disposable electronics or mobile charging. The application of carbon nanotubes and graphene to supercapacitors is also discussed and reviewed in this work. Carbon nanotubes, in combination with graphene, can create a more porous film with extraordinary capacitive performance, paving the way to many practical applications from mobile phones to electric cars. In conclusion, we show that carbon nanomaterials, developed by inexpensive synthesis and process methods such as printing and roll-to-roll techniques, are ideal for the development of flexible devices for energy generation and storage – the key to the portable electronics of the future.

High-performance graphene-based supercapacitors made by a scalable blade-coating approach

Graphene oxide (GO) sheets can form liquid crystals (LCs) in their aqueous dispersions that are more viscous with a stronger LC feature. In this work we combine the viscous LC-GO solution with the blade-coating technique to make GO films, for constructing graphene-based supercapacitors in a scalable way. Reduced GO (rGO) films are prepared by wet chemical methods, using either hydrazine (HZ) or hydroiodic acid (HI). Solid-state supercapacitors with rGO films as electrodes and highly conductive carbon nanotube films as current collectors are fabricated and the capacitive properties of different rGO films are compared. It is found that the HZ-rGO film is superior to the HI-rGO film in achieving high capacitance, owing to the 3D structure of graphene sheets in the electrode. Compared to gelled electrolyte, the use of liquid electrolyte (H2SO4) can further increase the capacitance to 265 F per gram (corresponding to 52 mF per cm2) of the HZ-rGO film.