The impact of plasma inhomogeneity on the sp2 content of thin film (∼micron) boron doped diamond (BDD) electrodes, grown using microwave chemical vapour deposition (MW-CVD) under different methane (CH4) concentrations (1% and 5%), is investigated. The sp2 surface content (critical for interpreting electrochemical data) is comparatively assessed using a variety of electrochemical measurements: capacitance; solvent window analysis and quinone surface coverage. For all growths, distinctive regions containing appreciably differing amounts of sp2 carbon are identified, across the wafer. For example, on the 1% CH4 wafer, some areas exhibit electrochemical signatures indicative of high quality, minimal sp2 content BDD, whereas others show regions comprising significant sp2 carbon. Note Raman microscopy was unable to identify these variations. On the 5% CH4 wafer, no region was found to contain minimal levels of sp2 carbon. Changes in sp2 content across the BDD films indicates spatial variations in parameters such as temperature, methane and atomic hydrogen concentrations during growth, in this case linked directly to the use of a commonly employed multi-moded (overmoded) chamber for MW-CVD BDD synthesis, operated under low power density conditions. Varying sp2 levels can have significant impact on the resulting electrochemical behaviour of the BDD.Download high-res image (414KB)Download full-size image

The fabrication of sub-micron pores in single crystal diamond membranes, which span the entirety of the membrane, is described for the first time, and the translocation properties of polymeric particles through the pore investigated. The pores are produced using a combination of laser micromachining to form the membrane and electron beam induced etching to form the pore. Single crystal diamond as the membrane material, has the advantages of chemical stability and durability, does not hydrate and swell, has outstanding electrical properties that facilitate fast, low noise current-time measurements and is optically transparent for combined optical-conductance sensing. The resulting pores are characterized individually using both conductance measurements, employing a microcapillary electrochemical setup, and electron microscopy. Proof-of-concept experiments to sense charged polystyrene particles as they are electrophoretically driven through a single diamond pore are performed, and the impact of this new pore material on particle translocation is explored. These findings reveal the potential of diamond as a platform for pore-based sensing technologies and pave the way for the fabrication of single nanopores which span the entirety of a diamond membrane.We demonstrate for the first-time fabrication of a sub-micron pore which spans the entirety of a single crystal diamond membrane and investigate the impact of this new pore material on particle translocation.Download high-res image (216KB)Download full-size image

Generator-detector electrodes can be used to both perturb and monitor pH dependant metal–ligand binding equilibria, in situ. In particular, protons generated at the generator locally influence the speciation of metal (Cu2+) in the presence of ligand (triethylenetetraamine), with the detector employed to monitor, in real time, free metal (Cu2+) concentrations.

The development of a voltammetric boron doped diamond (BDD) pH sensor is described. To obtain pH sensitivity, laser micromachining (ablation) is utilized to introduce controlled regions of sp2 carbon into a high quality polycrystalline BDD electrode. The resulting sp2 carbon is activated to produce electrochemically reducible quinone groups using a high temperature acid treatment, followed by anodic polarization. Once activated, no further treatment is required. The quinone groups show a linear (R2 = 0.999) and Nernstian (59 mV/(pH unit)) pH-dependent reductive current–voltage response over a large analyzable pH range, from pH 2 to pH 12. Using the laser approach, it is possible to optimize sp2 coverage on the BDD surface, such that a measurable pH response is recorded, while minimizing background currents arising from oxygen reduction reactions on sp2 carbon in the potential region of interest. This enables the sensor to be used in aerated solutions, boding well for in situ analysis. The voltammetric response of the electrode is not compromised by the presence of excess metal ions such as Pb2+, Cd2+, Cu2+, and Zn2+. Furthermore, the pH sensor is stable over a 3 month period (the current time period of testing), can be stored in air between measurements, requires no reactivation of the surface between measurements, and can be reproducibly fabricated using the proposed approach. The efficacy of this pH sensor in a real-world sample is demonstrated with pH measurements in U.K. seawater.

•Quinone oxidation utilised for assessing sp2 surface content of BDD electrodes•Laser ablation used to introduce increasing amounts of sp2 carbon into BDD surface•Linear relationship observed between quinone surface coverage and sp2 content•Comparative assessment of sp2 content in BDD electrodes of varying qualitySurface coverage measurements of electroactive quinone groups present on sp2 carbon sites, are used to inform on the sp2 surface content of boron doped diamond (BDD) electrodes. Laser micromachining of an electrode surface is used to systematically increase the amount of sp2 carbon present by increasing the area machined. A linear relationship between quinone surface coverage and surface area lasered is determined (R2 = 0.9999). This approach can also be used for comparative assessment of electrodes containing different amounts of surface sp2 carbon.A linear relationship between the oxidation signal for quinone groups present on boron doped diamond (BDD) and sp2 carbon content is shown, demonstrating this electrochemical approach can be utilised to comparatively assess sp2 surface content in BDD electrodes.

The application of electrochemical X-ray fluorescence (EC-XRF), for the detection of palladium (Pd) contamination in a range of solutions containing electrochemically active compounds, present in excess and relevant to the pharmaceutical and food industries, is reported. In EC-XRF, EC is used to electrochemically pre-concentrate metal on an electrode under forced convection conditions, whilst XRF is employed to spectroscopically quantify the amount of metal deposited, which quantitatively correlates with the original metal concentration in solution. Boron doped diamond is used as the electrode due to its very wide cathodic window and the fact that B and C are non-interfering elements for XRF analysis. The effect of several parameters on the Pd XRF signal intensity are explored including: deposition potential (Edep), deposition time (tdep) and Pd2+ concentration, [Pd2+]. Under high deposition potentials (Edep = −1.5 V), the Pd XRF peak intensity varies linearly with both tdep and [Pd2+]. Quantification of [Pd2+] is demonstrated in the presence of excess acetaminophen (ACM), L-ascorbic acid, caffeine and riboflavin. We show the same Pd XRF signal intensity (for [Pd2+] = 1.1 μM and tdep = 325 s) is observed, i.e. same amount of Pd is deposited on the electrode surface, irrespective of whether these redox active molecules are present or absent. For tdep = 900 s we report a limit of detection for [Pd2+] of 3.6 ppb (34 nM). Even lower LODs are possible by increasing tdep or by optimising the X-ray source specifically for Pd. The work presented for Pd detection in the presence of ACM, achieves the required detection sensitivity stipulated by international pharmacopeia guidelines.

The use of two different electrodeposition approaches to form nickel hydroxide, Ni(OH)2, nanoparticles (NPs) of different crystallographic orientations on single-walled carbon nanotubes is demonstrated via: (i) the electrochemical generation of OH– (∼mM), in the presence of Ni2+, resulting in the formation of disordered α-phase Ni(OH)2 NPs by precipitation (direct approach); (ii) the electrodeposition of Ni NPs that are converted to Ni(OH)2 through potential cycling in alkaline media to form the more thermodynamically favorable, ordered β-phase Ni(OH)2 NPs (indirect approach). NPs produced by the direct approach exhibit remarkable electrocatalytic activity toward both methanol and ethanol oxidation, with excellent specific activities (SAs) of ∼2.8 kA g–1 for 0.5 M methanol and ∼3.7 kA g–1 for 0.5 M ethanol. In contrast, NPs produced by the indirect approach show SA values about an order of magnitude lower. This study demonstrates the capability of electrochemistry for the tailored synthesis of Ni(OH)2 nanostructures for electrocatalytic applications and a powerful, but simple, combinatorial approach for quick activity screening.

