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Abstract Aiming to advance the technical maturity of CO2 electrolysis to formic acid, various gas diffusion layers (GDLs) are investigated for their suitability as carbon‐based substrate for gas diffusion electrodes (GDEs) and their effect on the electroreduction of CO2 to formate. Particular attention lies on the elucidation for the effect of the GDL thickness, hydrophobic treatment, and presence of a microporous layer (MPL) on the GDE performance in terms of Faradaic efficiency. Based on the investigation it is found that the GDL thickness has no discernible influence on the Faradaic efficiency, while a GDE with a hydrophobic treatment of 10 % PTFE outperforms a GDE based on a GDL with 30 % PTFE. Furthermore, the presence of a MPL is found to be of marked importance to achieve relevant current densities given its effect on the focus of the catalyst layer on the GDE surface after spray coating, the wetting, and the electrical conductivity.

An efficient immobilization of Glucose oxidase (GOx) on an appropriate substrate is one of the main challenges of developing fuel cells that allow energy to be obtained from renewable substrates such as carbohydrates in physiological environments. The research importance of biofuel cells relies on their experimental robustness and high compatibility with biological organisms such as tissues or the bloodstream with the aim of obtaining electrical energy even from living systems. In this work, we report the use of 5,10,15,20 tetrakis (1-methyl-4-pyridinium) porphyrin and glutathione capped CdTe Quantum dots (GSH-CdTeQD) as a support matrix for the immobilization of GOx on carbon surfaces. Fluorescent GSH-CdTeQD particles were synthesized and their characterization by UV-Vis spectrophotometry showed a particle size between 5–7 nm, which was confirmed by DLS and TEM measurements. Graphite and Toray paper electrodes were modified by a drop coating of porphyrin, GSH-CdTeQD and GOx, and their electrochemical activity toward glucose oxidation was evaluated by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Additionally, GOx modified electrode activity was explored by scanning electrochemical microscopy, finding that near to 70% of the surface was covered with active enzyme. The modified electrodes showed a glucose sensitivity of 0.58 ± 0.01 μA/mM and an apparent Michaelis constant of 7.8 mM. The addition of BSA blocking protein maintained the current response of common interferent molecules such as ascorbic acid (AA) with less than a 5% of interference percentage. Finally, the complex electrodes were employed as anodes in a microfluidic biofuel cell (μBFC) in order to evaluate the performance in energy production. The enzymatic anodes used in the μBFC allowed us to obtain a current density of 7.53 mAcm−2 at the maximum power density of 2.30 mWcm−2; an open circuit potential of 0.57 V was observed in the biofuel cell. The results obtained suggest that the support matrix porphyrin and GSH-CdTeQD is appropriate to immobilize GOx while preserving the enzyme's catalytic activity. The reported electrode arrangement is a viable option for bioenergy production and/or glucose quantification. [ABSTRACT FROM AUTHOR]

This work presents the construction and evaluation of a membraneless nanofluidic fuel cell made with fiberglass using flow-through porous electrodes based on Toray paper, coupled with a microelectronic interface to supply energy to low-power demand applications. The device performance is optimized for different operating conditions related with flow rate, stoichiometry and concentration and employing formic acid as fuel. Evaluation tests were performed with a homemade testing station using a commercial varying resistance. [ABSTRACT FROM AUTHOR]

The pressing demand for more sustainable energy provision and the ongoing transition toward renewable resources underline the critical need for effective energy storage solutions. To address this challenge, scientists persistently explore new compounds and hybrids and, in such a dynamic research field, 2D materials, particularly transition metal di‐chalcogenides (TMDCs), show great potential for electrochemical energy storage uses. Simultaneously, also conductive polymers (CPs) are interesting and versatile supercapacitor materials, especially polyaniline (PANI), which is extensively studied for this purpose. In this work, a powerful method to combine TMDCs and PANI into covalently grafted hybrids starting from aniline functionalized few‐layers 1T‐MoS2, attained by a facile direct arylation with iodoaniline, is presented. The hybrids provide circa 70 F g−1 specific capacitance in a pseudo device setup, coupled with a robust capacitance retention of well over 80% for up to 5000 cycles. These findings demonstrate the potential of similar covalent composites to work as active components for novel, innovative energy storage technologies. At the same time, the successful synthesis marks the efficacy of direct covalent grafting of conductive polymer on the surface of 2D TMDCs for stable functional materials. [ABSTRACT FROM AUTHOR]

Impaired power quality is known to increase the power consumption of water electrolysis cells without affecting the hydrogen production rate. Owing to a lack of large‐signal dynamic water electrolyzer models, simulations on the topic often consider only the static polarization curve omitting actual cell dynamics. This article aims to bridge the gap by experimentally studying the dynamic phenomena leading to additional power consumption of a polymer electrolyte membrane water electrolyzer cell using sinusoidal current ripple. The effect of ripple amplitude is analyzed with high‐speed current and voltage waveform measurements, and the frequency dependence is determined using electrochemical impedance spectroscopy. The complex cell impedance is found to be the only parameter needed for determining the additional power consumption at frequencies above 30Hz$30 \,\mathrm{Hz}$. This finding enables a simple prediction of additional power consumption for arbitrary current waveforms at frequencies relevant for water electrolyzer rectifiers. At frequencies below 30Hz$30 \,\mathrm{Hz}$, the static polarization curve begins to influence the voltage waveform of the specific cell, thereby reducing the predictive power of the impedance model. The results prove the use of the static polarization curve is generally inaccurate for modeling water electrolysis power consumption with ripple current. [ABSTRACT FROM AUTHOR]

