Converting Energy with Glycerol and CO2 in a Microfluidic Fuel Cell Equipped with CuBiO4/CuO Photocathode: Bypassing Bubbles Challenge of Concurrent Water Splitting.

The imperative to address CO2 emissions has prompted the search for alternative approaches to capture this gas with minimal energy consumption. In this context, leveraging the CO2 reduction reaction (CO2RR) as an oxidant in fuel cells has emerged as a sophisticated strategy to convert this gas into usable energy. This study introduces a hybrid microfluidic photo fuel cell (µPFC) designed for the efficient conversion of CO2 and glycerol into electrical energy. The prototype integrates 3D-printed components with glass sealing, enabling precise control over the reactant flow and the use of light-sensitive catalysts. The anodic glycerol electrooxidation was investigated on Pt/C dispersed on carbon paper (CP), while the CO2RR was carried out on CuBiO4/CP and CuBiO4/CuO/CP in the presence of solar light. Half-cell measurements demonstrate the photoactivity of CuBiO4/CuO/CP and CuBiO4/CP electrodes for the CO2RR under light exposure at low onset potential in a neutral pH solution, generating a positive theoretical open-circuit voltage of 0.89-0.91 V when coupled to glycerol electrooxidation in an alkaline medium. The use of the mixed medium in the membraneless system equipped with the photosensitive catalysts allowed the building of this galvanic cell. However, the feasibility of using CuBiO4/CP is hindered by the disruption of the colaminar channel caused by hydrogen bubbles produced during concurrent water splitting. In contrast, the µPFC equipped with a CuBiO4/CuO/CP photocathode demonstrates a stable and reproducible performance, delivering a maximum power density of 0.9 mW cm-2. The formation of the CuBiO4/CuO heterojunction effectively suppresses photocatalytic water splitting, allowing for efficient CO2 conversion without disruption of the laminar flow channel. This innovative approach highlights the potential of µPFCs as sustainable energy converters for the utilization of CO2 in aqueous solutions, offering a pathway toward carbon-neutral energy production.

Clarifying Glycerol Electrooxidation Studies on Pd-Based Catalysts: Insights Into Catalytic Performance and Practical Challenges.

Escalating biodiesel production led to a surplus of glycerol, prompting its exploration as a valuable resource in industrial applications. Electrochemical systems have been studied, specifically employing noble metal catalysts like palladium for glycerol electrooxidation. Despite numerous studies on Pd-based catalysts for glycerol electrooxidation, a comprehensive analysis addressing critical questions related to the economic feasibility, global sourcing of Pd, and the thematic cohesion of publications in this field is lacking. Moreover, a standardized framework for comparing the results of various studies is absent, hindering progress on glycerol technologies. This critical overview navigates the evolution of Pd-based catalysts for glycerol electrooxidation, examining catalytic activity, stability, and potential applications. It critically addresses the geographical sources of Pd, the motivation behind glycerol technology exploration, thematic coherence in existing publications, and the meaningful comparison of results. It correlates the use of Pd-based catalysts with the natural source of Pd and the origin of glycerol derived from biodiesel. The proposed standardized approach for comparing electrochemical parameters and establishing experimental protocols provides a foundation for meaningful study comparisons. This critical overview underscores the need to address fundamental questions to accelerate the transition of glycerol technologies from laboratories to practical applications.

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.

Enhanced Power Generation Using a Dual-Surface-Modified Hematite Photoanode in a Direct Glyphosate Photo Fuel Cell.

Given the current and escalating global energy and environmental concerns, this work explores an innovative approach to mitigate a widely employed commercial herbicide using a direct glyphosate (Gly) photocatalytic fuel cell (PFC). The device generates power continuously by converting solar radiation, degrading and mineralizing commercial glyphosate-based fuel, and reducing sodium persulfate at the cathode. Pristine and modified hematite photoanodes were coupled to Pt/C nanoparticles dispersed in a carbon paper (CP) support (Pt/C/CP) dark cathode by using an H-type cell. The Gly/persulfate PFC shows a remarkable current and power generation enhancement after dual-surface modification of pristine hematite with segregated Hf and FeNiOx cocatalysts. The optimized photoanode elevates maximum current density (Jmax) from 0.35 to 0.71 mA cm-2 and maximum power generation (Pmax) from 0.04 to 0.065 mW cm-2, representing 102.85 and 62.50% increase in Jmax and Pmax, respectively, as compared to pristine hematite. The system demonstrated stability over a studied period of 4 h; remarkably, the photodegradation of Gly proved substantial, achieving ∼98% degradation and ∼6% mineralization. Our findings may significantly contribute to reducing Gly's environmental impact in agribusiness since it may convert the pollutant into energy at zero bias. The proposed device offers a sustainable solution to counteract Gly pollution while concurrently harnessing solar energy for power generation.