Scanning electrochemical cell microscopy is utilised as a read–write pipette-based probe to both electrochemically modify the local surface chemistry of boron doped diamond and “read” the resulting modification, at the micron scale. In this specific application, localised electrochemical oxidation results in conversion of the H-terminated surface to –O, electrochemically visualised by monitoring the current change for reduction of Ru(NH3)63+. This methodology, in general, provides a platform for read–write analysis of electrodes, opening up new analytical avenues, particularly as the pipette can be viewed as a microfluidic device.

The development and application of a new methodology, in situ electrochemical X-ray fluorescence (EC-XRF), is described that enables direct identification and quantification of heavy metals in solution. A freestanding film of boron-doped diamond serves as both an X-ray window and the electrode material. The electrode is biased at a suitable driving potential to electroplate metals from solution onto the electrode surface. Simultaneously, X-rays that pass through the back side of the electrode interrogate the time-dependent electrodeposition process by virtue of the XRF signals, which are unique to each metal. In this way it is possible to unambiguously identify which metals are in solution and relate the XRF signal intensity to a concentration of metal species in solution. To increase detection sensitivity and reduce detection times, solution is flown over the electrode surface by use of a wall-jet configuration. Initial studies focused on the in situ detection of Pb2+, where concentration detection limits of 99 nM were established in this proof-of-concept study (although significantly lower values are anticipated with system refinement). This is more than 3 orders of magnitude lower than that achievable by XRF alone in a flowing solution (0.68 mM). In situ EC-XRF measurements were also carried out on a multimetal solution containing Hg2+, Pb2+, Cu2+, Ni2+, Zn2+, and Fe3+ (all at 10 μM concentration). Identification of five of these metals was possible in one simple measurement. In contrast, while anodic stripping voltammetry (ASV) also revealed five peaks, peak identification was not straightforward, requiring further experiments and prior knowledge of the metals in solution. Time-dependent EC-XRF nucleation data for the five metals, recorded simultaneously, demonstrated similar deposition rates. Studies are now underway to lower detection limits and provide a quantitative understanding of EC-XRF responses in real, multimetal solutions. Finally, the production of custom-designed portable in situ EC-XRF instrumentation will make heavy metal analysis at the source a very realistic possibility.

The quantification of genotoxic impurities (GIs) such as hydrazine (HZ) is of critical importance in the pharmaceutical industry in order to uphold drug safety. HZ is a particularly intractable GI and its detection represents a significant technical challenge. Here, we present, for the first time, the use of electrochemical analysis to achieve the required detection limits by the pharmaceutical industry for the detection of HZ in the presence of a large excess of a common active pharmaceutical ingredient (API), acetaminophen (ACM) which itself is redox active, typical of many APIs. A flow injection analysis approach with electrochemical detection (FIA-EC) is utilized, in conjunction with a coplanar boron doped diamond (BDD) microband electrode, insulated in an insulating diamond platform for durability and integrated into a two piece flow cell. In order to separate the electrochemical signature for HZ such that it is not obscured by that of the ACM (present in excess), the BDD electrode is functionalized with Pt nanoparticles (NPs) to significantly shift the half wave potential for HZ oxidation to less positive potentials. Microstereolithography was used to fabricate flow cells with defined hydrodynamics which minimize dispersion of the analyte and optimize detection sensitivity. Importantly, the Pt NPs were shown to be stable under flow, and a limit of detection of 64.5 nM or 0.274 ppm for HZ with respect to the ACM, present in excess, was achieved. This represents the first electrochemical approach which surpasses the required detection limits set by the pharmaceutical industry for HZ detection in the presence of an API and paves the wave for online analysis and application to other GI and API systems.

Voltammetric studies of dopamine (DA) oxidation on pristine and acid-treated single-walled carbon nanotube (SWNT) network electrodes were undertaken in order to investigate both the effect of network density and acid treatment times on the voltammetric characteristics for DA oxidation and the susceptibility of the electrodes to fouling. Through careful control of catalysed chemical vapour deposition growth parameters, multiply interconnected and randomly oriented SWNT networks of two significantly different densities were grown (high density, HD, coverage ≫10 μm length of SWNT per μm−2 and low density, LD, coverage = 5 (±1) μmSWNT μm−2). Acid treatment was performed to provide materials with different electrochemical properties and SWNT coverage, as determined by field emission-scanning electron microscopy, atomic force microscopy and micro-Raman spectroscopy. A high concentration of DA (100 μM) was deliberately employed to accelerate the fouling phenomenon associated with DA oxidation in order to evaluate the lifetime of the electrodes. HD pristine SWNT networks were found to promote more facile electron transfer (ET) and were less susceptible to blocking, compared to LD pristine SWNT networks. Acid treatment resulted in both a further enhancement of the ET rate and a reduction in susceptibility towards electrode fouling. However, lengthy acid treatment detrimentally affected ET, due to a decrease in network density and significant damage to the SWNT network structure. These studies highlight the subtle interplay between SWNT coverage and degree of acid functionalisation when seeking to achieve the optimal SWNT electrode for the voltammetric detection of DA.

The development of a novel analytical technique, electrochemical X-ray fluorescence (EC-XRF), is described and applied to the quantitative detection of heavy metals in solution, achieving sub-ppb limits of detection (LOD). In EC-XRF, electrochemical preconcentration of a species of interest onto the target electrode is achieved here by cathodic electrodeposition. Unambiguous elemental identification and quantification of metal concentration is then made using XRF. This simple electrochemical preconcentration step improves the LOD of energy dispersive XRF by over 4 orders of magnitude (for similar sample preparation time scales). Large area free-standing boron doped diamond grown using microwave plasma chemical vapor deposition techniques is found to be ideal as the electrode material for both electrodeposition and XRF due to its wide solvent window, transparency to the XRF beam, and ability to be produced in mechanically robust freestanding thin film form. During electrodeposition it is possible to vary both the deposition potential (Edep) and deposition time (tdep). For the metals Cu2+ and Pb2+ the highest detection sensitivities were found for Edep = −1.75 V and tdep = 4000 s with LODs of 0.05 and 0.04 ppb achieved, respectively. In mixed Cu2+/Pb2+ solutions, EC-XRF shows that Cu2+ deposition is unimpeded by Pb2+, across a broad concentration range, but this is only true for Pb2+ when both metals are present at low concentrations (10 nM), boding well for trace level measurements. In a dual mixed metal solution, EC-XRF can also be employed to either selectively deposit the metal which has the most positive formal reduction potential, E0, or exhaustively deplete it from solution, enabling uninhibited detection of the metal with the more negative E0.

A novel electrochemical approach to modifying aqueous solution pH in the vicinity of a detector electrode in order to optimize the electrochemical measurement signal is described. A ring disk electrode was employed where electrochemical decomposition of water on the ring was used to generate a flux of protons which adjusts the local pH controllably and quantifiably at the disk. Boron doped diamond (BDD) functioned as the electrode material given the stability of this electrode surface especially when applying high potentials (to electrolyze water) for significant periods of time. A pH sensitive iridium oxide electrode electrodeposited on the disk electrode demonstrated that applied positive currents on the BDD ring, up to +50 μA, resulted in a local pH decrease of over 4 orders of magnitude, which remained stable over the measurement time of 600 s. pH generation experiments were found to be in close agreement with finite element simulations. The dual electrode arrangement was used to significantly improve the stripping peak signature for Hg in close to neutral conditions by the generation of pH = 2.0, locally. With the ability to create a localized pH change electrochemically in the vicinity of the detector electrode, this system could provide a simple method for optimized analysis at the source, e.g., river and sea waters.

