Black TiO2 Photoanodes for Direct Methanol Photo Fuel Cells.

Photocatalytic fuel cells (PFCs) are considered the next generation of energy converter devices, since they can harvest solar energy through relatively low-cost semiconductor material to convert the chemical energy of renewable fuels and oxidants directly into electricity. Here, we report black TiO2 nanoparticle (NP) photoanodes for simple single-compartment PFCs and microfluidic photo fuel cells (µPFCs) fed by methanol. We show that Ti3+ and oxygen vacancy (OV) defects at the TiO2 NPs are easily controlled by annealing in a NaBH4-containing atmosphere. This optimized noble-metal-free black TiO2 photoanode shows superior PFC performance for methanol oxidation and O2 reduction with a maximum power density (Pmax) ∼2000% higher compared to the undoped TiO2. At flow conditions, the black TiO2 photoanode showed a Pmax ∼90 times higher than the µFC equipped with regular TiO2 in the dark. The PFC and µPFC operate spontaneously with little activation polarization, and black TiO2 photoanodes are stable under light irradiation. The improved photoactivity of the black TiO2 photoanode is a consequence of the self-doping with Ti3+/OV defects, which significantly red-shifted the bandgap energy, induced intragap electronic states, and widened both the valence band and conduction band, enhancing the overall absorption of visible light and decreasing the interfacial charge transfer resistance.

Newly designed dual-mode electrochemical sensor onto a single polydimethylsiloxane-based chip.

Here we present a planar polydimethylsiloxane (PDMS)-based millifluidic device in which the channel (at a serpentine-shape) and a new design of electrochemical sensor (dual-mode detection) are assembled into a single chip. The platform makes use of a fully integrated reservoir to place the reference electrode, separating it from the flowing stream. The device was properly characterized aiming to evaluate the influences of channel geometries and diameters, and the electrochemical properties were improved compared with the classical reference electrode configuration. To investigate the applicability of the proposed millifluidic device, amperometric detection was used for the analysis of tap and lake water as well as groundwater samples to determine salicylic acid - selected as a model analyte. Our experimental results have demonstrated a successful prospect as amperometric detection in PDMS-based chip and showed high tolerance to disturbance by external action provided in the use of electronic micropipette and no surface inactivation from sample-interference.

3D-Printed glycerol microfluidic fuel cell.

A 3D-printed microfluidic fuel cell is presented. Fused deposition modeling is used to build a microchannel with a 0.015 cm2 cross-sectional area for stable colaminar flow conditions. A new 3D-Printed cell fed by glycerol displays a power density of 175 mW cm-2 at 0.9 V and 1.8 V of open-circuit voltage.

Electrochemical cell designed for in situ integrate microextraction and electroanalysis: Trace-level determination of norfloxacin in aqueous samples.

In this work, a newly designed electrochemical cell was assembled for in situ integrated microextraction and electroanalysis. Ionic liquids (ILs) were used as extractors to perform the microextraction, which enabled the pre-concentration of norfloxacin from tap water samples. The featured device can be used to replace conventional liquid-liquid microextraction, reducing the number of steps involved in the process. In addition, the pre-concentration of target analyte was performed in a single drop, which was directly decanted onto the electrode surface after agitation, allowing for further determination at trace concentration levels. The analytical performance of the proposed device was evaluated and the norfloxacin was determined at the trace-level in tap water samples with suitable accuracy (recovery values were 86-115%).

Insulating 3D-printed templates are turned into metallic electrodes: application as electrodes for glycerol electrooxidation.

We turned printed plastic pieces into a conductive material by electrochemical polymerization of aniline on the plastic surface assisted by graphite. The conductive piece was then turned into a metallic electrode by potentiodynamic electrodeposition. As a proof-of-concept, we built indirect-3D-printed Pd, Pt and Au electrodes, which were used for glycerol electrooxidation.

New Electrochemical Flow-Cell Configuration Integrated into a Three-Dimensional Microfluidic Platform: Improving Analytical Application in the Presence of Air Bubbles.

A newly configured electrochemical flow cell to be used for (end-channel) amperometric detection in a microfluidic device is presented. The design was assembled to place the reference electrode in a separated compartment, isolated from the flow in the microchannel, while the working and counter electrodes remain in direct contact with both compartments. Moreover, a three-dimensional coil-shaped microfluidic device was fabricated using a nonconventional protocol. Both devices working in association enabled us to solve the drawback caused by the discrete injection when the automatic micropipette was used. The high performance of the proposed electrochemical flow cell was demonstrated after in situ modifying the surface of the platinum working electrode with surfactant (e.g., using Tween 20 at 0.10%). As the reference electrode remained out of contact with the flowing solution, there was no trouble by air bubble formation (generated by accidental insertion or by presence of surfactants) throughout the measurements. This device was characterized regarding its analytical performance by evaluating the amperometric detection of acetaminophen, enabling determination from 6.60 to 66.0 µmol L-1. This issue is important since at high concentration (e.g., as assessed in clinical analysis) the acetaminophen is known to passivate the working electrode surfaces by electrogenerated products, impairing the accuracy of the electrochemical measurements.