Stephen E. Fosdick

Hollow-channel paper analytical devices.

We present a microfluidic paper analytical device (μPAD) that relies on flow in hollow channels, rather than through a cellulose network, to transport fluids. The flow rate in hollow channels is 7 times higher than in regular paper channels and can be conveniently controlled from 0 to several mm/s by balancing capillary and pressure forces. More importantly, the pressure of a single drop of liquid (~0.2 mbar) is sufficient to induce fast pressure-driven flow, making hollow channels suitable for point of care diagnostics. We demonstrate their utility for simple colorimetric glucose and BSA assays in which the time for liquid transport is reduced by a factor of 4 compared to normal cellulose channels.

Bipolar Electrodes for Rapid Screening of Electrocatalysts

We report a method for rapid screening of arrays of electrocatalyst candidates. The approach is based on simultaneous activation of the oxygen reduction reaction (ORR) and Ag electrodissolution at the cathodic and anodic poles, respectively, of bipolar electrodes (BPEs). Because the electrochemical activity of the two poles is directly coupled via the BPE, the extent of Ag electrodissolution is directly related to the ORR activity. The screening process lasts ~12 min. Because Ag dissolution provides a permanent record of catalyst activity, the screening results can be determined by simple optical microscopy after the electrochemical experiment. The method has the potential to provide quantitative information about electrocatalyst activity.

Correlated Electrochemical and Optical Tracking of Discrete Collision Events

Optical tracking of collisions between insulating microbeads and an ultramicroelectrode surface are correlated to electrochemical measurements and 3D simulations. The experiments are based on partial blocking of the electrode surface by the beads. Results obtained using these three methods provide details regarding the radial distribution of landing locations, the extent of current blockage, collision frequency, motion of beads on the electrode surface following collisions, and aggregation behavior both prior to collisions and afterward on the electrode surface.

Parallel Screening of Electrocatalyst Candidates Using Bipolar Electrochemistry

Here we report simultaneous screening of bimetallic electrocatalyst candidates for the oxygen reduction reaction (ORR) using bipolar electrochemistry. The analysis is carried out by dispensing different bimetallic precursor compositions onto the cathodic poles of an array of bipolar electrodes (BPEs) and then heating them in a reducing atmosphere to yield the catalyst candidates. Because BPEs do not require a direct electrical connection for activation, up to 33 electrocatalysts can be screened simultaneously by applying a voltage to the electrolyte solution in which the BPE array is immersed. The screening of the electrocatalyst candidates can be achieved in about 10 min. The current required to drive the ORR arises from oxidation of Cr microbands present at the anodic poles of the BPEs. Therefore, the most effective electrocatalysts result in oxidation (dissolution) of the most microbands, and simply counting the microbands remaining at the end of the screen provides information about the onset potential required to reduce oxygen. Here, we evaluated three Pd-M (M = Au, Co, W) bimetallic electrocatalysts. In principle, arbitrarily large libraries of electrocatalysts can be screened using this approach.

Wire, mesh, and fiber electrodes for paper-based electroanalytical devices.

Here, we report the use of microwire and mesh working electrodes in paper analytical devices fabricated by origami paper folding (oPADs). The important new result is that Au wires and carbon fibers having diameters ranging from micrometers to tens of micrometers can be incorporated into oPADs and that their electrochemical characteristics are consistent with the results of finite element simulations. These electrodes are fully compatible with both hollow channels and paper channels filled with cellulose fibers, and they are easier to incorporate than typical screen-printed carbon electrodes. The results also demonstrate that the Au electrodes can be cleaned prior to device fabrication using aggressive treatments and that they can be easily surface modified using standard thiol-based chemistry.

Two-Dimensional Bipolar Electrochemistry

This paper introduces the concept of two-dimensional bipolar electrochemistry and discusses its principle of operation. The interesting new result is that electrochemical reactions can be localized at particular locations on the perimeter of a two-dimensional bipolar electrode (2D-BPE), configured at the intersection of two orthogonal microfluidic channels, by controlling the electric field within the contacting electrolyte solution. Experimentally determined maps of the electric field in the vicinity of the 2D-BPEs are in semiquantitative agreement with finite element simulations.

Paper-Based Bipolar Electrochemistry

We demonstrate that carbon electrodes screen-printed directly on cellulose paper can be employed to perform bipolar electrochemistry. In addition, an array of 18 screen-printed bipolar electrodes (BPEs) can be simultaneously controlled using a single pair of driving electrodes. The electrochemical state of the BPEs is read-out using electrogenerated chemiluminescence. These results are important because they demonstrate the feasibility of coupling bipolar electrochemistry to microfluidic paperbased analytical devices () to perform highly multiplexed, low-cost measurements.

Pressure-driven bipolar electrochemistry.

Here we report that pressure-driven flow alone (no external electrical energy) can be used to drive faradaic electrochemical reactions in microchannels with charged walls. Specifically, we show that solution flow can generate streaming potentials on the order of volts and that this is sufficient to carry out reactions on the anodic and cathodic poles of a bipolar electrode (BPE). The existence of faradaic reactions is proven by electrodissolution of Ag from the anodic end of the BPE.

Electrochemical Properties of Metal-Oxide-Coated Carbon Electrodes Prepared by Atomic Layer Deposition

Here we report on the electrochemical properties of carbon electrodes coated with thin layers of Al2O3 and SnO2. These oxide films were deposited using atomic layer deposition (ALD) and range in thickness from 1 to 6 nm. Electrochemical experiments show that the thinnest oxide layers contain defects that penetrate to the underlying carbon electrode. However, oxygenation of the carbon surface prior to ALD increases the surface concentration of nucleation sites for oxide growth and suppresses the defect density. Films of Al2O3 just ∼3-4 nm in thickness are free of pinholes. Slightly thicker coatings of SnO2 are required for equivalent passivation. Both Al2O3 and SnO2 films are stable in both neutral and acidic electrolytes even after repeated voltammetric scanning. The results reported here open up the possibility of studying the effect of oxide supports on electrocatalytic reactions.