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.

Glycerol Electrolyzer with Graphite Anode and Cathode Produces Carbonyl Compounds and Hydrogen: Background Electrocatalysis of a "Nonparticipating" Current Collector.

This study unveils a novel role of bare graphite as a catalyst in glycerol electrooxidation and hydrogen evolution reactions, challenging the prevailing notion that current collectors employed in electrolyzers are inert. Half-cell experiments elucidate the feasibility of glycerol oxidation and hydrogen production on bulk graphite electrodes at potentials exceeding 1.7 V. The investigation of varying glycerol concentrations (0.05 to 1.5 mol L-1) highlights a concentration-dependent competition between glycerol electrooxidation and oxygen evolution reactions. Employing an H-type glycerol electrolyzer, polarization curves reveal significant activation polarization attributed to the low electroactivity of the anode. Glycerol electrolysis at different concentrations yields diverse product mixtures, including formate, glycolate, glycerate, and lactate at the anode, with concurrent hydrogen generation at the cathode. The anolyte composition changes with glycerol concentration, resulting in less-oxidized compounds at higher concentrations and more oxidized compounds at lower concentrations. The cell voltage also influences the product formation selectivity, with an increased voltage favoring more oxidized compounds. The glycerol concentration also affects hydrogen production, with lower concentrations yielding higher hydrogen amounts, peaking at 3.5 V for 0.05 mol L-1. This model quantitatively illustrates graphite's contribution to current and product generation in glycerol electrolyzers, emphasizing the significance of background current and products originating from current collectors if in contact with the reactants. These results have an impact on the efficiency of the electrolyzer and raise questions regarding possible extra non-noble "nonparticipating" current collectors that could affect overall performance. This research expands our understanding of electrocatalysis on graphite surfaces with potential applications in optimizing electrolyzer configurations for enhanced efficiency and product selectivity.

Assessment of Graphite, Graphene, and Hydrophilic-Treated Graphene Electrodes to Improve Power Generation and Wastewater Treatment in Microbial Fuel Cells.

In this study, graphite, graphene, and hydrophilic-treated graphene electrodes were evaluated in a dual-chamber microbial fuel cell (DC-MFC). Free-oxygen conditions were promoted in anodic and cathodic chambers. Hydrochloric acid at 0.1 M and pH 1.1 was used as a catholyte, in addition to deionized water in the cathodic chamber. Domestic wastewater was used as a substrate, and a DuPontTM Nafion 117 membrane was used as a proton exchange membrane. The maximum power density of 32.07 mW·m-2 was obtained using hydrophilic-treated graphene electrodes and hydrochloric acid as catholyte. This power density was 1.4-fold and 32-fold greater than that of graphene (22.15 mW·m-2) and graphite (1.02 mW·m-2), respectively, under the same operational conditions. In addition, the maximum organic matter removal efficiencies of 69.8% and 75.5% were obtained using hydrophilic-treated graphene electrodes, for hydrochloric acid catholyte and deionized water, respectively. Therefore, the results suggest that the use of hydrophilic-treated graphene functioning as electrodes in DC-MFCs, and hydrochloric acid as a catholyte, favored power density when domestic wastewater is degraded. This opens up new possibilities for improving DC-MFC performance through the selection of suitable new electrode materials and catholytes.

Interchangeable Biomass Fuels for Paper-Based Microfluidic Fuel Cells: Finding Their Power Density Limits.

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 ∼2.2-3.9 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.

Water Kefir Grains-Microbial Biomass Source for Carbonaceous Materials Used as Sulfur-Host Cathode in Li-S Batteries.

