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Microfluidic paper-based analytical devices (µPADs) have been successfully developed using dual detection: electrochemical and colorimetric systems. The µPADs have the potential to be used as Pb(II), Cd(II), and Cu(II) sensors to test the quality of water. The fabrication process uses hot embossing and screen-printing methods. The working electrode in the electrochemical zone was enhanced by the bismuth metal deposition process, while in the colorimetric zone, the gold nanoparticles modified with thioctic acid and dansylhydrazine (TA-Au-DNS) were used as a colorimetric sensor to detect Cu. The basic material of µPADs was characterized using a Fourier-transform infrared (FTIR) and a contact angle meter (CAM). In the electrochemical zone, the signals of square wave anodic stripping voltammetry (SWASV) resulted in good detection of Pb(II) and Cd(II) (from 0 to 100 ppb) with a limit of detection of 1.588 and 1.42 ppb, respectively. In the colorimetric zone, the performance of TA-Au-DNS for detecting Cu metal was obtained from readings through the red-green-blue (RGB) sensor as a miniature of µPADs reader. The LOD, LOQ, and average Vx0 (linearity values) in the detection of Cu(II) (from 58 to 100 ppb) are 8.51 ppb, 28.36 ppb, and 0.41%, respectively.

Transition metal dichalcogenide (TMD) heterostructures have been discovered to have improved catalytic activity towards the hydrogen evolution reaction (HER). This study explores the stability and HER catalytic activity including reaction kinetics of heterolayers of different TMDs (MoS2, MoSe2 and WS2). The stability of the heterolayers varied with those having an overlayer of electrodeposited MoS2 being more stable as compared to those with MoSe2 overlayer which degraded with each scan in acidic media. Investigation into the HER kinetics of the heterolayers involved Tafel analysis and electrochemical rate constant calculation. There was an improvement in Tafel values calculated in comparison to reported values for these heterolayers. WS2/MoS2 and MoSe2/MoS2 heterolayers registered rate constants of (3.20 ± 0.10) × 10−4 cm s−1 and (1.73 ± 0.03) × 10−4 cm s−1 respectively, which was an improvement of up to an order of magnitude compared to the reported rate constant of electrodeposited MoS2 of (3.17 ± 0.30) × 10−5 cm s−1. All this highlights the improved HER catalytic activity of the heterolayers.

The commercialisation of polymer electrolyte fuel cells (PEFCs) has been hampered by the high cost of platinum metal. Due to its high durability and catalytic activity, platinum is widely used to catalyse the oxygen reduction and hydrogen oxidation reactions essential to the operation of these cells. Core@shell nanoparticles with thin layers of platinum deposited on cores composed of cheaper materials have offered an attractive route towards the reduction of overall loading of platinum, with the retention of active catalyst surface area. This review surveys approaches taken to prepare idealised active and durable core@shell nanocatalysts by tweaking core compositions. A critical reflection on the current status of the field, as well as predictions as to likely directions for future developments, are discussed as a conclusion to the review.

A hydrogen economy powered by fuel cells is emerging as an alternative to the current fossil-fuel based energy system where hydrogen, produced through renewable sources, is used to generate electricity via fuel cells. A commonly investigated fuel cell, the Polymer Electrolyte Fuel Cell (PEMFC), usually uses platinum and other platinum group metal nanomaterials to catalyze the rate limiting Oxygen Reduction Reaction (ORR) of this process. The high prices and durability limitations of these catalysts have prevented their mass commercialization. Biosynthesis of nanomaterials has emerged as a potentially attractive “eco-friendly” alternative to conventional chemical synthesis methods. Various attempts have been made to biosynthesize nanoparticles for use in fuel cells. However, the processing methods used during and post synthesis increase their costs and limit their overall efficacies. We report bimetallic Pt/Pd nanoparticles (NPs) biosynthesized by E. coli [E. coli-Pt/Pd (10 wt%:10 wt%)] that shows promise for direct use as a PEMFC catalyst. This catalyst outperformed single metal versions of the same, i.e., E. coli-Pt (20 wt%) and E. coli-Pd (20 wt%) when tested as an electrocatalyst ex-situ. Direct use of E. coli-synthesized nanoparticles in PEMFCs is limited by the inherent resistances of the bacteria and the internal localization of nanoparticles. Transmission electron microscopy images and impedances (resistivity) tests showed that by initially synthesizing Pd nanoparticles on the E. coli cells, followed by Pt, gave a cell surface-localized metallic shell that improved conductivity of the catalyst. Catalyst Pt synthesis is likely mediated by initially-formed Pd-NPs reducing Pt (IV) under H2 resulting in alloying; this was evidenced by XRD data that showed XRD peaks for E. coli-Pt/Pd (10%:10%) which lie in between XRD peaks for Pt-only and Pd-only nanoparticles on the same planes. Protrusions of agglomerated nanoparticles were seen on the cell surface to form sites for catalytic activity. The catalyst, used in the ORR without optimization, performed significantly worse (~100 times) than a commercial catalyst (extensively developed for purpose) but which contained 5 times as much Pt. This serves as a starting point for a more engineered approach to bio-synthesizing nanoparticles for PEMFC catalysts.