3D printing technology based electrochemical device can provide ease of fabrication, cost effectiveness, rapid detection and lower limit of detection. Herein, a novel, customized, portable and inexpensive 3D printed electrochemical device, has been presented. Fibrous carbon Toray paper, deposited with gold nanoparticles through electrodeposition, used as a working electrode which Further device was tested with 1 mM sodium hypochlorite using cyclic voltammetry (CV) and square wave voltammetry (SWV) in 0.1 M PBS. Hypochlorite has a pivotal role in supporting the growing chemical and paper industries and finds diverse uses in several clinical applications. It is primarily used for disinfecting food, water and surfaces. The scan rate study was carried out from 20 mVs−1 to 250 mVs−1 using cyclic voltammetry technique. The diffusion coefficient obtained from scan rate effect was 1.39 × 10−6 cm2s−1. The concentration range was evaluated with SWV technique, in a linear range of 0.6 μM–40 μM, with a detection limit of 0.7 μM. The device was further analyzed to ensure non-interference from co-existing chemicals like sodium chloride, potassium nitrate, sodium carbonate, sodium nitrite. Real sample analysis was done with sea, artificial sea and tap water with impressive recovery values. In summary, the developed working electrode can be customized and modified based on testing analyte; thus, the proposed device can be used for various other biochemical analytes. [Display omitted] • Miniaturized 3D printed electroanalytical device was fabricated. • Gold nanoparticles were electrodeposited on Toray paper used as working electrode. • 1 mL of the sample was used throughout all analysis. • Lower limit of detection 0.07 μM was obtained using the device. • Hypochlorite detection in sea, artificial sea and tap water samples was carried out. [ABSTRACT FROM AUTHOR]

The direct electrochemical reduction of nicotinamide adenine dinucleotide (NAD+) results in various products, complicating the regeneration of the crucial 1,4‐NADH cofactor for enzymatic reactions. Previous research primarily focused on steady–state polarization to examine potential impacts on product selectivity. However, this study explores the influence of dynamic conditions on the selectivity of NAD+ reduction products by comparing two dynamic profiles with steady‐state conditions. Our findings reveal that the main products, including 1,4‐NADH, several dimers, and ADP‐ribose, remained consistent across all conditions. A minor by–product, 1,6‐NADH, was also identified. The product distribution varied depending on the experimental conditions (steady state vs. dynamic) and the concentration of NAD+, with higher concentrations and overpotentials promoting dimerization. The optimal yield of 1,4‐NADH was achieved under steady–state conditions with low overpotential and NAD+ concentrations. While dynamic conditions enhanced the 1,4‐NADH yield at shorter reaction times, they also resulted in a significant amount of unidentified products. Furthermore, this study assessed the potential of using pulsed electrochemical regeneration of 1,4‐NADH with enoate reductase (XenB) for cyclohexenone reduction. [ABSTRACT FROM AUTHOR]

In the present investigation, Cu2O-based composites were successfully prepared through a multistep method where cubic Cu2O nanoparticles (CU Cu2O) have been grown on Reduced Graphene Oxide (RGO) nanosheets. The structural and morphological properties of the materials have been studied through a comprehensive characterization, confirming the coexistence of crystalline Cu2O and RGO. Microscopical imaging revealed the intimate contact between the two materials, affecting the size and the distribution of Cu2O nanoparticles on the support. The features of the improved morphology strongly affected the electrochemical behavior of the composites, increasing the activity and the faradaic efficiencies towards the electrochemical CO2 reduction reaction process. CU Cu2O/RGO 2:1 composite displayed selective CO formation over H2, with higher currents compared to pristine Cu2O (−0.34 mA/cm2 for Cu2O and −0.64 mA/cm2 for CU Cu2O/RGO 2:1 at the voltage of −0.8 vs. RHE and in a CO2 atmosphere) and a faradaic efficiency of 50% at −0.9 V vs. RHE. This composition exhibited significantly higher CO production compared to the pristine materials, indicating a favorable *CO intermediate pathway even at lower voltages. The systematic investigation on the effects of nanostructuration on composition, morphology and catalytic behavior is a valuable solution for the formation of effective interphases for the promotion of catalytic properties providing crucial insights for future catalysts design and applications. [ABSTRACT FROM AUTHOR]

In this report, we elucidated the hydrogen evolution reaction (HER) catalytic activity of different metal-azaphthalocyanine unimolecular layer (AZUL) catalysts and compared the overpotentials in alkaline electrolyte membrane water electrolysis (AEMWE). While the overpotentials are bit higher compared to Pt/C, the system utilizing the FeAzPc-4N with Sustainion® showed a low overpotential of 2.02 V at 1.0 A/cm2 and faraday efficiency of 96.3% even among the previous alternative catalysts. It is noteworthy that the AZUL catalysts are not using precious metals and even comparing with other transition metal electrocatalysts, metal atom usage is much lower because only the single transition metal atom in the azapthalocyanine macrocycle works as a catalytic site. [ABSTRACT FROM AUTHOR]