Nowadays, the use of biomass to produce cathode materials for lithium-sulfur (Li-S) batteries is an excellent alternative due to its numerous advantages. Generally, biomass-derived materials are abundant, and their production processes are environmentally friendly, inexpensive, safe, and easily scalable. Herein, a novel biomass-derived material was used as the cathode material in Li-S batteries. The synthesis of the new carbonaceous materials by simple carbonization and washing of water kefir grains, i.e., a mixed culture of micro-organisms, is reported. The carbonaceous materials were characterized morphologically, texturally and chemically by using scanning electron microscopy, N2 adsorption-desorption, thermogravimetric analysis, X-ray diffraction, and both Raman and X-ray photoelectron spectroscopy. After sulfur infiltration using the melt diffusion method, a high sulfur content of ~70% was achieved. Results demonstrated that the cell fitted with a cathode prepared following a washing step with distilled water after carbonization of the water kefir grains only, i.e., not subjected to any chemical activation, achieved good electrochemical performance at 0.1 C. The cell reached capacity values of 1019 and 500 mAh g-1 sulfur for the first cycle and after 200 cycles, respectively, at a high mass loading of 2.5 mgS cm-2. Finally, a mass loading study was carried out.

Contribution of configurations, electrode and membrane materials, electron transfer mechanisms, and cost of components on the current and future development of microbial fuel cells.

Microbial fuel cells (MFCs) are a technology that can be applied to both the wastewater treatment and bioenergy generation. This work discusses the contribution of improvements regarding the configurations, electrode materials, membrane materials, electron transfer mechanisms, and materials cost on the current and future development of MFCs. Analysis of the most recent scientific publications on the field denotes that dual-chamber MFCs configuration offers the greatest potential due to the excellent ability to be adapted to different operating environments. Carbon-based materials show the best performance, biocompatibility of carbon-brush anode favors the formation of the biofilm in a mixed consortium and in wastewater as a substrate resembles the conditions of real scenarios. Carbon-cloth cathode modified with nanotechnology favors the conductive properties of the electrode. Ceramic clay membranes emerge as an interesting low-cost membrane with a proton conductivity of 0.0817 S cm-1, close to that obtained with the Nafion membrane. The use of nanotechnology in the electrodes also enhances electron transfer in MFCs. It increases the active sites at the anode and improves the interface with microorganisms. At the cathode, it favors its catalytic properties and the oxygen reduction reaction. These features together favor MFCs performance through energy production and substrate degradation with values above 2.0 W m-2 and 90% respectively. All the recent advances in MFCs are gradually contributing to enable technological alternatives that, in addition to wastewater treatment, generate energy in a sustainable manner. It is important to continue the research efforts worldwide to make MFCs an available and affordable technology for industry and society.

Biogenic synthesis of selenium nanoparticles by Shewanella sp. HN-41 using a modified bioelectrochemical system

BACKGROUND Synthesis of selenium nanoparticles from selenite by Shewanella sp. HN-41 demonstrated that particle size depended on the reaction time and biomass of cells. The slow reaction and low biomass tended to form small particles. In this study, Shewanella sp. HN-41 was introduced into the anode of a nonexternal circuit bioelectrochemical system (nec_BES) to convert chemical energy from lactate to low electron current to the cathode, where selenite was reduced. RESULTS Our experiment with two systems, one bioelectrochemical system with a cathode flushed with nitrogen and the other with a no-nitrogen-flushing cathode, showed that the former could not produce Se nanoparticles after 21 d, but the latter formed them with an average size of 37.7 nm. The SEM and TEM images demonstrated that the particle size of 10 nm occupied over 10% and most of the particles were in the range of 30­60 nm. The XRD result and SAED image demonstrated no clear peaks of crystal and proved that the Se nanoparticles are amorphous. CONCLUSIONS : The clean Se nanoparticles were synthesized and completely separated from bacterial cells in the bioelectrochemical system. This study opened a new approach for the biological synthesis of metal nanoparticles. Finally, the Se products in the range of 30­60 nm can be tested for antimicrobial activities in medical applications

Role of the solvent in the activation of Li2S as cathode material: a DFT study.

