Electrochemical Impedance Imaging on Conductive Surfaces.

Electrochemical impedance spectroscopy (EIS) is a powerful tool to measure and quantify the system impedance. However, EIS only provides an average result from the entire electrode surface. Here, we demonstrated a reflection impedance microscope (RIM) that allows us to image and quantify the localized impedance on conductive surfaces. The RIM is based on the sensitive dependence between the materials' optical properties, such as permittivity, and their local surface charge densities. The localized charge density variations introduced by the impedance measurements will lead to optical reflectivity changes on electrode surfaces. Our experiments demonstrated that reflectivity modulations are linearly proportional to the surface charge density on the electrode and the measurements show good agreement with the simple free electron gas model. The localized impedance distribution was successfully extracted from the reflectivity measurements together with the Randles equivalent circuit model. In addition, RIM is used to quantify the impedance on different conductive surfaces, such as indium tin oxide, gold film, and stainless steel electrodes. A polydimethylsiloxane-patterned electrode surface was used to demonstrate the impedance imaging capability of RIM. In the end, a single-cell impedance imaging was obtained by RIM.

Electrochemical Approach to Measure Physiological Fluid Flow Rates.

In vivo measurement of the flow rate of physiological fluids such as the blood flow rate in the heart is vital in critically ill patients and for those undergoing surgical procedures. The reliability of these measurements is therefore quite crucial. However, current methods in practice for measuring flow rates of physiological fluids suffer from poor repeatability and reliability. Here, we assessed the feasibility of a flow rate measurement method that leverages time transient electrochemical behavior of a tracer that is injected directly into a medium (the electrochemical signal caused due to the tracer injectate will be diluted by the continued flow of the medium and the time response of the current-the electrodilution curve-will depend on the flow rate of the medium). In an experimental flow loop apparatus equipped with an electrochemical cell, we used the AC voltammetry technique and tested the feasibility of electrodilution-based measurement of the flow rate using two mediums-pure water and anticoagulated blood-with 0.9 wt% saline as the injectate. The electrodilution curve was quantified using three metrics-change in current amplitude, total time, and change in the total charge for a range of AC voltammetry settings (peak voltages and frequencies). All three metrics showed an inverse relationship with the flow rate of water and blood, with the strongest negative correlation obtained for change in current amplitude. The findings are a proof of concept for the electrodilution method of the flow rate measurement and offer the potential for physiological fluid flow rate measurement in vivo.

Low-Loading of Pt Nanoparticles on 3D Carbon Foam Support for Highly Active and Stable Hydrogen Production.

Minimizing Pt loading is essential for designing cost-effective water electrolyzers and fuel cell systems. Recently, three-dimensional macroporous open-pore electroactive supports have been widely regarded as promising architectures to lower loading amounts of Pt because of its large surface area, easy electrolyte access to Pt sites, and superior gas diffusion properties to accelerate diffusion of H2 bubbles from the Pt surface. However, studies to date have mainly focused on Pt loading on Ni-based 3D open pore supports which are prone to corrosion in highly acidic and alkaline conditions. Here, we investigate electrodeposition of Pt nanoparticles in low-loading amounts on commercially available, inexpensive, 3D carbon foam (CF) support and benchmark their activity and stability for electrolytic hydrogen production. We first elucidate the effect of deposition potential on the Pt nanoparticle size, density and subsequently its coverage on 3D CF. Analysis of the Pt deposit using scanning electron microscopy images reveal that for a given deposition charge density, the particle density increases (with cubic power) and particle size decreases (linearly) with deposition overpotential. A deposition potential of -0.4 V vs. standard calomel electrode (SCE) provided the highest Pt nanoparticle coverage on 3D CF surface. Different loading amounts of Pt (0.0075-0.1 mgPt/cm2) was then deposited on CF at -0.4 V vs. SCE and subsequently studied for its hydrogen evolution reaction (HER) activity in acidic 1M H2SO4 electrolyte. The Pt/CF catalyst with loading amounts as low as 0.06 mgPt/cm2 (10-fold lower than state-of-the-art commercial electrodes) demonstrated a mass activity of 2.6 ampere per milligram Pt at 200 mV overpotential, nearly 6-fold greater than the commercial Pt/C catalyst tested under similar conditions. The 3D architectured electrode also demonstrated excellent stability, showing <7% loss in activity after 60 h of constant current water electrolysis at 100 mA/cm2.