Several commonly known physiological analytes, such as ascorbic acid (AA), dopamine (D), uric acid (UA), and xanthine (X), are known to have significant impact on human metabolism. Therefore, it is quite imperative to develop a miniaturized, multiplexed, noninterfering, and inexpensive sensing platform to monitor these compounds. Reminiscing this, herein, a miniaturized electrochemical sensing platform over a poly methyl methacrylate substrate has been depicted for specific and selective sensing of AA, D, UA, and X. First, to create three electrode zones for electrochemical sensing, three microchannels were engraved on a PMMA sheet by CO2 laser ablation process. Subsequently, these microchannels were filled with suitable electrode materials leading to a miniaturized electrochemical sensing platform. In the present article, the Toray carbon gas diffusion layer was the working electrode (WE), while screen-printed conductive carbon paste and silver chloride (Ag/AgCl) ink served as the counter electrode and the reference electrode, respectively. The electrocatalytic oxidation of these analytes exhibits an excellent electro-catalytic oxidation behavior. The effect of variable concentrations and interference from the coexisting analytes was also examined. The linear concentration ranges for these compounds (AA, D, UA, and X) under the optimized parameters were 100–1000, 40–1000, 20–1000, and 10– 100 μM, respectively, while the detection limits were 89.65, 38.94, 18.71, and 9.01 μM}correspondingly. The platform was also tested with real human serum samples. Such a multiplexed and miniaturized electrochemical sensing platform can be used in point-of-care devices for simultaneous sensing of multiple analytes. [ABSTRACT FROM AUTHOR]

Photoelectrochemistry is used to develop solar energy technologies for fuel production and chemical transformations. Semiconductor materials such as TiO2, WO3, BiVO4, Fe2O3, and Cu2O are often investigated in devices designed to convert light energy into chemical energy, including for the production of hydrogen by photoelectrochemical (PEC) water splitting. The oxide electrodes are of significant interest due to their potential for efficient PEC reactions with high durability and their relatively low costs compared to other semiconductor materials. This review highlights the roles played by macroporous photoelectrodes in the development of highly efficient photoelectrodes and advanced PEC systems using polymer electrolytes. Three‐dimensional conductive fiber substrates, such as titanium felt and carbon paper, outperform their two‐dimensional counterparts owing to their larger interfacial areas that enhance PEC properties. The macroporous structures facilitate mass‐transport‐limited reactions when integrated with polymer electrolytes in membrane electrode assemblies. Such configurations are promising for PEC splitting of pure water, and for transforming gaseous molecules such as water vapor, volatile organic compounds, and methane. Optimizing the configuration, including electrode materials selection and ionomer‐coating treatment, can potentially improve the performance of polymer electrolyte membrane PEC cells. Porous transport photoelectrodes integrated with proton/anion‐exchange membranes offer significant opportunities for advanced PEC applications. [ABSTRACT FROM AUTHOR]

Acetogenic bacteria produce CO2‐based chemicals in aqueous media by hydrogenotrophic conversion of CO2, but CO is the preferred carbon and electron source. Consequently, coupling CO2 electrolysis with bacterial fermentation within an integrated bio‐electrocatalytical system (BES) is promising, if CO2 reduction catalysts are available for the generation of CO in the complex biotic electrolyte. A standard stirred‐tank bioreactor was coupled to a zero‐gap PEM electrolysis cell for CO2 conversion, allowing voltage control and separation of the anode in one single cell. The cathodic CO2 reduction and the competing hydrogen evolution enabled in‐situ feeding of C. ragsdalei with CO and H2. Proof‐of‐concept was demonstrated in first batch processes with continuous CO2 gassing, as autotrophic growth and acetate formation was observed in the stirred BES in a voltage range of −2.4 to −3.0 V. The setup is suitable also for other bioelectrocatalytic reactions. Increased currents and lower overvoltages are however required. Atomically‐dispersed M−N−C catalysts show promise, if degradation throughout autoclaving can be omitted. The development of selective and autoclavable catalysts resistant to contamination and electrode design for the complex electrolyte will enable efficient bioelectrocatalytic power‐to‐X systems based on the introduced BES. [ABSTRACT FROM AUTHOR]

Abstract: In-plane permeability of gas diffusion backing (GDB) of proton exchange membrane fuel cells (PEMFCs) was investigated experimentally. Toray-paper and SGL-paper were selected as GDB test samples. Several Toray-papers were treated in-house with polytetrafluoroethylene (PTFE) using the immersion technique, dried either under atmospheric or vacuum pressure, and then sintered. The dependence of PTFE distribution in the through-plane direction on the PTFE drying conditions was examined using scanning electron microscopy (SEM)-based energy dispersive X-ray spectroscopy (EDS) imaging. The EDS image maps revealed that the PTFE distribution strongly depended on the drying condition, and PTFE drying under vacuum pressure yielded a relatively uniform PTFE distribution. The measured in-plane permeability suggests that the homogeneous distribution of PTFE achieved by the vacuum drying produces a porosity-leveling effect. In addition, the relationship between the in-plane permeability and porosity of the Toray-paper samples followed the Kozeny–Carman relation, whereas due to non-fibrous solids such as binder, that of the SGL-paper samples did not. [Copyright &y& Elsevier]