Lithium-sulfur batteries are considered one of the possible next-generation energy-storage solutions, but to be commercially available many drawbacks have yet to be solved. One solution with great potentiality is the use of lithium sulfide as cathode material since it can be coupled to Li-free anodes, such as graphite, Si or Sn. Nevertheless, Li2S, like sulfur, is electronically and ionically insulating, with a high activation potential for its initial oxidation step. To overcome this issue, different strategies have been explored, one of them being the use of catalytic surfaces. In the present article, we study using first principles calculations the effect of the dielectric constant of the solvent on the activation energy of the cleavage reaction of Li2S on different catalytic surfaces. To the best of our knowledge, this is the first time that such a study is undertaken. We find that the effect of the solvent should be twofold: on one side, it should decrease the interaction between the Li2S molecule and the surface. On the other side, since the species arising in the dissociation reaction are charged, the solvent should decrease the activation barrier for the dissociation of the Li2S molecule, when compared with the reaction in vacuum. These theoretical findings are discussed in connection with experimental results from the literature, where the behaviour of the Li-S cathode is studied in different solvents.

Comprehensive performance, bacterial community structure of single-chamber microbial fuel cell affected by COD/N ratio and physiological stratifications in cathode biofilm.

This study compares the effects and bacterial community structure of single-chamber microbial fuel cells (MFCs) in the treatment of NH4+-containing wastewater with different chemical oxygen demand (COD)/N ratios, whilst simultaneously conducting stratification research on the cathode biofilm. To this end, five nitrifier pre-enriched single-chamber MFC reactors are established to treat five different COD/N wastewaters, respectively. The results show that MFCs with low COD/N have better NH4+-N removal, electrochemical performance, but the removal stability and COD removal effect are lower than MFCs with high COD/N. High-throughput sequencing reveals that the anode community structure is weakly affected by the COD/N and is dominated by Geobacter; however, the cathode community is complex and susceptible to the COD/N. Furthermore, the pH profile in the cathode biofilm is characterized by a pH microelectrode and fluorescence in situ hybridization (FISH) is used to confirm that the distribution trend of nitrifiers and denitrifiers in cathode biofilm.

Hollow cathode plasma nitriding of medical grade Ti6Al4V: A comprehensive study.

Ti6Al4V used in biomedical applications still has several surface-related problems, such as poor bone compatibility and low wear resistance. In this work, the formation of a protective layer of titanium nitride obtained by plasma treatment in hollow cathode was studied, and the best experimental conditions were verified by a statistical factorial design of experiments. The samples were characterized in terms of their physical and chemical properties, correlating the effects of time (min) and temperature (°C). An achieved ideal condition was further analysed in terms of in vitro cytotoxicity, micro-abrasion, and electrochemical properties. The carried-out assessment has shown that nitrided condition has an improvement in wettability, microhardness, along with TixNy formation and roughness increment, when compared to pristine condition.

Composition analysis of the cathode active material of spent Li-ion batteries leached in citric acid solution: A study to monitor and assist recycling processes.

Spent Li-ion batteries (LIBs) despite being produced with valuable metals from non-renewable natural resources are considered hazardous solid wastes because they contain metals and organic solvents pollutants for the environment. Due to this, it becomes necessary to know the chemical composition of these spent batteries to assist in the proper disposal and/or recycling process. This study aimed to provide quantitative data regarding the chemical composition of the cathode active material (CAM) of eight different spent LIBs used in cell phones and propose relationship with their energy capacity, year of manufacture and brand. CAM powder was leached using an environmentally friendly process with citric acid (2.0 mol L-1) and H2O2 (0.25 mol L-1), and the metals concentrations were determined by inductively coupled plasma optical emission spectrometry (ICP OES). Co (43-67 wt%), Li (5.3-6.8 wt%), Mn (0.8-8.2 wt%), Ni (0.1-11.7 wt%) and Al (0.06-3.2 wt%) were present in higher concentrations, whereas Cr (0.0005-0.002 wt%), Cu (0.01-0.05 wt%), Mg (0.005-0.02 wt%), Ti (0.001-0.07 wt%), Ga (0.0009-0.03 wt%) and Zn (0.009-0.05 wt%) were present in lower concentrations. The result obtained showed a considerable variation between CAM elemental composition, which may be related to type of electrolyte, energy capacity and year of manufacture. Since this difference in chemical composition is not shown on product labels, this work using a green leaching process and a suitable analytical method may assist in the recycling processes and avoid the inappropriate disposal of the material.

