Electrochemical "read-write" microscale patterning of boron doped diamond electrodes.

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)6(3+). 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.

Electrochemical X-ray fluorescence spectroscopy for trace heavy metal analysis: enhancing X-ray fluorescence detection capabilities by four orders of magnitude.

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 Cu(2+) and Pb(2+) 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 Cu(2+)/Pb(2+) solutions, EC-XRF shows that Cu(2+) deposition is unimpeded by Pb(2+), across a broad concentration range, but this is only true for Pb(2+) 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, E(0), or exhaustively deplete it from solution, enabling uninhibited detection of the metal with the more negative E(0).

Examination of the factors affecting the electrochemical performance of oxygen-terminated polycrystalline boron-doped diamond electrodes.

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] > 10(20) 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 × 10(20) 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)6(4-) electrolysis, the first time this has been reported at an oxygen-terminated surface.

Boron doped diamond ultramicroelectrodes: a generic platform for sensing single nanoparticle electrocatalytic collisions.

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.

Electrochemical mapping reveals direct correlation between heterogeneous electron-transfer kinetics and local density of states in diamond electrodes.

Conducting carbon materials: a multi-microscopy approach shows that local heterogeneous electron-transfer rates at conducting diamond electrodes correlate with the local density of electronic states. This model of electroactivity is of considerable value for the rational design of conducting diamond electrochemical technologies, and also provides key general insights on electrode structure controls in electrochemical kinetics.

Fabrication and characterization of an all-diamond tubular flow microelectrode for electroanalysis.

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.

Factors controlling stripping voltammetry of lead at polycrystalline boron doped diamond electrodes: new insights from high-resolution microscopy.

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/Pb(2+) 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 Pb(2+) 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/Pb(2+) 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.