Abstract: We present an efficient, easy to construct, air-breathing biocathode for dioxygen reduction using the enzyme bilirubin oxidase encapsulated in a silicate gel film on Toray paper. Functionalised single-walled carbon nanotubes were used for improving electron transfer between the enzyme and the Toray paper. A current density of 1.2 mA cm−2 was measured under air without any mediators. The biocathode was connected with a Nafion-covered Zn-anode to form a zinc–oxygen battery. The biobattery has an open circuit voltage of 1.75 V and gives a maximum power density of 5.25 mW cm−2 at ca 0.4 V, which is the best result published so far for such a device. The device was used to power a two-LED bicycle lamp. [Copyright &y& Elsevier]

Abstract: This work investigates the degradation of an individual gas diffusion layer (GDL) by repeated freezing cycles. The pore size distribution, gas permeability, surface structure, and contact angle on the surface of the GDL were measured in four different types of GDL: SGL paper with a microporous layer (MPL); SGL paper with 5wt% of polytetrafluoroethylene (PTFE) loading; Toray paper without PTFE loading; and Toray paper with 20wt% of PTFE loading. After repeated freezing cycles, the porosity of the GDL without PTFE was reduced by 27.2% due to the volumetric expansion of the GDL. The peak of the log differential intrusion moved toward a smaller pore diameter slightly because of the repeated freezing process. The crack of the MPL increased in its width and length after repeated freezing cycles. The through-plane gas permeability of the GDL with the MPL doubled after repeated freezing cycles due to the growth of the crack in the MPL, but was very small for the GDLs with Toray paper. Besides, the GDLs with PTFE loading showed a relatively larger decrease in the contact angle on the surface than the GDL without PTFE loading due to the separation of PTFE from the carbon fiber during the repeated freezing process. [Copyright &y& Elsevier]

The increasing concentration of CO2 in the atmosphere and its impact on the climate are matters of significant concern. Extensive research is being conducted on molecular catalysts to electrochemically reduce CO2 into valuable products to disrupt the unidirectional carbon flow. This study compares two manganese bipyridine catalysts, tailored with four or two benzylic diethylamine groups in the secondary coordination sphere. Either of these amine‐bearing scaffolds positioned close to the Mn center serves as effective proton relays to facilitate the formation of the corresponding Mn hydride intermediate. Alongside competitive H2 evolution, the reaction of this crucial intermediate with CO2 leads to formate. Our findings underscore the pronounced influence of external Brønsted acids on product selectivity. Notably, when employing the catalyst bearing four amine groups, the HCOO−/H2 ratio varies from 81 : 3 with 1.0 M iPrOH to 16 : 64 with 1.0 M PhOH, while the Mn complex adorned with two amine pendant groups consistently favors HCOO−, irrespective of the utilized proton sources. Infrared spectroelectrochemistry and density‐functional theory calculations unveil distinct disparities in the reactivity of the Mn hydrides toward CO2 due to the change of ligand bulkiness in the two cases. This work substantiates the importance of modulating spatial accessibility while modifying the second sphere encompassing molecular catalysts. [ABSTRACT FROM AUTHOR]

The electrochemical reduction of carbon dioxide to formic acid is a promising pathway to improve CO2 utilization and has potential applications as a hydrogen storage medium. In this work, a zero-gap membrane electrode assembly architecture is developed for the direct electrochemical synthesis of formic acid from carbon dioxide. The key technological advancement is a perforated cation exchange membrane, which, when utilized in a forward bias bipolar membrane configuration, allows formic acid generated at the membrane interface to exit through the anode flow field at concentrations up to 0.25 M. Having no additional interlayer components between the anode and cathode this concept is positioned to leverage currently available materials and stack designs ubiquitous in fuel cell and H2 electrolysis, enabling a more rapid transition to scale and commercialization. The perforated cation exchange membrane configuration can achieve >75% Faradaic efficiency to formic acid at <2 V and 300 mA/cm2 in a 25 cm2 cell. More critically, a 55-hour stability test at 200 mA/cm2 shows stable Faradaic efficiency and cell voltage. Technoeconomic analysis is utilized to illustrate a path towards achieving cost parity with current formic acid production methods. Electrochemical reduction of CO2 to formic acid is a promising and sustainable pathway for valuable chemical generation. However, direct production of formic acid rather than formate is challenging. Herein the authors report a zero-gap membrane electrode assembly architecture with perforated cation exchange membrane for the direct electrochemical synthesis of formic acid from CO2. [ABSTRACT FROM AUTHOR]

