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Owing to their biocompatibility, optical, and catalytic properties, Au nanoparticles (NPs) have been the subject of much research. Since smaller NPs have enhanced catalytic properties and NP morphology greatly impacts their effectiveness, controlled and reproducible methods of generating Au NPs are still being sought. Herein, Au NPs were electrochemically generated at a water|ionic liquid (w|IL) immiscible micro-interface, 25 µm in diameter, using a redox active IL and compared to results at a water|oil (w|o) one. The liquid|liquid interface is advantageous as it is pristine and highly reproducible, as well as an excellent means of species and charge separation. In this system, KAuCl4 dissolved in the aqueous phase reacts under external potential control at the water|P8888TB (tetraoctylphosphonium tetrakis(pentafluorophenyl)borate) with trioctyl(ferrocenylhexanoyl)phosphonium tetrakis(pentafluorophenyl)borate (FcIL), an electron donor and redox active IL. FcIL was prepared with a common anion to P8888TB, which greatly enhances its solubility in the bulk IL. Simple ion transfer of AuCl4− and AuCl(4−γ)(OH)γ− at the w|P8888TB micro-interface were characterized voltammetrically as well as their heterogeneous electron transfer reaction with FcIL. This interfacial reaction generates Au NPs whose size can be thermodynamically controlled by modifying the pH of the aqueous phase. Critically, at low pH, nanoclusters, <1.7 nm in diameter, were generated owing to inhibited thermodynamics in combination with the supramolecular fluidic nature of the IL microenvironment that was observed surrounding the as-prepared NPs. [ABSTRACT FROM AUTHOR]

Cu nanoparticles (NPs) have been shown to be excellent electrocatalysts, particularly for CO2 reduction – a critical reaction for sequestering anthropogenic, atmospheric carbon. Herein, the micro interface between two immiscible electrolyte solutions (ITIES) is exploited for the simultaneous electropolymerization of 2,2′:5′,2′′-terthiophene (TT) and reduction of Cu2+ to Cu nanoparticles (NPs) generating a flexible electrocatalytic composite electrode material. TT acts as an electron donor in 1,2-dichloroethane (DCE) through heterogeneous electron transfer across the water|DCE (w|DCE) interface to CuSO4 dissolved in water. The nanocomposite formation process was probed using cyclic voltammetry as well as electrochemical impedance spectroscopy (EIS). CV and EIS data show that the film forms quickly; however, the interfacial reaction is not spontaneous and does not proceed without an applied potential. At high [TT] the heterogeneous electron transfer wave was recorded voltammetrically but not at low [TT]. However, probing the edge of the polarizable potential window was found to be sufficient to initiate electrogeneration/electropolymerization. SEM and TEM were used to image and analyze the final Cu NP/poly-TT composites and it was discovered that there is a concomitant decrease in NP size with increasing [TT]. Preliminary electrocatalysis results at a nanocomposite modified large glassy carbon electrode saw a > 2 × increase in CO2 reduction currents versus an unmodified electrode. These data suggest that this strategy is a promising means of generating electrocatalytic materials for carbon capture. However, films electrosynthesized at a micro and ~ 1 mm ITIES demonstrated poor reusability. [ABSTRACT FROM AUTHOR]

Miniaturization of electrochemical detection methods for point-of-care-devices is ideal for their integration and use within healthcare environments. Simultaneously, the prolific pathogenic bacteria Pseudomonas aeruginosa poses a serious health risk to patients with compromised immune systems. Recognizing these two factors, a proof-of-concept electrochemical method employing a micro-interface between water and oil (w/o) held at the tip of a pulled borosilicate glass capillary is presented. This method targets small molecules produced by P. aeruginosa colonies as signalling factors that control colony growth in a pseudo-multicellular process known as quorum sensing (QS). The QS molecules of interest are 4-hydroxy-2-heptylquinoline (HHQ) and 2-heptyl-3,4-dihydroxyquinoline (PQS, Pseudomonas quinolone signal). Hydrophobic HHQ and PQS molecules, dissolved in the oil phase, were observed electrochemically to facilitate proton transfer across the w/o interface. This interfacial complexation can be exploited as a facile electrochemical detection method for P. aeruginosa and is advantageous as it does not depend on the redox activity of HHQ/PQS. Interestingly, the limit-of-linearity is reached as [H+] ≈ [ligand]. Density functional theory calculations were performed to determine the proton affinities and gas-phase basicities of HHQ/PQS, as well as elucidate the likely site of stepwise protonation within each molecule. [ABSTRACT FROM AUTHOR]