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.

Miniaturized 3D-Printed Cell Enables Water/Ethanol Quantification Using Electrochemical Impedance Spectroscopy.

A miniaturized and low-cost electrochemical 3D-printed system for rapid and accurate quantification of ethanol content in ethanol fuel using electrochemical impedance spectroscopy (EIS) was developed. The monolithic design of the system incorporates insulating thermoplastic electrode separators, with only the cover being mobile, allowing for easy assembly and handling. The portable device, measuring approximately 26 × 24 mm, has a maximum capacity of 1 mL, making it suitable for lab-on-a-chip and portable analysis. By utilizing the dielectric constant of ethanol and ethanol fuel mixtures with water, the miniaturized EIS cell quantifies ethanol content effectively. To validate its performance, we compared measurements from four gas stations with a digital densimeter, and the values obtained from the proposed system matched perfectly. Our miniaturized and low-cost electrochemical 3D-printed device can be printed and assembled in two hours, offering a cost-effective solution for fast and precise ethanol quantification. Its versatility, affordability, and compatibility with lab-on-a-chip platforms make it easily applicable, including for fuel quality control and on-site analysis in remote locations.

Multi-electrode platform for selective electrochemical sensing: 3D-printed insulating plastic is turned into a five-electrodes chip.

We report a method to turn a 3D-printed plastic piece into a five-electrodes chip for multiple analytes detection. A chip containing Pd, Ni, and Ru working electrodes is used to sense hydroquinone, acetaminophen, salicylic acid, and hydroxychloroquine at once. The analysis is sequentially achieved simply by changing the proper electrode connection, without changing mobile parts, neither adding reactants, nor electrolytes. This strategy is an alternative for low-cost selective electrochemical detection.

Glycerol Is Converted into Energy and Carbonyl Compounds in a 3D-Printed Microfluidic Fuel Cell: In Situ and In Operando Bi-Modified Pt Anodes.

The combination of energy and chemical conversion can be achieved by designing glycerol fuel cells. However, the anode must promote the reaction at onset potentials low enough to allow a spontaneous reaction, when coupled to the cathodic reaction, and must be selective. Here, we build a three-dimensional (3D)-printed glycerol microfluidic fuel cell that produces power concomitantly to glycolate and formate at zero bias. The balance between energy and the two carbonyl compounds is tuned by decorating the Pt/C/CP anode in situ (before feeding the cell reactants) or in operando (while feeding the cell with reactants) with Bi. The Bi-modified anodes improve glycerol conversion and output power while decreasing the formation of the carbonyl compounds. The in operando method builds dendrites of rodlike Bi oxides that are inactive for the anodic reaction and cover active sites. The in situ strategy promotes homogeneous Bi decoration, decreasing activation losses, increasing the open-circuit voltage to 1.0 V, and augmenting maximum power density 6.5 times and the glycerol conversion to 72% at 25 °C while producing 0.2 mmoL L-1 of glycolate and formate (each) at 100 µL min-1. Such a performance is attributed to the low CO poisoning of the anode, which leads the glycerol electrooxidation toward a more complete reaction, harvesting more electrons at the device. Printing the microfluidic fuel cell takes 23 min and costs ∼US$1.85 and can be used for other coupled reactions since the methods of modification presented here are applied to any existing and assembled systems.

Simultaneous separation and electroanalysis in a single polydimethylsiloxane-based platform.