The potato processing industry is among the biggest water-consuming industries, using an average of 17 L of water per 1 kg of processed product. Taking into account that the potato is the fourth-most-important non-cereal food crop with a global production of 376 million tons a year, this branch is a large wastewater producer. Potato-processing wastewater is highly loaded and thus difficult to treat through conventional methods, especially when a low energetic input for environmental benignancy is required. In this review, it was shown that microbial fuel cells (MFCs) are an excellent technology for sustainable potato wastewater treatment. MFCs allow for potato wastewater COD removal with efficiencies as high as 99%, which is accompanied by electricity production that may reach 3.7 W/m2. Thus, the recently published research reviewed in this paper indicates that simultaneous power production and removal of chemical oxygen demand make MFCs superior to conventional treatment methods. Encouraging results and the unique advantages of MFC technology, like significant water and energy use reduction, give a promising perspective on potato-processing wastewater treatments. [ABSTRACT FROM AUTHOR]

Aiming to advance the technical maturity of CO2 electrolysis to formic acid, various gas diffusion layers (GDLs) are investigated for their suitability as carbon‐based substrate for gas diffusion electrodes (GDEs) and their effect on the electroreduction of CO2 to formate. Particular attention lies on the elucidation for the effect of the GDL thickness, hydrophobic treatment, and presence of a microporous layer (MPL) on the GDE performance in terms of Faradaic efficiency. Based on the investigation it is found that the GDL thickness has no discernible influence on the Faradaic efficiency, while a GDE with a hydrophobic treatment of 10 % PTFE outperforms a GDE based on a GDL with 30 % PTFE. Furthermore, the presence of a MPL is found to be of marked importance to achieve relevant current densities given its effect on the focus of the catalyst layer on the GDE surface after spray coating, the wetting, and the electrical conductivity. [ABSTRACT FROM AUTHOR]

The purpose of this work is to evaluate single and double-cell membraneless microfluidic fuel cells (MMFCs) that operate in the presence of simulated body fluids SBF, human serum and blood enriched with ethanol as fuels. The study was performed using the alcohol dehydrogenase enzyme immobilised by covalent binding through an array composed of carbon Toray paper as support and a layer of poly(methylene blue)/tetrabutylammonium bromide/Nafion and glutaraldehyde (3D bioanode electrode). The single MMFC was tested in a hybrid microfluidic fuel cell using Pt/C as the cathode. A cell voltage of 1.035 V and power density of 3.154 mW cm −2 were observed, which is the highest performance reported to date. The stability and durability were tested through chronoamperometry and polarisation/performance curves obtained at different days, which demonstrated a slow decrease in the power density on day 10 (14%) and day 20 (26%). Additionally, the cell was tested for ethanol oxidation in simulated body fluid (SBF) with ionic composition similar to human blood plasma. Those tests resulted in 0.93 V of cell voltage and a power density close to 1.237 mW cm −2 . The double cell MMFC (Stack) was tested using serum and human blood enriched with ethanol. The stack operated with blood in a serial connection showed an excellent cell performance (0.716 mW cm −2 ), demonstrating the feasibility of employing human blood as energy source. [ABSTRACT FROM AUTHOR]

The redox potential (ERedox) of a ferrocene (Fc) derivative differs, depending on its functional group. In this study, the various Fc derivatives are considered as mediators of anodic catalysts to promote glucose oxidation reaction (GOR) in glucose/oxygen enzymatic biofuel cells (EBFCs). Initially, their lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energies are calculated using density functional theory to predict their ERedox pattern. According to the calculations, the LUMO and HOMO energies of Fc derivatives combined with electron-donating groups (EDGs) are higher than those of Fc derivatives combined with electron-withdrawing groups (EWGs), including the results that Fc(NH2) has the highest molecular orbital (MO), while Fc(CHO) has the lowest. To verify the prediction for ERedox pattern, electrochemical evaluations are conducted. When glucose is provided, the onset potential (EOnset) of GOR is measured, while the ERedox of Fc derivatives and EOnset of GOR are linearly proportional to each other ( R 2 = 0.98) and DFT calculations. As the energies increase, the above two potentials are shifted more negatively. More specifically, the ERedox of Fc(NH2) and EOnset of GOR show the most negative values at (−0.112 and −0.17) V, respectively, while the ERedox of Fc(CHO) and EOnset of GOR show the most positive values at (0.496 and 0.40) V, respectively. Then, when this correlation is adopted for EBFCs, EBFCs using Fc(NH2) combined with EDG show 3.7 times higher maximum power density than those using Fc(COOH), as representatives combined with EWG. Based on that, it is well established how DFT and electrochemical evaluations should be used to design anodic catalysts including Fc derivatives as mediators for GOR. [ABSTRACT FROM AUTHOR]