A closed-loop process to recover Li and Co compounds and to resynthesize LiCoO2 from spent mobile phone batteries.

In the last decades, the demand for lithium-ion batteries (LIBs) has been growing fast to attend the markets of electric and hybrid vehicles and of electric portable devices. As scarce metals like cobalt and lithium are employed in their manufacturing the recycling of spent LIBs is a strategic solution for the sustainability of these minerals and also the maintenance of the LIBs production. Therefore, efforts should be driven to produce low cost, environment-friendly and industrially scalable recycling processes. In this study, a closed-loop process with these characteristics was developed to recover cobalt and lithium compounds from LiCoO2 cathodes of spent cell phone lithium-ion batteries. The process employs citric acid as green leaching agent to recover cobalt as CoC2O4.2H2O and Co3O4 and lithium as Li2CO3. Lithium compound was recovered from a proposed new and original method based on simple chemical procedures as evaporation-calcination and water dissolution. The developed process also allows the resynthesis of LiCoO2 as a stoichiometric, well crystallized and structurally ordered compound from the recovered Co and Li compounds, in a closed-loop recycling process. The obtained results indicate that the developed process has great potential to be scaled up to a recycling industrial plant of spent lithium-ion batteries.

Treatment of an azo dye effluent by peroxi-coagulation and its comparison to traditional electrochemical advanced processes.

Peroxi-coagulation (PC) is an interesting new process that has not been widely studied in the literature. This work presents the application of this technology to treat an azo dye synthetic effluent, studying the effect of different parameters including initial pH, current density (j), initial dye concentration and supporting electrolyte. The two former variables significantly affected the colour removal of the wastewater, followed by the initial dye concentration and the kind of electrolyte, in a lesser extent. The optimum operating conditions achieved were initial pH of 3.0, j = 33.3 mA cm-2, 100 mg L-1 of methyl orange (MO) and Na2SO4 as supporting electrolyte. The performance of PC was also compared to other electrochemical advanced processes, under similar experimental conditions. Results indicate that the kinetic decay of the MO increases in the following order: electrocoagulation (EC) < electrochemical oxidation (EO) with electrogenerated H2O2 << PC < electro-Fenton (EF). This behaviour is given to the high oxidant character of the homogenous OH radicals generated by EF and PC approaches. The EO process with production of H2O2 (EO-H2O2) is limited by mass transport and the EC, as a separation method, takes longer times to achieve similar removal results. Energy requirements about 0.06 kWh gCOD-1, 0.09 kWh gCOD-1, 0.7 kWh gCOD-1 and 0.1 kWh gCOD-1 were achieved for PC, EF, EO-H2O2 and EC, respectively. Degradation intermediates were monitored and carboxylic acids were detected for PC and EF processes, being rapidly removed by the former technology. PC emerges as a promising and competitive alternative for wastewaters depollution, among other oxidative approaches.

H2 production in membraneless bioelectrochemical cells with optimized architecture: The effect of cathode surface area and electrode distance.

In this work we report on the hydrogen production capacity of single-chamber microbial electrohydrogenesis cell (MEC) with optimized design characteristics, in particular cathode surface area and anode-cathode spacing using acetate as substrate. The results showed that the maximal H2 production rates and best energetic performances could be obtained using the smallest, 71 cm2 stainless steel cathode and 4 cm electrode distances, employing a 60 cm2 bioanode. Cyclic voltammetric analysis was employed to investigate the dominant electron transfer mechanism of the architecturally optimized system.