J. P. Esquivel

Silicon-based microfabricated microbial fuel cell toxicity sensor

Microbial fuel cells (MFCs) have been used for several years as biosensors for measuring environmental parameters such as biochemical oxygen demand and water toxicity. The present study is focused on the detection of toxic matter using a novel silicon-based MFC. Like other existing toxicity sensors based on MFCs, this device is capable of detecting the variation on the current produced by the cell when toxic compounds are present in the medium. The MFC approach presented in this work aims to obtain a simple, compact and planar device for its further application as a biosensor in the design and fabrication of equipment for toxicity monitoring. It consists on a proton exchange membrane placed between two microfabricated silicon plates that act as current collectors. An array of square 80 μm × 80 μm vertical channels, 300 μm deep, have been defined trough the plates over an area of 6 mm × 6 mm. The final testing assembly incorporates two perspex pieces positioned onto the plates as reservoirs with a working volume of 144 μL per compartment. The operation of the microdevice as a direct electron transfer MFC has been validated by comparing its performance against a larger scale MFC, run under the same conditions. The device has been tested as a toxicity sensor by setting it at a fixed current while monitoring changes in the output power. A drop in the power production is observed when a toxic compound is added to the anode compartment. The compact design of the device makes it suitable for its incorporation into measurement equipment either as an individual device or as an array of sensors for high throughput processing.

Microfluidic fuel cells on paper: meeting the power needs of next generation lateral flow devices

Lateral flow test strips have dominated the rapid diagnostics landscape for decades. Recently, the emergence of paper microfluidics has brought new functionalities to these porous materials, and the search for instrument-free point-of-care devices has driven the development of different types of energy sources to fulfill their power needs. This work presents the development of microfluidic fuel cells as paper-based power sources in a standard lateral flow test format. These fuel cells benefit from the laminar flow occurring in a porous material by capillarity to separately react with two parallel streams, anolyte and catholyte, without an ionic exchange membrane or external pumps. It has been shown that the devices are capable of delivering power densities in the range of 1–5 mW cm−2 using solutions of methanol and KOH. The incorporation of a conjugate pad to store the KOH electrolyte in a solid form and a methanol-rich agar gel on top of the reaction membrane allows the fuel cell to function soaking a single sample pad with just water. The presented microfluidic fuel cell approach would enable a more straightforward integration with typical lateral flow test strips and a cost-effective manufacturing. This work represents the starting point in the development of a power source for capillary-based autonomous sensing systems capable of harvesting the energy needed for the measurement from the biological sample to be analyzed.

Membraneless glucose/O2 microfluidic enzymatic biofuel cell using pyrolyzed photoresist film electrodes

Biofuel cells typically yield lower power and are more difficult to fabricate than conventional fuel cells using inorganic catalysts. This work presents a glucose/O2 microfluidic biofuel cell (MBFC) featuring pyrolyzed photoresist film (PPF) electrodes made on silicon wafers using a rapid thermal process, and subsequently encapsulated by rapid prototyping techniques into a double-Y-shaped microchannel made entirely of plastic. A ferrocenium-based polyethyleneimine polymer linked to glucose oxidase (GOx/Fc-C6-LPEI) was used in the anode, while the cathode contained a mixture of laccase, anthracene-modified multi-walled carbon nanotubes, and tetrabutylammonium bromide-modified Nafion (MWCNTs/laccase/TBAB-Nafion). The cell performance was studied under different flow-rates, obtaining a maximum open circuit voltage of 0.54 ± 0.04 V and a maximum current density of 290 ± 28 μA cm(-2) at room temperature under a flow rate of 70 μL min(-1) representing a maximum power density of 64 ± 5 μW cm(-2). Although there is room for improvement, this is the best performance reported to date for a bioelectrode-based microfluidic enzymatic biofuel cell, and its materials and fabrication are amenable to mass production.

Tolerant Chalcogenide Cathodes of Membraneless Micro Fuel Cells

The most critical issues to overcome in micro direct methanol fuel cells (μDMFCs) are the lack of tolerance of the platinum cathode and fuel crossover through the polymer membrane. Thus, two novel tolerant cathodes of a membraneless microlaminar-flow fuel cell (μLFFC), Pt(x)S(y) and CoSe(2), were developed. The multichannel structure of the system was microfabricated in SU-8 polymer. A commercial platinum cathode served for comparison. When using 5 M CH(3)OH as the fuel, maximum power densities of 6.5, 4, and 0.23 mW cm(-2) were achieved for the μLFFC with Pt, Pt(x)S(y), and CoSe(2) cathodes, respectively. The Pt(x)S(y) cathode outperformed Pt in the same fuel cell when using CH(3)OH at concentrations above 10 M. In a situation where fuel crossover is 100 %, that is, mixing the fuel with the reactant, the maximum power density of the micro fuel cell with Pt decreased by 80 %. However, for Pt(x)S(y) this decrease corresponded to 35 % and for CoSe(2) there was no change in performance. This result is the consequence of the high tolerance of the chalcogenide-based cathodes. When using 10 M HCOOH and a palladium-based anode, the μLFFC with a CoSe(2) cathode achieved a maxiumum power density of 1.04 mW cm(-2). This micro fuel cell does not contain either Nafion membrane or platinum. We report, for the first time, the evaluation of Pt(x)S(y)- and CoSe(2)-based cathodes in membraneless micro fuel cells. The results suggest the development of a novel system that is not size restricted and its operation is mainly based on the selectivity of its electrodes.