The electrocatalytic CO2 reduction reaction (CO2RR) to formic acid has gained significant attention as a potential environmentally friendly approach to reducing CO2 emissions and producing carbon-neutral liquid fuels. However, several challenges must be addressed to achieve the production of high-purity and high-concentration formic acid through CO2RR. One major challenge is the formation of a formate mixture instead of pure formic acid in conventional reactors. This requires costly downstream purification and concentration processes to obtain pure formic acid. To overcome this problem, a three-compartment reactor design has been proposed where a solid-state electrolyte (SSE) is inserted between the anode and cathode compartments to recover pure formic acid directly. This reactor design involves the use of an anion exchange membrane (AEM) and a cation exchange membrane (CEM) to separate the anode and cathode compartments, and a center compartment filled with high-conductivity SSE to minimize ohmic resistance. Several studies have implemented this reactor design for continuous CO2RR and have reported remarkable improvements in the concentration and purity of the formic acid product. In this review, we summarize the recent progress of the SSE reactor design for CO2RR to produce pure formic acid (HCOOH) and propose further research to scale up this technology for industrial-scale applications in the future. [ABSTRACT FROM AUTHOR]

The use of enzyme-based biosensors for the detection and quantification of analytes of interest such as contaminants of emerging concern, including over-the-counter medication, provides an attractive alternative compared to more established techniques. However, their direct application to real environmental matrices is still under investigation due to the various drawbacks in their implementation. Here, we report the development of bioelectrodes using laccase enzymes immobilized onto carbon paper electrodes modified with nanostructured molybdenum disulfide (MoS2). The laccase enzymes were two isoforms (LacI and LacII) produced and purified from the fungus Pycnoporus sanguineus CS43 that is native to Mexico. A commercial purified enzyme from the fungus Trametes versicolor (TvL) was also evaluated to compare their performance. The developed bioelectrodes were used in the biosensing of acetaminophen, a drug widely used to relieve fever and pain, and of which there is recent concern about its effect on the environment after its final disposal. The use of MoS2 as a transducer modifier was evaluated, and it was found that the best detection was achieved using a concentration of 1 mg/mL. Moreover, it was found that the laccase with the best biosensing efficiency was LacII, which achieved an LOD of 0.2 µM and a sensitivity of 0.108 µA/µM cm2 in the buffer matrix. Moreover, the performance of the bioelectrodes in a composite groundwater sample from Northeast Mexico was analyzed, achieving an LOD of 0.5 µM and a sensitivity of 0.015 µA/µM cm2. The LOD values found are among the lowest reported for biosensors based on the use of oxidoreductase enzymes, while the sensitivity is the highest currently reported. [ABSTRACT FROM AUTHOR]

The urine/urea oxidation reaction through catalysts with a higher performance in direct urea microfluidic fuel cells (DUµFC) is a promising method for power generation due to the large amount of human and animal urine containing 2–2.5 wt% urea. This paper presents a study that used urea as fuel in a DUµFC in the presence of palladium supported by reduced graphene oxide (rGO) for power generation. Some parameters, such as urea, KOH and H2SO4 concentration and flux rate, among others, are optimized in order to carry out the evaluation of urine samples as fuel in an air-breathing microfluidic fuel cell. The results show that the Pd/rGo catalyst mixed with Nafion® in the anodic compartment is dispersed and attached to the paper fibers, generating electrical contact and giving rise to the reactions of interest. In addition, XRD analysis confirmed the successful deposition of Pd and rGo on the substrate. These electrochemical results are promising, since, despite the decrease in the general performance of the DUµFC under ideal conditions with respect to normal cells, the generation of energy from urine was demonstrated. [ABSTRACT FROM AUTHOR]

Platinum group metal (PGM)-free oxygen reduction reaction (ORR) catalysts are of utmost importance for the rapid development of anion-exchange membrane fuel cell (AEMFC) technology. In this work, we demonstrate the improved ORR performance and stability of Co and Fe oxide-decorated/N-doped reduced graphene oxide (CoOx-Fe3O4/N-rGO) prepared via a hydrothermal method at the low temperature of 150 °C. The catalysts were characterized thoroughly using transmission electron microscopy, high-angle annular dark field-scanning electron microscopy, X-ray diffraction, N2 physisorption, Raman spectroscopy, and X-ray photoelectron spectroscopy to obtain information about morphology, elemental distribution, phases, porosity, defects, and surface elemental compositions. Significant ORR activity improvement (130 mV@-1.5 mA cm−2) was achieved with this catalyst compared to the pristine graphene oxide, and the ORR limiting current was even 12%@0.5 V higher than the commercial Pt/C. The enhanced ORR activity of CoOx-Fe3O4/N-rGO was attributed to the uniform dispersion of Co, Fe, and N on reduced graphene oxide (rGO) sheets. Furthermore, ORR accelerated stress tests revealed excellent durability, suggesting that this material could be a promising and durable catalyst. With a cathode layer of the CoOx-Fe3O4/N-rGO catalyst, we achieved a peak power density of 676 mW cm−2 in an operando H2-O2 AEMFC. To the best of our knowledge, this is the highest reported power density per cathode catalyst mass in a reported PGM-free cathode catalyst. Finally, we quantified the various cell polarization losses as a function of cathode catalyst loadings to obtain insights for future work with AEMFCs based on this catalyst. The improvement in the AEMFC performance using CoOx-Fe3O4/N-rGO as a cathode catalyst can be attributed to the synergistic effects of (i) the high turnover frequency of the transition metals (Co and Fe) for ORR and (ii) the enhancement provided by N doping to the metal distribution and stability. [ABSTRACT FROM AUTHOR]