Channel-based microfluidic devices integrating the separation step and detection system are key factors to expand microanalysis application. However, these devices still depend on macroscale external equipment for pre-treatment of the sample, separation, or detection. The integration of all steps in only one stage is critical to improving feasibility. Herein, we use a low-cost protocol to solve part of the challenge by designing a dual-mode system onto single polydimethylsiloxane (PDMS)-based platform - overall dimensions of 65 mm length × 20 mm width × 14 mm height and the inner diameter of 297±10 µm height × 605±19 µm width - for column-free separation and simultaneous detection. As a proof-of-concept, we used this all-in-one PDMS platform to separate - without the packet-based phase - and determine salicylic acid (SA) and caffeine (CAF) with a detection limit of 0.20 and 0.18 µmol L-1 and quantification limit of 0.70 and 0.60 µmol L-1 for SA and CAF, respectively. We separated the mixture using forced convection into a chemically treated microchannel while detecting the analytes in amperometric mode. Here, we report new insights into how integrating analytes separation and further electroanalysis into a single miniaturized device.

Harvesting Energy from an Organic Pollutant Model Using a New 3D-Printed Microfluidic Photo Fuel Cell.

The combination of a fuel cell and photocatalysis in the same device, called a photo fuel cell, is the next generation of energy converters. These systems aim to convert organic pollutants and oxidants into energy using solar energy as the driving force. However, they are mostly designed in conventional stationary batch systems, generating low power besides being barely applicable. In this context, membraneless microfluidics allows the use of flow, porous electrodes, and mixed media, improving reactant utilization and output power accordingly. Here, we report an unprecedented reusable three-dimensional (3D) printed microfluidic photo fuel cell (µpFC) assembled with low-content PtOx/Pt dispersed on a BiVO4 photoanode and a Pt/C dark cathode, both immobilized on carbon paper. We use fused deposition modeling for additive manufacturing a US$ 2.5 µpFC with a polylactic acid filament. The system shows stable colaminar flow and a short time light distance. As a proof-of-concept, we used the pollutant-model rhodamine B as fuel, and O2 in an acidic medium at the cathode side. The mixed-media 3D printed µpFC with porous electrodes produces remarkable 0.48 mW cm-2 and 4.09 mA cm-2 as maximum power and current densities, respectively. The system operates continuously for more than 5 h and converts 73.6% rhodamine by photoelectrochemical processes. The 3D printed µpFC developed here shows promising potential for pollutant mitigation concomitantly to power generation, besides being a potential platform of tests for new (photo)electrocatalysts.

"Bleaching" glycerol in a microfluidic fuel cell to produce high power density at minimal cost.

Glycerol/bleach flow-through microfluidic fuel cells are presented. Carbon paper-modified Pt/C nanoparticles were used as the anode and cathode. Glycerol oxidation in alkaline medium was tested against hypochlorite reduction in alkaline and acidic media. The mixed media system displayed a power density of 315 mW cm-2 and an open circuit voltage of 1.9-2.0 V.

How do random superficial defects influence the electro-oxidation of glycerol on Pt(111) surfaces?

The glycerol electrooxidation reaction (GEOR) has attracted huge interest in the last decade due to the very low price and availability of this polyol. In this work, we studied the GEOR on Pt(111) electrodes by introducing different densities of random defects. Our results showed that the generation of defects on Pt(111) slightly modified the GEOR onset potential, however it generates changes in the voltammetric oxidation charges and also in the relative production of CO2 to carbonyl containing compounds, C[double bond, length as m-dash]O. The voltammetric profiles in the forward scan show two oxidation peaks. FTIR data show that the first one is connected with the GlOH dissociative adsorption to form CO (and others intermediates) while the second one, at higher potentials, matches the onsets of the CO oxidation to CO2 and the C[double bond, length as m-dash]O production. FTIR also confirms that the lower activity of defected electrodes at lower potentials is connected to a higher CO poisoning. DFT calculations show that the presence of CO molecules on a Pt defected surface keeps water and GlOH molecules far from the surface and linked by H bonds. This paper is the last of a series of three works where we explore the GEOR on an important number of different Pt surfaces. These works show that it is difficult to oxidize GlOH at potentials lower than 0.6 V (under our experimental conditions) without suffering an important electrode poisoning (mainly by CO). Since the structure of nanoparticles might be mimicked by defected single crystals, these sets of reports provide a considerable amount of information concerning the influence of such surfaces towards GlOH reaction in acidic media. Therefore, if the well-known "nano"-effect does not produce substantial changes in the activity of Pt materials, they are not useful to be applied in a Direct Glycerol Fuel Cell (DGFC). On the other hand, it is very interesting that the density of electrode defects permits us to tune the relative production of CO2 to C[double bond, length as m-dash]O.