Electrochemical fabrication of metallic nanostructured electrodes for electroanalytical applications

The use of electrodeposited metal-based nanostructures for electroanalytical applications has recently received widespread attention. There are several approaches to creating nanostructured materials through electrochemical routes that include facile electrodeposition at either untreated or modified electrodes, or through the use of physical or chemical templating methods. This allows the shape, size and composition of the nanomaterial to be readily tuned for the application of interest. The use of such materials is particularly suited to electroanalytical applications. In this mini-review an overview of recently developed nanostructured materials developed through electrochemical routes is presented as well as their electroanalytical applications in areas of biological and environmental importance.

A combined scanning electron micrograph and electrochemical study of the effect of chemical interaction on the cyclability of lithium electrodes in an ionic liquid electrolyte

The effect of storage time on the cyclability of lithium electrodes in an ionic liquid electrolyte, namely 0.5 m LiBF4 in N-methyl-N-propyl pyrrolidinium bis(fluorosulfonyl)imide, [C3mpyr+][FSI–], was investigated. A chemical interaction was observed which is time dependent and results in a morphology change of the Li surface due to build up of passivation products over a 12-day period. The formation of this layer significantly impacts on the Li electrode resistance before cycling and the charging/discharging process for symmetrical Li|0.5 m LiBF4 in [C3mpyr+][FSI–]|Li coin cells. Indeed it was found that introducing a rest period between cycling, and thereby allowing the chemical interaction between the Li electrode and electrolyte to take place, also impacted on the charging/discharging process. For all Li surface treatments the electrode resistance decreased after cycling and was due to significant structural rearrangement of the surface layer. These results suggest that careful electrode pretreatment in a real battery system will be required before operation.

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.

Predicting active material utilisation in LiFePO4 electrodes using a multi-scale mathematical model

A mathematical model is developed to simulate the discharge of a LiFePO4 cathode. This model contains 3 size scales, which match with experimental observations present in the literature on the multi-scale nature of LiFePO4 material. A shrinking-core is used on the smallest scale to represent the phase-transition of LiFePO4 during discharge. The model is then validated against existing experimental data and this validated model is then used to investigate parameters that influence active material utilisation. Specifically the size and composition of agglomerates of LiFePO4 crystals is discussed, and we investigate and quantify the relative effects that the ionic and electronic conductivities within the oxide have on oxide utilisation. We find that agglomerates of crystals can be tolerated under low discharge rates. The role of the electrolyte in limiting (cathodic) discharge is also discussed, and we show that electrolyte transport does limit performance at high discharge rates, confirming the conclusions of recent literature.

Study of the underlying electrochemistry of polycrystalline gold electrodes in aqueous solution and electrocatalysis by large amplitude Fourier transformed alternating current voltammetry

Polycrystalline gold electrodes of the kind that are routinely used in analysis and catalysis in aqueous media are often regarded as exhibiting relatively simple double-layer charging/discharging and monolayer oxide formation/ removal in the positive potential region. Application of the large amplitude Fourier transformed alternating current (FT-ac) voltammetric technique that allows the faradaic current contribution of fast electron-transfer processes to be emphasized in the higher harmonic components has revealed the presence of well-defined faradaic (premonolayer oxidation) processes at positive potentials in the double-layer region in acidic and basic media which are enhanced by electrochemical activation. These underlying quasi-reversible interfacial electron-transfer processes may mediate the course of electrocatalytic oxidation reactions of hydrazine, ethylene glycol, and glucose on gold electrodes in aqueous media. The observed responses support key assumptions associated with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis.

Electrocrystallization of phase I, CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane), on indium tin oxide and boron-doped diamond electrodes

The electrochemical reduction of TCNQ to TCNQ•- in acetonitrile in the presence of [Cu(MeCN)4]+ has been undertaken at boron-doped diamond (BDD) and indium tin oxide (ITO) electrodes. The nucleation and growth process at BDD is similar to that reported previously at metal electrodes. At an ITO electrode, the electrocrystallization of more strongly adhered, larger, branched, needle-shaped phase I CuTCNQ crystals is detected under potential step conditions and also when the potential is cycled over the potential range of 0.7 to −0.1 V versus Ag/AgCl (3 M KCl). Video imaging can be used at optically transparent ITO electrodes to monitor the growth stage of the very large branched crystals formed during the course of electrochemical experiments. Both in situ video imaging and ex situ X-ray diffraction and scanning electron microscopy (SEM) data are consistent with the nucleation of CuTCNQ taking place at a discrete number of preferred sites on the ITO surface. At BDD electrodes, ex situ optical images show that the preferential growth of CuTCNQ occurs at the more highly conducting boron-rich areas of the electrode, within which there are preferred sites for CuTCNQ formation.