In this study, a simple and scalable method to obtain heterogeneous indium nanoparticles and carbon-supported indium nanoparticles under mild conditions is described. Physicochemical characterization by X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed heterogeneous morphologies for the In nanoparticles in all cases. Apart from In0, XPS revealed the presence of oxidized In species on the carbon-supported samples, whereas these species were not observed for the unsupported samples. The best-in-class catalyst (In50/C50) exhibited a high formate Faradaic efficiency (FE) near the unit (above 97%) at −1.6 V vs. Ag/AgCl, achieving a stable current density around −10 mA·cmgeo−2, in a common H-cell. While In0 sites are the main active sites for the reaction, the presence of oxidized In species could play a role in the improved performance of the supported samples. [ABSTRACT FROM AUTHOR]

Cobalt oxide (Co3O4) serves as a promising electrocatalyst for oxygen evolution reactions (OER) in water-electrolytic hydrogen production. For more practical applications, advances in dry-deposition processes for the high-throughput fabrication of such Co3O4 electrocatalysts are needed. In this work, a thermal metal–organic deposition (MOD) technique is developed to form Co3O4 deposits on microscale-diameter carbon fibers constituting a carbon fiber paper (CFP) substrate for high-efficiency OER electrocatalyst applications. The Co3O4 electrocatalysts are deposited while uniformly covering the surface of individual carbon fibers in the reaction temperature range from 400 to 800 °C under an ambient Ar atmosphere. It is found that the microstructure of deposits is dependent on the reaction temperature. The Co3O4 electrocatalysts prepared at 500 °C and over exhibit values of 355–384 mV in overpotential (η10) required to reach a current density of 10 mA cm−2 and 70–79 mV dec−1 in Tafel slope, measured in 1 M KOH aqueous solution. As a result, it is highlighted that the improved crystallinity of the Co3O4 electrocatalyst with the increased reaction temperature leads to an enhancement in electrode-level OER activity with the high electrochemically active surface area (ECSA), low charge transfer resistance (Rct), and low η10, due to the enhanced electrical conductivity. On the other hand, it is found that the inherent catalytic activity of the surface sites of the Co3O4, represented by the turnover frequency (TOF), decreases with reaction temperature due to the high-temperature sintering effect. This work provides the groundwork for the high-throughput fabrication and rational design of high-performance electrocatalysts. [ABSTRACT FROM AUTHOR]

We report potentiodynamic studies to characterize copper, nickel and zinc leaching solutions from electronic waste. The metals were leached using oxygen and sulfuric acid (pH = 1.5). As is known, reduction potentials are determined using thermodynamics laws, and metal recovery strategies from electronic waste are usually considered according these thermodynamic values. Pourbaix-type diagrams are not appropriate to plan strategies in electrochemical processing. Therefore, knowledge of electrode potentials for the metal deposit/dissolution process is the basis for the selective recovery planning. For this reason, potentiodynamic studies, specifically cyclic voltammetry, are revealed as a good way to decide the best conditions for the process of electrochemical recovery of metals from electronic waste, which is also cost-efficient and has no interference from strange ions, such as lead, in this case. [ABSTRACT FROM AUTHOR]

The purpose of this work is to develop a bioanode using the enzymes of glucose oxidase (GOx) and alcohol dehydrogenase (ADH) as catalysts to oxidised glucose and alcohol present in different beverages. The study was carried out using the covalent bonding method for both enzymes via the functionalization of carbon nanofibers for the formation of carboxyl groups that can form bonds with the amine groups of the enzyme, as well as using tetrabutylammonium bromide (TBAB) with Nafion. The optimum operation parameters of both enzymes (pH and temperature) were determined for the later evaluation in a microfluidic fuel cell. In addition, using the scanning electrochemical microscopy technique, a local study of enzymatic processes is used to demonstrate that the enzymes immobilized on the same electrode remain active. The evaluation of the microfluidic fuel cell was carried out using different solutions, 0.01 M glucose, 0.01 M ethanol and a mixture of 0.01 M glucose and 0.01 M ethanol, all in phosphate buffer solutions at pH 7, where it was possible to obtain a maximum performance of 5.07 ± 0.1 mW cm−2, and there was a significant increase in current density compared to non-composite solutions (glucose or ethanol). In addition, different alcoholic beverages were used to evaluate the versatility and adaptability of the bi-enzymatic anode electrode with the perspective use in Lab-on-a-Chip systems. [ABSTRACT FROM AUTHOR]

Abstract: The microstructure of a TGP-H-120 Toray paper gas diffusion layer (GDL) was investigated using high resolution X-ray computed tomography (CT) technique, with a resolution of 1.8 μm and a field of view (FOV) of ∼1.8 × 1.8 mm. The images obtained from the tomography scans were further post processed, and image thresholding and binarization methodologies are presented. The validity of Otsu's thresholding method was examined. Detailed information on bulk porosity and porosity distribution of the GDL at various Polytetrafluoroethylene (PTFE) treatments and uniform/non-uniform compression pressures was provided. A sample holder was designed to investigate the effects of non-uniform compression pressure, which enabled regulating compression pressure between 0, and 3 MPa at a gas channel/current collector rib configuration. The results show the heterogeneous and anisotropic microstructure of the GDL, non-uniform distribution of PTFE, and significant microstructural change under uniform/non-uniform compression. These findings provide useful inputs for numerical models to include the effects of microstructural changes in the study of transport phenomena within the GDL and to increase the accuracy and predictability of cell performance. [Copyright &y& Elsevier]