A simple but sensitive technique has been demonstrated towards the electroanalytical quantification of the strength of garlic. This technique can also be used to quantify dialkyldisulfides. The cyclic voltammetry of bromide was found to be a sensitive electrochemical probe, electrogenerated bromine reacting with dialkyldisulfides to catalytically regenerate bromide, resulting in a significant increase in peak current. A linear response of current vs.concentration was observed between 0.1 and 15 mM dipropyldisulfide at edge plane pyrolytic graphite (EPPG) electrodes; a smaller range up to ca.5 mM was available at screen printed carbon electrodes (SPCEs), with a detection limit (from 3σ) of 0.067 mM. The response of diallyldisulfide was found to be essentially identical. Shaking garlic puree in acetonitrile for 5 minutes, followed by dilution with water then recording the voltammetry at the cheap, disposable SPCE gave a linear trend in current with respect to the quantity of garlic present, corresponding to the diallyldisulfide extracted. This has potential applications in monitoring the garlic content of medicinal supplements, batch-to-batch variation and the stability of garlic during storage. [ABSTRACT FROM AUTHOR]

Dynamic electrochemistry has been often viewed from outside the field as primarily a means to determine kinetic and thermodynamic information about redox-active species in solution. However, in recent years electrochemical applications have become increasingly diverse. In this brief review, we survey the use of voltammetry as a probe of distance, starting with scanning electrochemical microscopy (SECM) and arriving at the present day with characterisation of moving particles and nanoscale measurements. [ABSTRACT FROM AUTHOR]

We present the novel use of photoelectrochemistry to detect and monitor the motion of a single Daphnia magnaswimming in a confined volume of water. Using an array of individually-addressable electrodes under illumination and potentiostatted so that a photocurrent is generated, the motion of the daphnid is detected by means of measuring “dark” transients as the shadow cast by the moving sphere passes over each electrode. The method can be used to determine the size and speed of a single daphnid. [ABSTRACT FROM AUTHOR]

Microelectrode arrays find broad application in electroanalysis offering the enhanced sensitivity associated with microelectrodes, but with a high total current output. Such arrays are often constructed to make the electrodes ‘diffusionally independent’. To emphasize that this is a time dependent property, a two-dimensional simulation, in conjunction with the diffusional domain approach, is used to model potential step transient currents at microelectrode arrays. Two types of array, hexagonal and cubic, are considered. In both cases the absolute (not relative) microelectrode separation distance has a significant effect on transient current. Three different regimes of transient current versustime can be observed at microelectrode arrays. At short times the transient response of isolated microelectrodes is seen, then at intermediate times the steady-state response of independent electrodes can be observed. At longer times planar diffusion to the entire array takes over. It follows that only at timescales corresponding to the first two regimes can the electrodes be considered as diffusionally independent. To verify the theory the potential step experiment is performed at a regularly spaced hexagonal iridium microdisk array. Theory is found to be in a good agreement with the experimental results. [ABSTRACT FROM AUTHOR]

Multi-walled carbon nanotubes (CNTs) functionalized both by nickel and silver nanoparticles were obtained using a single step chemical deposition method in an ultrasonic bath. The new composite material was characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV). The electroactivity of the bi-functionalized CNTs multi-walled carbon nanotubes was assessed in respect to the electrooxidation of methanol. It was found that the carbon nanotube supported silver nanoparticles have significantly higher catalytic properties than the bulk metal of the same surface area. Furthermore, it was shown that the presence of only a very small proportion of magnetic nickel nanoparticles (1.5% of the total number of metallic nanoparticles) allows the bi-functionalized carbon nanotubes to be moved magnetically in solution, making them easily recoverable after use whilst keeping an optimal electrocatalytic surface area. [ABSTRACT FROM AUTHOR]

“Bamboo-like” multiwalled (b-MWCNT), “hollow-tube” multiwalled (h-MWCNT) and single-walled carbon nanotubes (SWCNT), chemically modified with 1-anthraquinonyl (AQ) or 4-nitrophenyl (NP) groups, are characterized using voltammetric, electron microscopic and Raman spectroscopic techniques. The pKa values of the AQ-modified CNTs are found to be shifted by greater than three units when compared to the pKa values of anthrahydroquinone (AHQ, the reduced form of AQ) in aqueous solution to beyond pH 14. These large changes in the surface pKa values of the modified CNTs are explored further by comparing the pKa values of CNTs modified with an anthraquinonyl-2-carboxylic acid group. These groups are attached to the CNT surface via the formation of an amide bond with an aminophenyl “spacer” unit derived from the chemical reduction of NP modified CNTs. The location of reactive sites on the CNT surface is investigated and their influence on the pKa of the modified materials is discussed. Comparison with modified pyrolytic graphite electrodes exposing pure edge-plane or pure basal-plane crystal faces indicates that the modifying aryl groups are predominantly located on edge-plane like defects at the tube ends of MWCNTs. The effect of polymer formation on electron transfer kinetics of b-MWCNTs and h-MWCNTs is also discussed. In contrast SWCNTs show both significant side-wall functionalisation and fast electron transfer kinetics which is attributed to their different electronic structure. [ABSTRACT FROM AUTHOR]

This communication presents initial results into the use of chronoamperometry of acoustically agitated particulate suspensions at a dual electrode as a means of approximately sizing the suspended particles. [ABSTRACT FROM AUTHOR]