Copper nanoparticles have emerged as promising electrocatalysts for energy storage and conversion. Generally, homogenous nanoparticle synthesis requires a stabilizing ligand, which may influence the electrocatalysis. Ligands can be avoided by...
We present a facile method to detect methamphetamine in aerosols by trapping aerosols in a soap bubble wall for electroanalysis. A microwire was placed through a soap bubble wall as a sensing electrode along with a 1 mm diameter platinum wire as the counter/reference electrode. The resulting electrochemical cell and electrode geometry are unique and allow for reproducible electrochemistry between bubble walls. We first provide a thorough investigation of the cell and electrode geometry and an electrochemical characterization of ferrocene methanol in a soap bubble wall composed of 0.1 M KCl and 0.1% Triton X-100 (v/v). To visualize the boundary where the bubble wets the microwire (the effective electrode area) with tens of nanometer resolution, we electrodeposited platinum on carbon microwire. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the bubble contact (i.e., cylindrical electrode height) is 157 ± 30 μm. Correlated digital microscopy suggests that the wetting reaches r ∼ 125 μm along the bubble wall laterally from the microwire. Beyond the wetting region, the bubble thickness is 18 ± 1 μm, as indicated by ultraviolet−visible spectroscopy experiments probing dissolved bis(bipyridine)ruthenium(II) chloride. We illustrate that the voltammetric character in this system is highly dependent on the bubble wetting parameters, which are tuned by changing the microwire material. We then applied this system to the collection and electrochemical detection of methamphetamine in liquid aerosols, where the bubble wall acts as a low volume collector.
We report a technique to amplify the electrochemical signal within micro-and nanodroplets via radical annihilation amplification. Toluene droplets filled with decamethylferrocene (DmFc) are suspended in an aqueous solution containing 10 mM NaClO 4 and 10 μM Na 2 C 2 O 4 . When a toluene droplet irreversibly collides with an ultramicroelectrode biased sufficiently positive for concurrent oxidation of DmFc and oxalate (C 2 O 4 2− ), blip-type responses are observed in the amperometric i-t trace even when the concentration of DmFc is 50 nM. The toluene droplet wetting the ultramicroelectrode effectively creates a microgap, where DmFc molecules are oxidized to DmFc + . In the continuous phase, the oxidation of oxalate (C 2 O 4 2− ) produces a strong reducing agent, CO 2 •− . Regeneration of DmFc via radical annihilation amplifies the current, similar to conventional nanogap experiments. This experiment allows one to observe the electrochemistry of hundreds to thousands of molecules trapped in a femtoliter droplet, enhancing the sensitivity of dropletbased electrochemistry by 5 orders of magnitude. Finite element simulations validate our experimental results and indicate the importance of the droplet geometry to amplification.
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