Replica molding for multilevel micro-/nanostructure replication

The development of micro- and nanofabrication processes with the capability to achieve three-dimensional structures is of great interest for a wide variety of applications. In this paper, a replica molding process for the replication of combined micro- and nanostructures in an epoxy-based photo resin is reported. First, multilevel masters were realized using standard micro- and nanofabrication processes. The structures from these masters were transferred to poly(dimethylsiloxane) (PDMS) stamps by soft lithography. Finally, the PDMS stamps were used for the replication of nano- and microstructures in the epoxy-based resin by UV casting. With this process, micro- and nanostructures of minimal dimensions of 50 nm were successfully replicated. Furthermore, the capabilities of the process were confirmed by the fabrication of a microfluidic device. In this system, the surface of micro channels was structured to modify its wetting properties and create hydrophobic and hydrophilic areas without any additional chemical treatment.

A micro alkaline direct ethanol fuel cell with platinum-free catalysts

This paper presents the fabrication and characterization of a micro alkaline direct ethanol fuel cell. The device has been conceived as a feasibility demonstrator, using microtechnologies for the fabrication of the current collectors and traditional techniques for the membrane electrode assembly production. The fuel cell works in passive mode, as expected for the simplicity required for micro power systems. Non-noble catalysts have been used in order to implement the main advantage of alkaline systems, showing the feasibility of such a device as a potential very-low-cost power device at mini- and micro scales. (Some figures may appear in colour only in the online journal)

Hybrid polymer electrolyte membrane for silicon-based micro fuel cells integration

A novel approach for a hybrid polymer electrolyte membrane compatible with silicon-based fuel cells is proposed in this study. The membrane consists of a polymer matrix of polydimethylsiloxane (PDMS) filled with a proton-conducting polymer. The fabrication steps of the hybrid membrane as well as its electrochemical characterization are explained in detail. The obtained proton conductivities demonstrate the validity of the present approach as a proof of concept for the obtaining of a new generation of fully integrated micro proton-exchange membrane fuel cells.

Comprehensive characterization and understanding of micro-fuel cells operating at high methanol concentrations.

Summary We report on the analysis of the performance of each electrode of an air-breathing passive micro-direct methanol fuel cell (µDMFC) during polarization, stabilization and discharge, with CH3OH (2–20 M). A reference electrode with a microcapillary was used for separately measuring the anode the cathode potential. Information about the open circuit potential (OCP), the voltage and the mass transport related phenomena are available. Using 2 M CH3OH, the anode showed mass transport problems. With 4 and 6 M CH3OH both electrodes experience this situation, whereas with 10 and 20 M CH3OH the issue is attributed to the cathode. The stabilization and fuel consumption time depends mainly on the cathode performance, which is very sensitive to fuel crossover. The exposure to 20 M CH3OH produced a loss in performance of more than 75% of the highest power density (16.3 mW·cm−2).

Formic acid microfluidic fuel cell based on well-defined Pd nanocubes

Microfluidic fuel cells (μFFC) are emerging as a promising solution for small-scale power demands. The T-shaped architecture of the μFFC promotes a laminar flow regimen between the catholyte and anolyte streams excluding the use of a membrane, this property allows a simplest design and the use of several micromachining techniques based on a lab-on-chip technologies. This work presents a combination of new materials and low cost fabrication processes to develop a light, small, flexible and environmental friendly device able to supply the energy demand of some portable devices. Well-defined and homogeneous Pd nanocubes which exhibited the (100) preferential crystallographic plane were supported on Vulcan carbon and used as anodic electrocatalyst in a novel and compact design of a SU-8 μFFC feeded with formic acid as fuel. The SU-8 photoresist properties and the organic microelectronic technology were important factors to reduce the dimensions of the μFFC structure. The results obtained from polarization and power density curves exhibited the highest power density (8.3 mW cm−2) reported in literature for direct formic acid μFFCs.

Effect of metal content on the electrocatalytic activity of AuxPdy mixtures and their use in a glucose membraneless microfluidic fuel cell

AuxPdy bimetallic mixtures with different elemental contents were synthesized on glassy carbon electrodes using electrochemical techniques, which are easy, quick, versatile and cheap. Pulse potential and staircase techniques such as cyclic voltammetry (Au60Pd40), square-wave voltammetry (Au50Pd50 and Au35Pd65) and second harmonic AC voltammetry (Au15Pd85) were used to easily change the metal proportion and reduce the Au content in the AuxPdy mixtures. Au60Pd40 exhibited the most negative potential (−0.4 V vs. NHE) towards the glucose electro-oxidation reaction. For this reason, it was used in the anode compartment of a microfluidic fuel cell and compared with single Au and Pd materials by cyclic voltammetry. Au60Pd40 showed a greater negative potential than that of the Au anode; meanwhile, Pd showed no electrocatalytic activity. The lattice parameters were calculated by X-ray diffraction patterns resulting in values of 3.83 and 4.03 A for Au and Pd, respectively, and 3.94 A for Au60Pd40, which provides evidence for the internal structural changes due to the incorporation of Pd to the Au matrix. The maximum power density obtained with a glucose membraneless microfluidic fuel cell (GMMFC) using 10 mM glucose and Au60Pd40 as the anode was 0.28 mW cm−2.