RESUMO
Here, we comprehensively investigated methanol electrooxidation on Cu-based catalysts, allowing us to build the first microfluidic fuel cell (µFC) equipped with a Cu anode and a metal-free cathode that converts energy from methanol. We applied a simple, fast, small-scale, and surfactant-free strategy for synthesizing Cu-based nanoparticles at room temperature in steady state (ST), under mechanical stirring (MS), or under ultrasonication (US). The morphology evaluation of the Cu-based samples reveals that they have the same nanoparticle (NP) needle-like form. The elemental mapping composition spectra revealed that pure Cu or Cu oxides were obtained for all synthesized materials. In addition to having more Cu2O on the surface, sample US had more Cu(OH)2 than the others, according to X-ray diffractograms and X-ray photoelectron spectroscopy. The sample US is less carbon-contaminated because of the local heating of the sonic bath, which also enhances the cleanliness of the Cu surface. The activity of the Cu NPs was investigated for methanol electrooxidation in an alkaline medium through electrochemical and spectroelectrochemical measurements. The potentiodynamic and potentiostatic experiments showed higher current densities for the NPs synthesized in the US. In situ FTIR experiments revealed that the three synthesized NP materials eletcrooxidize methanol completely to carbonate through formate. Most importantly, all pathways were led without detectable CO, a poisoning molecule not found at high overpotentials. The reaction path using the US electrode experienced an additional round of formate formation and conversion into carbonate (or CO2 in the thin layer) after 1.0 V (vs. Ag/Ag/Cl), suggesting improved catalysis. The high activity of NPs synthesized in the US is attributed to effective dissociative adsorption of the fuel due to the site's availability and the presence of hydroxyl groups that may fasten the oxidation of adsorbates from the surface. After understanding the surface reaction, we built a mixed-media µFC fed by methanol in alkaline medium and sodium persulfate in acidic medium. The µFC was equipped with Cu NPs synthesized in ultrasonic-bath-modified carbon paper as the anode and metal-free carbon paper as the cathode. Since the onset potential for methanol electrooxidation was 0.45 V and the reduction reaction revealed 0.90 V, the theoretical OCV is 0.45 V, which provides a spontaneous coupled redox reaction to produce power. The µFC displayed 0.56 mA cm-2 of maximum current density and 26 µW cm-2 of peak power density at 100 µL min-1. This membraneless system optimizes each half-cell individually, making it possible to build fuel cells with noble metal-free anodes and metal-free cathodes.
RESUMO
Paper batteries are self-pumping emerging tools for powering portable analytical systems. These disposable energy converters must be low-cost and must achieve enough energy to power electronic devices. The challenge is reaching high energy while keeping the low cost. Here, for the first time, we report a paper-based microfluidic fuel cell (PµFC) equipped with Pt/C on a carbon paper (CP) anode and a metal-free CP cathode fed by biomass-derived fuels to deliver high power. The cells were engineered in a mixed-media configuration, where methanol, ethanol, ethylene glycol, or glycerol is electro-oxidized in an alkaline medium, while Na2S2O8 is reduced in an acidic medium. This strategy allows for optimizing each half-cell reaction independently. The colaminar channel of the cellulose paper was chemically investigated by mapping the composition, which reveals a majority of elements from the catholyte and anolyte on each respective side and a mixture of both at the interface, assuring the existing colaminar system. Moreover, the colaminar flow was studied by investigating the flow rate by considering recorded videos for the first time. All PµFCs show 150-200 s to build a stable colaminar flow, which matches the time to reach a stable open circuit voltage. The flow rate is similar for different concentrations of methanol and ethanol, but it decreases with the increase in ethylene glycol and glycerol concentrations, suggesting a longer residence time for the reactants. The cells perform differently for the different concentrations, and their limiting power densities are composed of a balance among anode poisoning, residence time, and viscosity of the liquids. The sustainable PµFCs can be interchangeably fed by the four biomass-derived fuels to deliver â¼2.2-3.9 mW cm-2. This allows choosing the proper fuel due to their availability. The unprecedented PµFC fed by ethylene glycol delivered 6.76 mW cm-2, which is the benchmark output power for a paper battery fed by alcohol.