A novel electrochemical approach to the direct detection of hydrogen sulfide (H2S), in aqueous solutions, covering a wide pH range (acid to alkali), is described. In brief, a dual band electrode device is employed, in a hydrodynamic flow cell, where the upstream electrode is used to controllably generate hydroxide ions (OH–), which flood the downstream detector electrode and provide the correct pH environment for complete conversion of H2S to the electrochemically detectable, sulfide (HS–) ion. All-diamond, coplanar conducting diamond band electrodes, insulated in diamond, were used due to their exceptional stability and robustness when applying extreme potentials, essential attributes for both local OH– generation via the reduction of water, and for in situ cleaning of the electrode, post oxidation of sulfide. Using a galvanostatic approach, it was demonstrated the pH locally could be modified by over five pH units, depending on the initial pH of the mobile phase and the applied current. Electrochemical detection limits of 13.6 ppb sulfide were achieved using flow injection amperometry. This approach which offers local control of the pH of the detector electrode in a solution, which is far from ideal for optimized detection of the analyte of interest, enhances the capabilities of online electrochemical detection systems.

Highly doped, boron doped diamond (BDD) is an electrode material with great potential, but the fabrication of suitable electrodes in a variety of different geometries both at the macro- and microscale, with an insulating material that does not compromise the material properties of the BDD, presents technical challenges. In this Technical Note, a novel solution to this problem is presented, resulting in the fabrication of coplanar macro- and microscale BDD electrodes, insulated by insulating diamond, at the single and multiple, individually addressable level. Using a laser micromachining approach, the required electrode(s) geometry is machined into an insulating diamond substrate, followed by overgrowth of high quality polycrystalline BDD (pBDD) and polishing to reveal approximately nanometer roughness, coplanar all-diamond structures. Electrical contacting is possible using both top and bottom contacts, where the latter are defined using the laser to produce non-diamond-carbon (NDC) in the vicinity of the back side of the BDD. We present the fabrication of individually addressable ring, band, and disk electrodes with minimum, reproducible controlled dimensions of 50 μm (limited only by the laser system employed). The pBDD grown into the insulating diamond recesses is shown to be free from NDC and possesses excellent electrochemical properties, in terms of extended solvent windows, electrochemical reversibility, and capacitance.

The effect of systematic anodic pre-treatments of pristine single walled carbon nanotube (SWNT) forests on the electrochemical response towards a variety of redox processes is investigated. An experimental arrangement is adopted whereby a microcapillary containing the solution of interest and a quasi reference-counter electrode is brought into contact with a small portion of the forest to enable measurements on the surface before and after controlled anodic polarisation (AP). AP of the surface is found to both improve the voltammetric response (faster apparent heterogeneous electron transfer kinetics) of surface sensitive redox processes, such as Fe2+/3+, and enhance the electrocatalytic response of the SWNTs towards oxygen reduction; the extent of which can be carefully controlled via the applied anodic potential. AP is expected to remove any trace organic (atmospheric) contaminants that may accumulate on the forest over extended periods as well as allowing the controlled introduction of defects, as confirmed by micro-Raman spectroscopy.

Double potential step chronoamperometry (DPSC) is demonstrated as a technique for investigating partitioning between a solute in aqueous solution and non-polar oil droplet(s) immobilised at an electrode. Here a species in aqueous solution which does not partition into the oil phase is converted at the electrode surface into another species which either does not or does partition into the oil drop. The first case is investigated experimentally by considering generation of the ionic redox species, FcTMA2+ from FcTMA+, while the second case is exemplified by studies of Br2 generation from Br−. The case of molecular partitioning at the three phase interface has received little attention hitherto. To maintain oil droplet stability a boron-doped diamond electrode is employed functionalised with Pt nanoparticles to impart electrocatalytic activity on the electrode towards Br2 production. An arrangement is utilised where the droplet(s) sit(s) on (but does not cover) the electrode surface. We show both experimentally and through finite element simulation how the charge–time profile for the generation and collection of electroactive species can be used to obtain information on the extent of partitioning and how this is affected by factors such as the number and size of droplets. Finally, we highlight the suitability of this approach for investigating reactions which take place within the droplet.

Boron doped diamond (BDD) disk ultramicroelectrodes have been used to sense single nanoparticle (NP) electrocatalytic collision events. BDD serves as an excellent support electrode due to its electrocatalytic inactivity and low background currents and thus can be used to detect the electroactivity of a wide range of colliding NPs, with high sensitivity. In particular, single NP collisions for hydrazine oxidation at Au and Pt NPs were shown to be markedly different.

In order to produce polycrystalline oxygen-terminated boron-doped diamond (BDD) electrodes suitable for electroanalysis (i.e., widest solvent window, lowest capacitive currents, stable and reproducible current responses, and capable of demonstrating fast electron transfer) for outer sphere redox couples, the following factors must be considered. The material must contain enough boron that the electrode shows metal-like conductivity; electrical measurements demonstrate that this is achieved at [B] > 1020 B atoms cm–3. Even though BDD contains a lower density of states than a metal, it is not necessary to use extreme doping levels to achieve fast heterogeneous electron transfer (HET). An average [B] ∼ 3 × 1020 B atoms cm–3 was found to be optimal; increasing [B] results in higher capacitive values and increases the likelihood of nondiamond carbon (NDC) incorporation. Hydrogen-termination causes a semiconducting BDD electrode to behave metal-like due to the additional surface conductivity hydrogen termination brings. Thus, unless [B] of the material is known, the electrical properties of the electrode may be incorrectly interpreted. Note, this layer (formed on a lapped electrode) is electrochemically unstable, an effect which is exacerbated at increased potentials. It is essential during growth that NDC is minimized as it acts to increase capacitive currents and decrease the solvent window. We found complete removal of NDC after growth using aggressive acid cleans, acid cycling, and diamond polishing impossible. Although hydrogen termination can mask the NDC signature in the solvent window and lower capacitive currents, this is not a practical procedure for improving sensitivity in electroanalysis. Finally, alumina polishing of lapped, NDC free, freestanding, BDD electrodes was found to be an effective way to produce well-defined, stable, and reproducible surfaces, which support fast (reversible) HET for Fe(CN)64– electrolysis, the first time this has been reported at an oxygen-terminated surface.

The electrochemical measurement of dopamine (DA), in phosphate buffer solution (pH 7.4), with a limit of detection (LOD) of ∼5 pM in 50 μL (∼ 250 attomol) is achieved using a band electrode comprised of a sparse network of pristine single-walled carbon nanotubes (SWNTs), which covers <1% of the insulating substrate. The SWNT electrodes are deployed as amperometric (anodic) detectors in microfluidic cells, produced by microstereolithography, designed specifically for flow injection analysis (FIA). The flow cells, have a channel (duct) geometry, with cell height of 25 μm, and are shown to be hydrodynamically well-defined, with laminar Poiseuille flow. In the arrangement where solution continuously flows over the electrode but the electrode is only exposed to the analyte for short periods of time, the SWNT electrodes do not foul and can be used repeatedly for many months. The LOD for dopamine (DA), reported herein, is significantly lower than previous reports using FIA–electrochemical detection. Furthermore, the SWNT electrodes can be used as grown, i.e., they do not require chemical modification or cleanup. The extremely low background signals of the SWNT electrodes, as a consequence of the sparse surface coverage and the low intrinsic capacitance of the SWNTs, means that no signal processing is required to measure the low currents for DA oxidation at trace levels. DA detection in artificial cerebral fluid is also possible with a LOD of ∼50 pM in 50 μL (∼2.5 fmol).

