A Comprehensive Investigation of Methanol Electrooxidation on Copper Anodes: Spectroelectrochemical Insights and Energy Conversion in Microfluidic Fuel Cells.

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.

On the synergistic effect of sulfonic functionalization and acidic adhesive conditioning to enhance the adhesion of PEEK to resin-matrix composites.

OBJECTIVE: The objective of this study was to evaluate the combined effect of the sulfuric acid etching and an acidic adhesive conditioning on the shear bond strength of PEEK to a resin-matrix composite. MATERIALS AND METHODS: Forty PEEK specimens were assigned randomly to 4 groups for H2SO4 etching followed by universal adhesive (pH at 2.5) conditioning for 0, 1, 3, and 5 min. Thirty PEEK specimens were divided into 3 groups for only acidic adhesive conditioning for 0, 1, 3, and 5 min. After the light-curing of the adhesive, a nanohybrid resin composite was applied onto the surfaces and then light-cured following the manufacturer`s guidelines. All specimens were stored in distilled water at 37 °C for 24 h mechanical testing. Shear bond strength tests were performed using a universal testing machine. Surfaces were analyzed by SEM, light interferometry, FTIR, and liquid contact angle measurement. Statistical analysis was performed by one-way ANOVA and Tukey's post hoc tests (p < 0.05). RESULTS: No adhesion was achieved between untreated PEEK a resin-matrix composite, regardless of the adhesive conditioning time points. Shear bond strength of H2SO4-etched PEEK to resin-matrix composite increased with time (0 mmin. 4.95 ± 2.86 MPa < 1 min: 9.35 ± 2.26 MPa < 3 min: 17.84 ± 2.82 MPa < 5 min: 21.43 ± 5.00 MPa). SEM images revealed a significant modification of PEEK surface topography after the H2SO4 etching. SIGNIFICANCE: The acidic adhesive was unable to modify the untreated PEEK surface to establish an effective adhesion although a synergistic effect was noticed when the universal (acidic) adhesive was applied over a H2SO4-etched PEEK surface, thus improving the PEEK to resin-matrix composite adhesion.

Biofilm behavior on sulfonated poly(ether-ether-ketone) (sPEEK).

Poly(ether-ether-ketone) (PEEK) has also shown to be very attractive for incorporating therapeutic compounds thanks to a sulfonation process which modifies the material structure resulting in a sulfonated-PEEK (sPEEK). Concerning biomedical applications, the objective of this work was to evaluate the influence of different sulfonation degree of sPEEK on the biofilm growth. PEEK samples were functionalized by using sulphuric acid (98%) and then dissolved into dimethyl-sulfoxide. A dip coating technique was used to synthesize sPEEK thin films. The sulfonation degree of the materials was analyzed by FT-IR, H NMR, TG and IEC. The surfaces were characterized by scanning electron microscopy, profilometry and contact angle analyses. Subsequently, the biofilm formation on sulfonated-PEEK based on Streptococcus mutans and Enterococcus faecalis was measured by spectrophotometry, colony forming units (CFUmL-1) and SEM. Results obtained from thermal and chemical analyses showed an intensification in sulfonation degree for sPEEK at 2 and 2.5h. The E. faecalis or S. mutans biofilm growth revealed statistically significant differences (p<0.05) between 2 and 3h sulfonation groups. A significant decrease (p<0.05) in CFUmL-1 was recorded for S. mutans or E. faecalis biofilm grown on 2.5 or 3h sPEEK. Regarding the thermal-chemical and microbiologic analyses, the sulfonation degree of sPEEK ranging from 2 up to 3h was successful capable to decrease the biofilm growth. That revealed an alternative strategy to embed anti-biofilm and therapeutic compounds into PEEK avoiding infections in biomedical applications.

Structure and properties of polypyrrole/bacterial cellulose nanocomposites.

An electrically conducting composite based on bacterial cellulose (BC) and polypyrrole (PPy) was prepared through in situ oxidative polymerization of pyrrole (Py) in the presence of BC membrane using ammonium persulfate (APS), as an oxidant. The electrical conductivity, morphology, mechanical properties and thermal stability of the composites obtained using APS (BC/PPy·APS) were evaluated and compared with BC/PPy composites prepared using as oxidant agent Iron III chloride hexahydrate (FeCl3·6H2O). The morphology of the BC/PPy·APS composites is characterized by spherical conducting nanoparticles uniformly distributed on the BC nanofiber surface, while the composites produced with FeCl3·6H2O (BC/PPy·FeCl3) is composed of a continuous conducting polymer layer coating the BC-nanofibers. The electrical conductivity of BC/PPy·FeCl3 was 100-fold higher than that found for BC/PPy·APS composites. In order to understand the site-specific interaction between PPy and BC functional groups, both composites were characterized by Fourier transform infrared (attenuated total reflectance mode) spectroscopy attenuation reflectance (FTIR-ATR) and X-ray photoelectron spectrometry (XPS). The affinity between functional groups of PPy·FeCl3 and BC is higher than that found for BC/PPy·APS composite. In addition, the tensile properties were also influenced by the chemical affinity of both components in the polymer composites.