Effect of the mediator in feedback mode-based SECM interrogation of indium tin-oxide and boron-doped diamond electrodes

Indium tin-oxide (ITO) and polycrystalline boron-doped diamond (BDD) have been examined in detail using the scanning electrochemical microscopy technique in feedback mode. For the interrogation of electrodes made from these materials, the choice of mediator has been varied. Using Ru(CN) 4− 6 (aq), ferrocene methanol (FcMeOH), Fe(CN) 3− 6 (aq) and Ru(NH 3) 3+ 6 (aq), approach curve experiments have been performed, and for purposes of comparison, calculations of the apparent heterogeneous electron transfer rates (k app) have been made using these data. In general, it would appear that values of k app are affected mainly by the position of the mediator reversible potential relative to the relevant semiconductor band edge (associated with majority carriers). For both the ITO (n type) and BDD (p type) electrodes, charge transfer is impeded and values are very low when using FcMeOH and Fe(CN) 3− 6 (aq) as mediators, and the use of Ru(NH 3) 3+ 6(aq) results in the largest value of k app. With ITO, the surface is chemically homogeneous and no variation is observed for any given mediator. Data is also presented where the potential of the ITO electrode is fixed using a ratio of the mediators Fe(CN) 3− 6(aq) and Fe(CN) 4− 6(aq). In stark contrast, the BDD electrode is quite the opposite and a range of k app values are observed for all mediators depending on the position on the surface. Both electrode surfaces are very flat and very smooth, and hence, for BDD, variations in feedback current imply a variation in the electrochemical activity. A comparison of the feedback current where the substrate is biased and unbiased shows a surprising degree of proportionality.

Creating gold nanoprisms directly on quartz crystal microbalance electrodes for mercury vapor sensing

A novel electrochemical route is used to form highly {111}-oriented and size-controlled Au nanoprisms directly onto the electrodes of quartz crystal microbalances (QCMs) which are subsequently used as mercury vapor sensors. The Au nanoprism loaded QCM sensors exhibited excellent response–concentration linearity with a response enhancement of up to ~ 800% over a non-modified sensor at an operating temperature of 28 °C. The increased surface area and atomic-scale features (step/defect sites) introduced during the growth of nanoprisms are thought to play a significant role in enhancing the sensing properties of the Au nanoprisms toward Hg vapor. The sensors are shown to have excellent Hg sensing capabilities in the concentration range of 0.123–1.27 ppmv (1.02–10.55 mg m − 3), with a detection limit of 2.4 ppbv (0.02 mg m − 3) toward Hg vapor when operating at 28 °C, and 17 ppbv (0.15 mg m − 3) at 89 °C, making them potentially useful for air monitoring applications or for monitoring the efficiency of Hg emission control systems in industries such as mining and waste incineration. The developed sensors exhibited excellent reversible behavior (sensor recovery) within 1 h periods, and crucially were also observed to have high selectivity toward Hg vapor in the presence of ethanol, ammonia and humidity, and excellent long-term stability over a 33 day operating period.

Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers

TCNQ·− radical anions (TCNQ = 7,7,8,8,-tetracyanoquinodimethane) form a wide range of semiconducting coordination polymers when coordinated to transition metals. Some such as CuTCNQ and AgTCNQ exhibit molecular switching and memory storage properties; others have intriguing magnetic properties and for example may behave as molecular magnets at low temperature. In this review, the electro- and photo-chemical synthesis and characterization of this important class of material is reviewed. In particular, the electrochemistry and the redox properties of TCNQ derivatives of coordination polymers based on Cu, Ag, Mn, Fe, Co, Ni, Zn and Cd transition metals are surveyed, with an emphasis on the mechanistic aspects of their electrochemical formation via nucleation–growth processes. Given that TCNQ is an extremely good electron acceptor, readily forming TCNQ•− and TCNQ2-, electrochemical reduction of TCNQ in the presence of a transition metal ion provides an ideal method for synthesis of metal-TCNQ materials by electrocrystallization from organic solvents and ionic liquids or solid-solid transformation using TCNQ modified electrodes from aqueous media containing transition metal electrolytes. The significance of the reversible formal potential (E0f) in these studies is discussed. The coupling of electrocrystallisation on electrode surfaces and microscopic characterization of the electrodeposited materials reveals a wide range of morphologies and phases which strongly influence their properties and applications. Since TCNQ also can be photo-reduced in the presence of suitable electron donors, analogous photochemical approaches to the synthesis of TCNQ-transition metal derivatives are available. The advantages of electrochemical and photochemical methods of synthesis relative to chemical synthesis are outlined.