The change in surface morphology of oxygen-terminated polycrystalline boron doped diamond (pBDD) during electrochemical oxidation of the neurotransmitter serotonin (5-HT), resulting in a corresponding deterioration of the current signal, is investigated for the first time using both high resolution ex situ and in situ microscopy under a range of different electrochemical conditions. In situ electrochemical-atomic force microscopy (EC-AFM) reveals the formation of a granular film over the surface, which grows faster at higher-doped regions of the electrode surface and increases in thickness with repetitive potential cycles. The film properties were investigated using both cyclic voltammetry, with a range of redox species varying in charge, and conducting-AFM. These studies reveal the film to be positively charged and electrically insulating. The extent to which the film forms during 5-HT oxidation could be significantly minimised using different electrochemical procedures, as verified by voltammetry and in situ EC-AFM. Finally, even after extensive film formation, the original current signal could be recovered simply by leaving the electrode at open circuit potential for a short period of time, highlighting the suitability of BDD electrodes for neurotransmitter detection.

The electrochemical properties of the closed ends and sidewalls of pristine carbon nanotube forests are investigated directly using a nanopipet electrochemical cell. Both are shown to promote fast electron transfer, without any activation or processing of the carbon nanotube material required, in contrast to the current model in the literature.

The development of the first all-diamond hydrodynamic flow device for electroanalytical applications is described. Here alternate layers of intrinsic (insulating), conducting (heavily boron doped), and intrinsic polycrystalline diamond are grown to create a sandwich structure. By laser cutting a hole through the material, it is possible to produce a tubular flow ring electrode of a characteristic length defined by the thickness of the conducting layer (for these studies ∼90 μm). The inside of the tube can be polished to 17 ± 10 nm surface roughness using a diamond impregnanted wire resulting in a coplanar, smooth, all-diamond surface. The steady-state limiting current versus volume flow rate characteristics for the one electron oxidation of FcTMA+ are in agreement with those expected for laminar flow in a tubular electrode geometry. For dopamine detection, it is shown that the combination of the reduced fouling properties of boron doped diamond, coupled with the flow geometry design where the products of electrolysis are washed away downstream of the electrode, completely eradicates fouling during electrolysis. This paves the way for incorporation of this flow design into online electroanalytical detection systems. Finally, the all diamond tubular flow electrode system described here provides a platform for future developments including the development of ultrathin ring electrodes, multiple apertures for increased current response, and multiple, individually addressable ring electrodes incorporated into the same flow tube.

We report wide-ranging studies to elucidate the factors and issues controlling stripping voltammetry of metal ions on solid electrodes using the well-known Pb/Pb2+ couple on polycrystalline boron doped diamond (pBDD) as an exemplar system. Notably, high-resolution microscopy techniques have revealed new insights into the features observed in differential pulse anodic stripping voltammetry (DPV−ASV) which provide a deeper understanding of how best to utilize this technique. DPV−ASV was employed in an impinging wall-jet configuration to detect Pb2+ in the nanomolar to micromolar concentration range at a pBDD macrodisk electrode. The deposition process was driven to produce a grain-independent homogeneous distribution of Pb nanoparticles (NPs) on the electrode surface; this resulted in the observation of narrow stripping peaks. Lower calibration gradients of current or charge versus concentration were found for the low concentrations, correlating with a lower than expected (from consideration of the simple convective-diffusive nature of the deposition process) amount of Pb deposited on the surface. This was attributed to the complex nature of nucleation and growth at solid surfaces in this concentration regime, complicating mass transport. Furthermore, a clear shift negative in the stripping peak potential with decreasing concentration was seen correlating with a change in the size of the deposited NP, suggesting an NP size-dependent redox potential for the Pb/Pb2+ couple. At high concentrations a nonlinear response was observed, with less Pb detected than expected, in addition to the observation of a second stripping peak. Atomic force microscopy (AFM) and field emission scanning electron microscopy revealed the second peak to be due to a change in deposition morphology from isolated NPs to grain-independent heterogeneous structures comprising both thin films and NPs; the second peak is associated with stripping from the thin-film structures. AFM also revealed a substantial amount of Pb remaining on the surface after stripping at high concentration, explaining the nonlinear relationship between stripping peak current (or charge) and concentration. Finally, the use of an in situ cleaning procedure between each measurement was advocated to ensure a clean Pb-free surface (verified by AFM and X-ray photoelectron spectroscopy analysis) between each run. The studies herein highlight important and complex physicochemical processes involved in the electroanalysis of heavy metals at solid electrodes, such as pBDD, that need to be accounted for when using stripping voltammetry methods.

The use of single walled carbon nanotube (SWNT) band electrodes in a channel flow cell, for low concentration detection, with hydrodynamic voltammetry is reported. A two dimensional SWNT network electrode is combined with a one piece channel flow cell unit, fabricated by microstereolithography. This configuration provides well defined hydrodynamics over a wide range of volume flow rates (0.05–25 mL min− 1). Limiting current measurements, from linear sweep voltammograms, are in good agreement with the channel electrode Levich equation, for the one electron oxidation of ferrocenylmethyl trimethylammonium (FcTMA+), over a wide concentration range, 1 × 10− 8 M to 2.1 × 10− 5 M, with a detection limit of 5 nM. At the highest flow rates, some influence of the slightly recessed electrode geometry arising from the SWNT electrode fabrication is noted. However, this can be accounted for by a full simulation of the hydrodynamics and solution of the resulting convection–diffusion equation. Application of this hydrodynamic configuration to the voltammetric detection of dopamine is also demonstrated.

Networks of pristine single walled carbon nanotubes (SWNTs) grown by catalysed chemical vapour deposition (cCVD) on an insulating surface and arranged in an ultramicroelectrode (UME) format are insensitive to the electro-oxidation of hydrazine (HZ) in aqueous solution, indicating a negligible metallic nanoparticle content. Sensitisation of the network towards HZ oxidation is promoted by the deliberate and controlled electrodeposition of “naked” gold (Au) nanoparticles (NPs). By controlling the deposition conditions (potential, time) it is possible to control the size and spacing of the Au NPs on the underlying SWNT network. Two different cases are considered: Au NPs at a number density of 250 ± 13 NPs μm−2 and height 24 nm ± 5 (effective surface coverage, θ = 92%) and (ii) Au NPs of number density ∼ 22 ± 3 NPs μm−2 and height 43 nm ± 8 nm (θ = 35%). For both morphologies the HZ oxidation half-wave potential (E1/2) is shifted significantly negative by ca. 200 mV, compared to a gold disc UME of the same geometric area, indicating significantly more facile electron transfer kinetics. E1/2 for HZ oxidation for the higher density Au NP-SWNT structure is shifted slightly more negative (by ∼25 mV) than E1/2 for the lower density Au NP electrode. This is attributed to the lower flux of HZ at NPs in the higher number density arrangement (smaller kinetic demand). Importantly, using this approach, the calculated HZ oxidation current density sensitivities for the Au NP-SWNT electrodes reported here are higher than for many other metal NP functionalised carbon nanotube electrodes.

