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.

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).

A hybrid sp 2 -sp 3 electrochemical sensor comprising patterned regions of nondiamond-carbon (sp 2 ) in a boron doped diamond (sp 3 ) matrix is described for the simultaneous voltammetric detection of dissolved oxygen (DO) and pH in buffered aqueous solutions. Using a laser micropatterning process it is possible to write mechanically robust regions of sp 2 carbon into a BDD electrode. These regions both promote the electrocatalytic reduction of oxygen and facilitate the proton coupled electron transfer of quinone groups, integrated into the surface of the sp 2 carbon. In this way, in one voltammetric sweep (time of measurement ∼4 s) it is possible to determine both the DO concentration and solution pH. By varying the sp 2 pattern the response can be optimized toward both analytes. Using a closely spaced sp 2 microspot array, a linear response toward DO, across the range 0.0 to 8.0 mg L −1 (0.0 to 0.25 mM; sensitivity = −8.77 × 10 −8 A L mg −1 , R 2 = 0.9991) and pH range 4−10 (sensitivity = 59.7 mV pH −1 , R 2 = 0.9983) is demonstrated. The electrode is also capable of measuring both DO concentration and pH in the more complex buffered environment of blood. Finally, we show how the peak position for ORR is independent of pH, and thus via measurement of the difference in ORR and pH peak position, internal referencing is possible. Such electrodes show great promise for use in applications ranging from biomedical sensing to water analysis.

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.

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.

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 (Cu(2+)) in the presence of ligand (triethylenetetraamine), with the detector employed to monitor, in real time, free metal (Cu(2+)) concentrations.

Boron doped diamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended solvent window, low background currents, corrosion resistance, etc., arise from the catalytically inert nature of the surface. However, if during the growth process, non-diamond-carbon (NDC) becomes incorporated into the electrode matrix, the electrochemical properties will change as the surface becomes more catalytically active. As such it is important that the electrochemist is aware of the quality and resulting key electrochemical properties of the BDD electrode prior to use. This paper describes a series of characterization steps, including Raman microscopy, capacitance, solvent window and redox electrochemistry, to ascertain whether the BDD electrode contains negligible NDC i.e. negligible sp 2 carbon. One application is highlighted which takes advantage of the catalytically inert and corrosion resistant nature of an NDC-free surface i.e. stable and quantifiable local proton and hydroxide production due to water electrolysis at a BDD electrode. An approach to measuring the local pH change induced by water electrolysis using iridium oxide coated BDD electrodes is also described in detail. Video LinkThe video component of this article can be found at

Ex-vivo pH profiling of the upper gastrointestinal (GI) tract (of a mouse) in both the absence and presence of pharmacological agents aimed at altering acid/bicarbonate production, is reported using an electrochemical pH probe, for the first time. Three pH electrodes were assessed for suitability using a GI tract biological mimic buffer solution containing 0.5 % mucin. These include a traditional glass pH probe, an iridium oxide (IrOx) coated electrode (both potentiometric) and a quinone (Q) surface-integrated boron doped diamond (BDD-Q) electrode (voltammetric). In mucin the timescale for both IrOx and glass to obtain stable pH readings was in the ~100's of s, most likely due to mucin adsorption, in contrast to 6 s with the BDD-Q electrode. Both the glass and IrOx pH electrodes were also compromised on robustness due to fragility and delamination (IrOx); contact with the GI tissue was an experimental requirement. BDD-Q was deemed the most appropriate. Ten measurements were made along the GI tract, esophagus (1), stomach (5) and duodenum (4). Under untreated conditions (buffer only), the BDD-Q probe tracked the pH from neutral in the esophagus, to acidic in the stomach and rising to more alkaline in the duodenum. In the presence of omeprazole, a proton pump inhibitor, the body regions of the stomach exhibited elevated pH levels. Under melatonin treatment (a bicarbonate agonist and acid inhibitor), both the body of the stomach and the duodenum showed elevated pH levels. This study demonstrates the versatility of the BDD-Q pH electrode for real-time ex-vivo biological tissue measurements. File list (2) download file view on ChemRxiv Mucin-pH paper v15_FINAL.pdf (759.94 KiB) download file view on ChemRxiv Mucin-pH paper SI v5_FINAL.pdf (690.31 KiB)