The effect of electrode material on the electrochemical formation of porous copper surfaces using hydrogen bubble templating

The electrodeposition of copper onto copper, gold, palladium and glassy carbon (GC) electrodes via a hydrogen bubble templating method is reported. It is found that the composition of the underlying electrode material significantly influences the morphology of the copper electrodeposit. Highly ordered porous structures are achieved with Cu and Au electrodes, however on Pd this order is disrupted and a rough randomly oriented surface is formed whereas on GC a bubble templating effect is not observed. Chronopotentiograms recorded during the electrodeposition process allows bubble formation and detachment from the surface to be monitored where distinctly different potential versus time profiles are observed at the different electrodes. The porous Cu surfaces are characterised with scanning electron microscopy, X-ray diffraction and cyclic voltammetric measurements recorded under alkaline conditions. The latter demonstrates that there are active sites present on electrodeposited copper whose coverage and reactivity depend on the underlying electrode material. The most active Cu surface is achieved at a Pd substrate for both the hydrogen evolution reaction and the catalytic reduction of ferricyanide ions with thiosulphate ions. This demonstrates that the highly ordered porous structure on the micron scale which typifies the morphology that can be achieved with the hydrogen bubbling template method is not required in producing the most effective material.

Gold nanoparticles modified electrodes for biosensors

Biomolecules are chemical compounds found in living organisms which are the building blocks of life and perform important functions. Fluctuation from the normal concentration of these biomolecules in living system leads to several disorders. Thus the exact determination of them in human fluids is essential in the clinical point of view. High performance liquid chromatography, flow injection analysis, capillary electrophoresis, fluorimetry, spectrophotometry, electrochemical and chemiluminescence techniques were usually used for the determination of biologically important molecules. Among these techniques, electrochemical determination of biomolecules has several advantages over other methods viz., simplicity, selectivity and sensitivity. In the past two decades, electrodes modified with polymer films, self-assembled monolayers containing different functional groups and carbon paste have been used as electrochemical sensors. But in recent years, nanomaterials based electrochemical sensors play an important role in the improvement of public health because of its rapid detection, high sensitivity and specificity in clinical diagnostics. To date gold nanoparticles (AuNPs) have received arousing attention mainly due to their fascinating electronic and optical properties as a consequence of their reduced dimensions. These unique properties of AuNPs make them as an ideal candidate for the immobilization of enzymes for biosensing. Further, the electrochemical properties of AuNPs reveal that they exhibit interesting properties by enhancing the electrode conductivity, facilitating electron transfer and improving the detection limit of biomolecules. In this chapter, we summarized the different strategies used for the attachment of AuNPs on electrode surfaces and highlighted the electrochemical determination of glucose, ascorbic acid (AA), uric acid (UA) and dopamine derivatives using the AuNPs modified electrodes.

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.

MnOx/carbon nanotube/reduced graphene oxide nanohybrids as high-performance supercapacitor electrodes

Nanohybrids consisting of both carbon and pseudocapacitive metal oxides are promising as high-performance electrodes to meet the key energy and power requirements of supercapacitors. However, the development of high-performance nanohybrids with controllable size, density, composition and morphology remains a formidable challenge. Here, we present a simple and robust approach to integrating manganese oxide (MnOx) nanoparticles onto flexible graphite paper using an ultrathin carbon nanotube/reduced graphene oxide (CNT/RGO) supporting layer. Supercapacitor electrodes employing the MnOx/CNT/RGO nanohybrids without any conductive additives or binders yield a specific capacitance of 1070 F g−1 at 10 mV s−1, which is among the highest values reported for a range of hybrid structures and is close to the theoretical capacity of MnOx. Moreover, atmospheric-pressure plasmas are used to functionalize the CNT/RGO supporting layer to improve the adhesion of MnOx nanoparticles, which results in theimproved cycling stability of the nanohybrid electrodes. These results provide information for the utilization of nanohybrids and plasma-related effects to synergistically enhance the performance of supercapacitors and may create new opportunities in areas such as catalysts, photosynthesis and electrochemical sensors