Optically transparent ultramicroelectrodes (OT-UMEs) comprising carbon nanotube (CNT) networks on quartz, are introduced and used to monitor quantitatively the interfacial concentration of tris(2,2′-bipyridine)ruthenium(II) during cyclic voltammetry. The OT-CNT-UMEs combine the attractive properties of small-scale electrodes, e.g., high diffusion rates and good signal-to-noise, with the ability to probe electrochemical processes optically, from the rear of the electrode. This enables optical measurements of the solution, close to the electrode surface, without significant interference from absorption or scattering processes.

We demonstrate, for the first time, the electrosynthesis of uniformly dispersed nickel hydroxide nanoparticles (NPs) on polycrystalline boron-doped diamond (pBDD). This has been achieved by electrogenerating OH− at the pBDD surface in the presence of Ni2+ to create local conditions near the electrode where highly supersaturated (relative saturation ratio > 105) nickel hydroxide solutions are generated for short periods of time (approximately seconds). This results in the deposition of nickel hydroxide NPs directly on the electrode surface, as confirmed by X-ray photoelectron spectroscopy. The NPs have a reasonably homogeneous size distribution and are deposited uniformly across the heterogeneous pBDD surface. We show that by simply increasing the electrogeneration time and, hence, increasing both the local concentration of OH− and extent of the precipitation reaction, it is possible to increase the size of the NPs. For example, after 1 s, NPs with dimensions of 12 ± 3 nm form, whereas after 15 s, NPs of size ∼39 ± 9 nm result. Longer times result in larger particles, which form aggregated structures. The effect of nickel hydroxide NP size on electrocatalytic activity was investigated by measuring the steady-state current for the oxidation of glucose in alkaline media. For NPs ≥ 25 nm in size, glucose oxidation is close to diffusion-controlled. However, for the smallest NPs produced (∼12 nm) the currents passed suggest kinetic limitations. For glucose at an effective surface coverage of nickel hydroxide of ∼20 nmol cm−2, equivalent to 15 ng of nickel hydroxide, this functionalized electrode showed a sensitivity of 330 μA mM−1 cm−2 and a limit of detection of 400 nM. The latter represents one of the lowest limits of detection for glucose for nickel hydroxide-based electrodes. The electrocatalytic oxidation properties of this electrode toward methanol and ethanol was also found to be very efficient, yielding very high density currents of ∼1010 A g−1 for 0.5 M ethanol and 990 A g−1 for 0.47 M methanol.

Individual nanowires (NWs) and native single-walled carbon nanotubes (SWNTs) can be readily used as well-defined nanoscale electrodes (NSEs) for voltammetric analysis. Here, the simple photolithography-free fabrication of submillimeter long Au, Pt, and Pd NWs, with sub-100 nm heights, by templated electrodeposition onto ultralong flow-aligned SWNTs is demonstrated. Both individual Au NWs and SWNTs are employed as NSEs for electron-transfer (ET) kinetic quantification, using cyclic voltammetry (CV), in conjunction with a microcapillary-based electrochemical method. A small capillary with internal diameter in the range 30–70 μm, filled with solution containing a redox-active mediator (FcTMA+ ((trimethylammonium)methylferrocene), Fe(CN)64–, or hydrazine) is positioned above the NSE, so that the solution meniscus completes an electrochemical cell. A 3D finite-element model, faithfully reproducing the experimental geometry, is used to both analyze the experimental CVs and derive the rate of heterogeneous ET, using Butler–Volmer kinetics. For a 70 nm height Au NW, intrinsic rate constants, k0, up to ca. 1 cm s–1 can be resolved. Using the same experimental configuration the electrochemistry of individual SWNTs can also be accessed. For FcTMA+/2+ electrolysis the simulated ET kinetic parameters yield very fast ET kinetics (k0 > 2 ± 1 cm s–1). Some deviation between the experimental voltammetry and the idealized model is noted, suggesting that double-layer effects may influence ET at the nanoscale.Keywords: electrochemistry; electrodeposition; electron transfer; kinetics; nanoscale electrodes; nanowires; single-walled carbon nanotubes

Here we demonstrate the use of microstereolithography (MSL), a 3D direct manufacturing technique, as a viable method to produce small-scale microfluidic components for electrochemical flow detection. The flow cell is assembled simply by resting the microfabricated component on the electrode of interest and securing with thread! This configuration allows the use of a wide range of electrode materials. Furthermore, our approach eliminates the need for additional sealing methods, such as adhesives, waxes, and screws, which have previously been deployed. In addition, it removes any issues associated with compression of the cell chamber. MSL allows a reduction of the dimensions of the channel geometry (and the resultant component) and, compared to most previously produced devices, it offers a high degree of flexibility in the design, reduced manufacture time, and high reliability. Importantly, the polymer utilized does not distort so that the cell maintains well-defined geometrical dimensions after assembly. For the studies herein the channel dimensions were 3 mm wide, 3.5 mm long, and 192 or 250 μm high. The channel flow cell dimensions were chosen to ensure that the substrate electrodes experienced laminar flow conditions, even with volume flow rates of up to 64 mL min−1 (the limit of our pumping system). The steady-state transport-limited current response, for the oxidation of ferrocenylmethyl trimethylammonium hexaflorophosphate (FcTMA+), at gold and polycrystalline boron doped diamond (pBDD) band electrodes was in agreement with the Levich equation and/or finite element simulations of mass transport. We believe that this method of creating and using channel flow electrodes offers a wide range of new applications from electroanalysis to electrocatalysis.

The characteristics of three different carbon electrodes, glassy carbon (GC), oxygen-terminated polycrystalline boron-doped diamond (pBDD) and “pristine” carbon nanotube networks (CNTN) as voltammetric sensors for detection of the neurotransmitter serotonin have been investigated. For each electrode, detection sensitivity was determined using cyclic voltammetry (CV), a technique often used to provide information on chemical identity in electrochemical assays. The CNTN electrodes were found to exhibit background current densities ca. two orders of magnitude smaller than the GC electrode and ca. twenty times smaller than pBDD, as a consequence of their “pristine” low capacitance and low surface coverage. This was a major factor in determining serotonin detection limits from CV, of 10 nM for the CNTN electrode, 500 nM for pBDD and 2 μM for GC. The two most sensitive electrodes (CNTN and pBDD) were further investigated in terms of resistance to electrode fouling. CV analysis showed that fouling was less on the pBDD electrode compared to the CNTN and, furthemore, for the case of pBDD could be significantly minimised by careful selection of the CV potential limits, in particular by scanning the electrode potential to suitably cathodic values after oxidation of the serotonin.

The electrodeposition mechanism of gold nanoparticles (NPs) on pristine single walled carbon nanotubes (SWNTs) at high driving forces has been elucidated using the microcapillary electrochemical method. Here, a small capillary (internal diameter ∼50−100 μm) filled with a gold plating solution, and positioned so that the capillary meniscus makes contact with a two-dimensional SWNT random network, was used to record current−time transients. Nucleation and growth transients were observed in which the current increased with time to a maximum value beyond which the current decreased (planar diffusion regime). With increased driving force, the current maximum shifted dramatically to increasingly shorter times. Atomic force microscopy (AFM) analysis indicated that this was not due to significant differences in NP growth rates, but rather to increased densities of NPs formed at more cathodic potentials. Detailed microscopic analysis showed that the size of the NPs initially increased with deposition time and the particle surface coverage was constant. However, at the highest driving forces the NP density decreased with deposition time and AFM revealed the presence of both larger and smaller particles at long times. This was attributed to electrochemically induced Ostwald ripening, whereby larger particles grow at the expense of smaller ones. As NP nucleation and growth on SWNT two dimensional network electrodes is highly directional and enforced in particular locations, it is inappropriate to analyze electrochemical data using conventional models. There is thus a need to complement chronoamperometric measurements with high resolution microscopy to fully interpret nucleation on complex electrode surfaces.

