We present the facile synthesis of Ni/NiO nanocomposites, via a solution combustion methodology, where the composition of metallic Ni within NiO is controlled by varying the annealing time, from 4 minutes up to 8 hours. The various Ni/NiO nanocomposites are studied via electrically wiring them upon screen-printed graphite macroelectrodes by physical deposition. Subsequently their electrochemical activity, towards the oxygen evolution reaction (OER), is assessed within (ultra-pure) alkaline media (1.0 M KOH). An optimal annealing time of 2 hours is found, which gives rise to an electrochemical oxidation potential (recorded at 10 mA cm−2) of 231 mV (vs. Ag/AgCl 1.46 vs. RHE). These values show the Ni/NiO nanocomposites to be significantly more electrocatalytic than a bare/unmodified SPE (460 mV vs. Ag/AgCl). A remarkable percentage increase (134%) in achievable current density is realised by the former over that of the latter. Tafel analysis and turn over frequency is reported with a likely underlying mechanism for the Ni/NiO nanocomposites towards the OER proposed. In the former case, Tafel analysis is overviewed for general multi-step overall electrochemical reaction processes, which can be used to assist other researchers in determining mechanistic information, such as electron transfer and rate determining steps, when exploring the OER. The optimal Ni/NiO nanocomposite exhibits promising stability at the potential of +231 mV, retaining near 100% of its achievable current density after 28 hours. Due to the facile and rapid fabrication methodology of the Ni/NiO nanocomposites, such an approach is ideally suited towards the mass production of highly active and stable electrocatalysts for application within the anodic catalyst layers of commercial alkaline electrolysers.
2D-MoSe2 and Pt/C containing additive manufactured electrodes, which exhibit electrocatalysis towards the hydrogen evolution and oxygen evolution reactions.
Molecularly Imprinted Polymers (MIPs) were synthesised for the selective detection of amoxicillin in aqueous samples. Different functional monomers were tested to determine the optimal composition via batch rebinding experiments. Two different sensor platforms were tested using the same MIP solution; one being bulk synthesized and surface modified Screen Printed Electrodes (SPEs) via drop casting the microparticles onto the electrode surface and the other being UV polymerized directly onto the SPE surface in the form of a thin film. The sensors were used to measure amoxicillin in conjunction with the Heat-Transfer Method (HTM), a low-cost and simple thermal detection method that is based on differences in the thermal resistance at the solid–liquid interface. It was demonstrated that both sensor platforms could detect amoxicillin in the relevant concentration range with Limits of Detection (LOD) of 1.89 ± 1.03 nM and 0.54 ± 0.10 nM for the drop cast and direct polymerisation methods respectively. The sensor platform utilising direct UV polymerisation exhibited an enhanced response for amoxicillin detection, a reduced sensor preparation time and the selectivity of the platform was proven through the addition of nafcillin, a pharmacophore of similar shape and size. The use of MIP-modified SPEs combined with thermal detection provides sensors that can be used for fast and low-cost detection of analytes on-site, which holds great potential for contaminants in environmental aqueous samples. The platform and synthesis methods are generic and by adapting the MIP layer it is possible to expand this sensor platform to a variety of relevant targets.
The electroanalytical detection of the neurotransmitter dopamine (DA) in the presence of uric acid (UA) is explored for the first time using commercially procured nanodiamonds (NDs). These are electrically wired via surface modification upon screen-printed graphite macroelectrodes (SPEs). The surface coverage of the NDs on the SPEs was explored in order to optimize electroanalytical outputs to result in well-resolved signals and in low limits of detection. The (electro)analytical outputs are observed to be more sensitive than those achieved at bare (unmodified) SPEs. Such responses, previously reported in the academic literature have been reported to be electrocatalytic and have been previously attributed to the presence of surface sp2 carbon and oxygenated species on the surface of the NDs. However, XPS analysis reveals the commercial NDs to be solely composed of nonconductive sp3 carbon. The low/negligible electroconductivity of the NDs was further confirmed when ND paste electrodes were fabricated and found to exhibit no electrochemical activity. The electroanalytical enhancement, when using NDs electronically wired upon SPEs, is attributed not to the NDs themselves being electrocatalytic, as reported previously, but rather changes in mass transport where the inert NDs block the underlying electroactive SPEs and create a random array of graphite microelectrodes. The electrode was applied to simultaneous sensing of DA and UA at pH 5.5. Figures of merit include (a) low working potentials of around 0.27 and 0.35 V (vs. Ag/AgCl); and (b) detection limits of 5.7 × 10−7 and 8.9 × 10−7 M for DA and UA, respectively. The electroanalytical enhancement of screen-printed electrodes modified with inert/non-conductive nanodiamonds is due to a change in mass transfer where the inert nanodiamonds facilitate the production of a random microelectrode array.