An important open question on the electrochemistry of single-walled carbon nanotube (SWNT) electrodes concerns the sites at which electron transfer (ET) occurs. This issue is addressed herein for the case of a simple outer sphere redox couple, (ferrocenymethyl)trimethylammonium (FcTMA+). Using relatively sparse networks (<1% surface coverage) of electrically connected SWNTs, coupled to a scanning electrochemical microscopy (SECM) substrate generation−tip collection setup, we show that high rates of mass transport can be generated to SWNTs, allowing kinetic effects to be observed in the voltammetric waveshape. By developing a numerical model that faithfully represents all aspects of the experimental geometry, highly accurate kinetic data can be obtained. Assuming that all SWNTs are active, a minimum average ET rate constant k0SWNT > 1.0 ± 0.6 cm s−1 is assigned, which is of similar size to other electrode materials and suggests that the sidewall of SWNTs has considerable ET activity.

Electrochemistry at carbon nanotubes (CNTs) is a large and growing field, but one in which there is still uncertainty about the fundamental activity of CNTs as electrode materials. On the one hand, there are many reports which focus on the favourable electrochemical properties of CNT electrodes, such as enhanced detection sensitivity, electrocatalytic effects and reduced fouling. On the other hand, other studies suggest that CNTs may be no more electroactive than graphitic powder. Furthermore, it has been proposed that the catalytic nanoparticles from which CNTs are formed may dominate the electrochemical characteristics in some instances. A considerable body of the literature presumes that the CNT sidewall is inert and that edge-plane-graphite-like open ends and defect sites are responsible for the electron transfer activity observed. In contrast, studies of well characterised single-walled nanotube (SWNT) electrodes, either as individual tubes or as two-dimensional networks, suggest sidewall activity. This review highlights how the various discrepancies in CNT electrochemistry may have arisen, by taking a historical view of the field and identifying crucial issues that still need to be solved. When assessing the behaviour of CNT electrodes, it is vitally important that careful consideration is given to the type of CNT used (SWNT or multi-walled), the quality of the material (presence of impurities), the effect of chemical processing steps in the fabrication of electrodes and the experimental arrangements adopted. Understanding these key features is an essential requirement to develop a fundamental understanding of CNT electrochemistry, to allow a wide range of electroanalytical applications, and to move the field forward rationally. As part of this process, high resolution electrochemical and electrical imaging techniques are expected to play a significant role in the future, as well as theoretical developments which examine the fundamentals of electron transfer at different types of CNTs and their characteristic surface sites.

Pt nanoparticle (NP)-modified polycrystalline boron-doped diamond (pBDD) disk electrodes have been fabricated and employed as amperometric sensors for the determination of dissolved oxygen concentration in aqueous solution. pBDD columns were cut using laser micromachining techniques and sealed in glass, in order to make disk electrodes which were then characterized electrochemically. Electrodeposition of Pt onto the diamond electrodes was optimized so as to give the maximum oxygen reduction peak current with the lowest background signal. Pt NPs, >0−10 nm diameter, were found to deposit randomly across the pBDD electrode, with no preference for grain boundaries. The more conductive grains were found to promote the formation of smaller nanoparticles at higher density. With the use of potential step chronoamperometry, in which the potential was stepped to a diffusion-limited value, a four electron oxygen reduction process was found to occur at the Pt NP-modified pBDD electrode. Furthermore the chronoamperometric response scaled linearly with dissolved oxygen concentration, varied by changing the oxygen/nitrogen ratio of gas flowed into solution. The sensor was used to detect dissolved oxygen concentrations with high precision over the pH range 4−10.

Electrochemical impedance spectroscopy (EIS), coupled with chemical vapour deposition (CVD) grown single-walled carbon nanotube (SWNT) network disk-shaped ultramicroelectrodes (UMEs), gives stable, very well-defined and highly reproducible EIS responses for electrolysis of a simple outer sphere redox couple (FcTMA+/2+). The resulting EIS data can be fitted accurately using a simple electrical circuit model, enabling information on double-layer capacitance, diffusion coefficient of the electroactive species and the rate constant of ET (k0) to be extracted in a single EIS experiment. These values are replicated for a range of mediator concentrations and UME sizes (in the range 25–100 μm diameter) demonstrating the robustness of the method. These initial studies bode well for impedance based electroanalysis using SWNT network UMEs.

In this paper we demonstrate that the nucleation density of single-walled carbon nanotubes (SWNTs), formed by thermal catalytic chemical vapor deposition, strongly depends on the grain size of Al underlayers covered with a native oxide (Al/Al2O3). By varying the substrate temperature during Al sputter deposition it was possible to investigate the effect of Al grain size on growth without inducing changes in the underlayer thickness, surface chemistry, or any other growth parameter. The resulting SWNT growth structures ranged from low-density 2D nanotube networks that lay across the surface of the substrate to high density 3D nucleation which gave rise to vertical “forest” growth. The height of the SWNT “forest” was observed to increase with increasing Al deposition temperature as follows, 200 > 100 > 60 > 20 °C on Si/Al but in the order 100 > 200 > 60 > 20 °C on SiO2/Al substrates for fixed growth conditions. The differences in the SWNT growth trends on Si and SiO2 substrates are believed to be due to the existence of an optimal Al/Al2O3 underlayer grain size for the formation of active catalytic nanoparticles, with larger Al/Al2O3 grains forming on SiO2 than Si at a fixed substrate temperature. Numerous surface analysis techniques including AFM, XPS, FESEM, TEM, and Raman spectroscopy have been employed to ascertain that the observed changes in nanotube growth for this system are related primarily to changes in underlayer morphology.

It has been well documented that single-crystal stable-temperature (ST)-cut quartz substrates can horizontally align single-walled carbon nanotubes (SWNTs) along the x direction ([100]) during catalyzed chemical vapor deposition. It has been suggested that alignment is due to either surface-guided growth along step edges and/or lattice directions, although recent atomic force microscopy (AFM) evidence suggests the latter is more appropriate [Liu, et al. J. Am. Chem. Soc. 2008, 130, 5428]. In light of this we explore the growth mechanism on single-crystal quartz in more detail, focusing particularly on the crystallography of the alignment surface and the effects of annealing treatments. X-ray diffraction (XRD) studies enable us to identify, for the first time, the crystallographic plane of ST-cut quartz as (011̅1), with a surface normal lying close to [121], which is 42.5° from the y axis ([010]). For this plane, formulation of both crystallographic orientation and polar diagrams, the latter which reveals the magnitude of the longitudinal piezoelectric effect, indicate a high degree of correlation between the preferential SWNT growth direction and both the atomic arrangement and piezoelectric effect, strongly supporting a crystal plane driven alignment process. This is further supported by the absence of steps on the surface, observed topographically using AFM. Further evidence for crystal plane controlled alignment comes from field emission scanning electron microscopy (FE-SEM) and AFM observations of bending of the SWNTs away from the preferred alignment direction at defined angles. These angles are in agreement with the Si−O−Si atomic bond angles in quartz. Additionally, surfaces which are shown by XRD to have either minimal distortion in the lattice or surface misorientation caused by, e.g., tilts, cracks, etc., are those that are found to align the SWNTs best. Improvement in surface crystallinity can be achieved by annealing in air at high temperature; optimal annealing conditions of 950 °C in air for 30 mins were determined, in agreement with XRD data and FE-SEM images.

Ultramicroelectrodes (UMEs) fabricated from networks of chemical vapor deposited single-walled carbon nanotubes (SWNTs) on insulating silicon oxide surfaces are shown to offer superior qualities over solid UMEs of the same size and dimensions. Disk shaped UMEs, comprising two-dimensional “metallic” networks of SWNTs, have been fabricated lithographically, with a surface coverage of <1% of the underlying insulating surface. The electrodes are long lasting and give highly reproducible responses (either for repeat runs with the same electrode or when comparing several electrodes with the same size). For redox concentrations ≤1 mM the steady-state behavior of SWNT network UMEs is as expected for conventional solid metal UMEs (e.g., Pt, Au), due to diffusional overlap between neighboring SWNTs. Importantly, the low intrinsic capacitance of the SWNTs and much reduced surface area lead to much faster response times and lower background currents. The well-defined geometry of the SWNT network electrode is also useful for studying electron transfer (ET) kinetics at SWNTs. Given the intrinsically high mass transport rates to SWNTs within a network electrode, the reversible nature of the CVs recorded for Ru(NH3)63+/2+ and FcTMA+/2+ suggests that ET driven solely by defects on the sidewalls of the SWNTs is highly unlikely.

The effect of AFM probe geometry on diffusion to micrometer-scale reactive (electrode) interfaces is considered. A disk-shaped substrate electrode was held at a potential to reduce a species of interest (aqueous Ru(NH3)63+) at a diffusion-controlled rate and the current response during AFM imaging provided information on local mass transport to the interface. This approach reveals how the AFM probe influences diffusion to a reactive surface, which is of importance in more clearly delineating the conditions under which in-situ AFM can be treated as a noninvasive probe of surface processes involving mass transport (e.g., electrode reactions and crystal dissolution and growth). An assessment has been made of three types of probes: V-shaped silicon nitride contact mode probes; single beam silicon probes; and batch-fabricated scanning electrochemical-atomic force microscopy (SECM-AFM) probes. Two disk electrodes, (6.1 µm and 1.6 µm diameter) have been considered as substrates. The results indicate that conventional V-shaped contact mode probes are the most invasive and that the batch-fabricated SECM-AFM probes are the least invasive to diffusion at both of the substrates used herein. The experimental data are complemented by the development of simulations based on a simple 2D model of the AFM probe and active surface site. The importance of probe parameters such as the cantilever size, tip cone height, and cone angle is discussed, and the implications of the results for studies in other areas, such as growth and dissolution processes, are considered briefly.

This paper describes in detail the use of electron beam lithography (EBL) to successfully batch microfabricate combined scanning electrochemical-atomic force microscopy (SECM-AFM) probes. At present, the process produces sixty probes at a time, on a 1/4 of a three-inch wafer. Using EBL, gold triangular-shaped electrodes can be defined at the tip apex, with plasma enhanced chemical vapor deposited silicon nitride serving as an effective insulating layer, at a thickness of 75 nm. The key features of the fabrication technique and the critical steps are discussed. The capability of these probes for SECM-AFM imaging in both tapping and constant distance mode is illustrated with dual topographical–electrochemical scans over an array of closely-spaced 1 μm diameter Pt disc electrodes, held at a suitable potential to generate an electroactive species at a transport-limited rate. As highlighted herein, understanding diffusion to heterogeneous electrode surfaces, including array electrodes, is currently topical and we present preliminary data highlighting the use of SECM-AFM as a valuable tool for the investigation of diffusion and reactivity at high spatial resolution.

Incorporation of non-luminescent dodecanethiolate-protected gold clusters into regioregular poly(3-hexylthiophene) films results in a 6-fold increase in the visible photoluminescence (PL) of the polymer, which arises predominantly from NP-induced structural changes in the composite films.

The characteristics of three different carbon electrodes, glassy carbon (GC), oxygen-terminated polycrystalline boron-doped diamond (pBDD) and “pristine” carbon nanotube networks (CNTN) as voltammetric sensors for detection of the neurotransmitter serotonin have been investigated. For each electrode, detection sensitivity was determined using cyclic voltammetry (CV), a technique often used to provide information on chemical identity in electrochemical assays. The CNTN electrodes were found to exhibit background current densities ca. two orders of magnitude smaller than the GC electrode and ca. twenty times smaller than pBDD, as a consequence of their “pristine” low capacitance and low surface coverage. This was a major factor in determining serotonin detection limits from CV, of 10 nM for the CNTN electrode, 500 nM for pBDD and 2 μM for GC. The two most sensitive electrodes (CNTN and pBDD) were further investigated in terms of resistance to electrode fouling. CV analysis showed that fouling was less on the pBDD electrode compared to the CNTN and, furthemore, for the case of pBDD could be significantly minimised by careful selection of the CV potential limits, in particular by scanning the electrode potential to suitably cathodic values after oxidation of the serotonin.

Optically transparent ultramicroelectrodes (OT-UMEs) comprising carbon nanotube (CNT) networks on quartz, are introduced and used to monitor quantitatively the interfacial concentration of tris(2,2′-bipyridine)ruthenium(II) during cyclic voltammetry. The OT-CNT-UMEs combine the attractive properties of small-scale electrodes, e.g., high diffusion rates and good signal-to-noise, with the ability to probe electrochemical processes optically, from the rear of the electrode. This enables optical measurements of the solution, close to the electrode surface, without significant interference from absorption or scattering processes.

The electrochemical properties of the closed ends and sidewalls of pristine carbon nanotube forests are investigated directly using a nanopipet electrochemical cell. Both are shown to promote fast electron transfer, without any activation or processing of the carbon nanotube material required, in contrast to the current model in the literature.

Electrochemistry at carbon nanotubes (CNTs) is a large and growing field, but one in which there is still uncertainty about the fundamental activity of CNTs as electrode materials. On the one hand, there are many reports which focus on the favourable electrochemical properties of CNT electrodes, such as enhanced detection sensitivity, electrocatalytic effects and reduced fouling. On the other hand, other studies suggest that CNTs may be no more electroactive than graphitic powder. Furthermore, it has been proposed that the catalytic nanoparticles from which CNTs are formed may dominate the electrochemical characteristics in some instances. A considerable body of the literature presumes that the CNT sidewall is inert and that edge-plane-graphite-like open ends and defect sites are responsible for the electron transfer activity observed. In contrast, studies of well characterised single-walled nanotube (SWNT) electrodes, either as individual tubes or as two-dimensional networks, suggest sidewall activity. This review highlights how the various discrepancies in CNT electrochemistry may have arisen, by taking a historical view of the field and identifying crucial issues that still need to be solved. When assessing the behaviour of CNT electrodes, it is vitally important that careful consideration is given to the type of CNT used (SWNT or multi-walled), the quality of the material (presence of impurities), the effect of chemical processing steps in the fabrication of electrodes and the experimental arrangements adopted. Understanding these key features is an essential requirement to develop a fundamental understanding of CNT electrochemistry, to allow a wide range of electroanalytical applications, and to move the field forward rationally. As part of this process, high resolution electrochemical and electrical imaging techniques are expected to play a significant role in the future, as well as theoretical developments which examine the fundamentals of electron transfer at different types of CNTs and their characteristic surface sites.

Scanning electrochemical cell microscopy is utilised as a read–write pipette-based probe to both electrochemically modify the local surface chemistry of boron doped diamond and “read” the resulting modification, at the micron scale. In this specific application, localised electrochemical oxidation results in conversion of the H-terminated surface to –O, electrochemically visualised by monitoring the current change for reduction of Ru(NH3)63+. This methodology, in general, provides a platform for read–write analysis of electrodes, opening up new analytical avenues, particularly as the pipette can be viewed as a microfluidic device.

Generator-detector electrodes can be used to both perturb and monitor pH dependant metal–ligand binding equilibria, in situ. In particular, protons generated at the generator locally influence the speciation of metal (Cu2+) in the presence of ligand (triethylenetetraamine), with the detector employed to monitor, in real time, free metal (Cu2+) concentrations.

The change in surface morphology of oxygen-terminated polycrystalline boron doped diamond (pBDD) during electrochemical oxidation of the neurotransmitter serotonin (5-HT), resulting in a corresponding deterioration of the current signal, is investigated for the first time using both high resolution ex situ and in situ microscopy under a range of different electrochemical conditions. In situ electrochemical-atomic force microscopy (EC-AFM) reveals the formation of a granular film over the surface, which grows faster at higher-doped regions of the electrode surface and increases in thickness with repetitive potential cycles. The film properties were investigated using both cyclic voltammetry, with a range of redox species varying in charge, and conducting-AFM. These studies reveal the film to be positively charged and electrically insulating. The extent to which the film forms during 5-HT oxidation could be significantly minimised using different electrochemical procedures, as verified by voltammetry and in situ EC-AFM. Finally, even after extensive film formation, the original current signal could be recovered simply by leaving the electrode at open circuit potential for a short period of time, highlighting the suitability of BDD electrodes for neurotransmitter detection.

Boron doped diamond (BDD) disk ultramicroelectrodes have been used to sense single nanoparticle (NP) electrocatalytic collision events. BDD serves as an excellent support electrode due to its electrocatalytic inactivity and low background currents and thus can be used to detect the electroactivity of a wide range of colliding NPs, with high sensitivity. In particular, single NP collisions for hydrazine oxidation at Au and Pt NPs were shown to be markedly different.

Voltammetric studies of dopamine (DA) oxidation on pristine and acid-treated single-walled carbon nanotube (SWNT) network electrodes were undertaken in order to investigate both the effect of network density and acid treatment times on the voltammetric characteristics for DA oxidation and the susceptibility of the electrodes to fouling. Through careful control of catalysed chemical vapour deposition growth parameters, multiply interconnected and randomly oriented SWNT networks of two significantly different densities were grown (high density, HD, coverage ≫10 μm length of SWNT per μm−2 and low density, LD, coverage = 5 (±1) μmSWNT μm−2). Acid treatment was performed to provide materials with different electrochemical properties and SWNT coverage, as determined by field emission-scanning electron microscopy, atomic force microscopy and micro-Raman spectroscopy. A high concentration of DA (100 μM) was deliberately employed to accelerate the fouling phenomenon associated with DA oxidation in order to evaluate the lifetime of the electrodes. HD pristine SWNT networks were found to promote more facile electron transfer (ET) and were less susceptible to blocking, compared to LD pristine SWNT networks. Acid treatment resulted in both a further enhancement of the ET rate and a reduction in susceptibility towards electrode fouling. However, lengthy acid treatment detrimentally affected ET, due to a decrease in network density and significant damage to the SWNT network structure. These studies highlight the subtle interplay between SWNT coverage and degree of acid functionalisation when seeking to achieve the optimal SWNT electrode for the voltammetric detection of DA.

Networks of pristine single walled carbon nanotubes (SWNTs) grown by catalysed chemical vapour deposition (cCVD) on an insulating surface and arranged in an ultramicroelectrode (UME) format are insensitive to the electro-oxidation of hydrazine (HZ) in aqueous solution, indicating a negligible metallic nanoparticle content. Sensitisation of the network towards HZ oxidation is promoted by the deliberate and controlled electrodeposition of “naked” gold (Au) nanoparticles (NPs). By controlling the deposition conditions (potential, time) it is possible to control the size and spacing of the Au NPs on the underlying SWNT network. Two different cases are considered: Au NPs at a number density of 250 ± 13 NPs μm−2 and height 24 nm ± 5 (effective surface coverage, θ = 92%) and (ii) Au NPs of number density ∼ 22 ± 3 NPs μm−2 and height 43 nm ± 8 nm (θ = 35%). For both morphologies the HZ oxidation half-wave potential (E1/2) is shifted significantly negative by ca. 200 mV, compared to a gold disc UME of the same geometric area, indicating significantly more facile electron transfer kinetics. E1/2 for HZ oxidation for the higher density Au NP-SWNT structure is shifted slightly more negative (by ∼25 mV) than E1/2 for the lower density Au NP electrode. This is attributed to the lower flux of HZ at NPs in the higher number density arrangement (smaller kinetic demand). Importantly, using this approach, the calculated HZ oxidation current density sensitivities for the Au NP-SWNT electrodes reported here are higher than for many other metal NP functionalised carbon nanotube electrodes.

Double potential step chronoamperometry (DPSC) is demonstrated as a technique for investigating partitioning between a solute in aqueous solution and non-polar oil droplet(s) immobilised at an electrode. Here a species in aqueous solution which does not partition into the oil phase is converted at the electrode surface into another species which either does not or does partition into the oil drop. The first case is investigated experimentally by considering generation of the ionic redox species, FcTMA2+ from FcTMA+, while the second case is exemplified by studies of Br2 generation from Br−. The case of molecular partitioning at the three phase interface has received little attention hitherto. To maintain oil droplet stability a boron-doped diamond electrode is employed functionalised with Pt nanoparticles to impart electrocatalytic activity on the electrode towards Br2 production. An arrangement is utilised where the droplet(s) sit(s) on (but does not cover) the electrode surface. We show both experimentally and through finite element simulation how the charge–time profile for the generation and collection of electroactive species can be used to obtain information on the extent of partitioning and how this is affected by factors such as the number and size of droplets. Finally, we highlight the suitability of this approach for investigating reactions which take place within the droplet.

The effect of systematic anodic pre-treatments of pristine single walled carbon nanotube (SWNT) forests on the electrochemical response towards a variety of redox processes is investigated. An experimental arrangement is adopted whereby a microcapillary containing the solution of interest and a quasi reference-counter electrode is brought into contact with a small portion of the forest to enable measurements on the surface before and after controlled anodic polarisation (AP). AP of the surface is found to both improve the voltammetric response (faster apparent heterogeneous electron transfer kinetics) of surface sensitive redox processes, such as Fe2+/3+, and enhance the electrocatalytic response of the SWNTs towards oxygen reduction; the extent of which can be carefully controlled via the applied anodic potential. AP is expected to remove any trace organic (atmospheric) contaminants that may accumulate on the forest over extended periods as well as allowing the controlled introduction of defects, as confirmed by micro-Raman spectroscopy.