This study reports the performance of simple low-cost synthesized bifunctional Cu/Cu2O nanoparticles (NPs) used as a catalyst for energy-harvesting applications through of a microfluidic fuel cell (µFC), and further, as cholesterol (Chol) sensor. TEM characterization of the NPs showed spheres between 4 and 10 nm, while XRD and XPS analysis confirmed the composition and preferential crystallographic plane of Cu/Cu2O. In addition, 25.26 m2 g−1 surface area was obtained, which is greater than those commercial materials. NPs showed high activity toward the cholesterol oxidation reaction when were used as a sensor, obtaining a linear interval between 0.5 and 1 mM and 850 µA mM−1 mg−1 of sensitivity and 8.9 µM limit of quantification LOQ. These values are comparable to results previously reported. Moreover, Cu/Cu2O NPs were used as anode in a µFC with 0.96 V of cell voltage and 6.5 mA cm−2 and 1.03 mW cm−2 of current and power density, respectively. This performance is the highest currently reported for cholesterol application as an alternative fuel, and the first one reported for a microfluidic fuel cell system as far as is known. Results showed that the obtained Cu-based NPs presented an excellent performance for the dual application both µFC and sensor, which has potential applications in biomedicine and as an alternative energy source. [ABSTRACT FROM AUTHOR]

In this paper, a three-dimensional model of a high-temperature anion-exchange membrane fuel cell (HT-AEMFC) operating at 110 °C is presented. All major transport phenomena along with the electrochemical reactions that occur in the cell are modeled. Since the water is exclusively in the form of steam and there is no phase transition to deal with in the cell, the water management is greatly simplified. The cell performance under various current loads is evaluated, and the results are validated against the experimental data. The cell performance is examined across a range of operating conditions, including cell temperature, inlet flow rate, and inlet relative humidity (RH). The critical link between the local distributions of species and local current densities along the channels is identified. The distribution of reactants continuously drops in the gas flow direction along the flow channels, causing a non-uniform local current distribution that becomes more pronounced at high current loads, where the rate of water generation increases. The findings show that while a higher inlet flow rate enhances the cell performance, a lower flow rate causes it to drop because of reactant depletion in the anode. The sensitivity analysis reveals that the performance of an AEMFC is highly dependent on the humidity of the gas entering the cell. While high inlet RH on the cathode side enhances the cell performance, high inlet RH on the anode side deteriorates it. [ABSTRACT FROM AUTHOR]

Abstract: This paper describes the use of an in situ analytical technique based on simultaneous displacement and resistance measurement of gas diffusion layers (GDLs) used in polymer electrolyte fuel cells (PEFCs), when exposed to varying compaction pressure. In terms of the losses within fuel cells, the ohmic loss makes up a significant portion. Of this loss, the contact resistance between the GDL and the bipolar plate (BPP) is an important constituent. By analysing the change in thickness and ohmic resistance of GDLs under compression, important mechanical and electrical properties are obtained. Derived parameters such as the ‘displacement factor’ are used to characterise a representative range of commercial GDLs. Increasing compaction pressure leads to a non-linear decrease in resistance for all GDLs. For Toray paper, compaction becomes more irreversible with pressure with no elastic region observed. Different GDLs have different intrinsic resistance; however, all GDLs of the same class share a common compaction profile (change in resistance with pressure). Cyclic compression of Toray GDL leads to progressive improvement in resistance and reduction in thickness that stabilises after ∼10 cycles. [Copyright &y& Elsevier]

Abstract: This paper describes the use of the electrostatic layer-by-layer (LbL) technique for the preparation of bioanodes with potential application in ethanol/O2 biofuel cells. More specifically, the LbL technique was employed for immobilization of dehydrogenase enzymes and polyamidoamine (PAMAM) dendrimers onto carbon paper support. Both mono (anchoring only the enzyme alcohol dehydrogenase, ADH) and bi-enzymatic (anchoring both ADH and aldehyde dehydrogenase, AldDH) systems were tested. The amount of ADH deposited onto the Toray® paper was 95ngcm−2 per bilayer. Kinetic studies revealed that the LbL technique enables better control of enzyme disposition on the bioanode, as compared with the results obtained with the bioanodes prepared by the passive adsorption technique. The power density values achieved for the mono-enzymatic system as a function of the enzyme load ranged from 0.02 to 0.063mWcm−2 for the bioanode containing 36 ADH bilayers. The bioanodes containing a gas diffusion layer (GDL) displayed enhanced performance, but their mechanical stability must be improved. The bi-enzymatic system generated a power density of 0.12mWcm−2. In conclusion, the LbL technique is a very attractive approach for enzyme immobilization onto carbon platform, since it enables strict control of enzyme disposition on the bioanode surface with very low enzyme consumption. [ABSTRACT FROM AUTHOR]

In this study, we demonstrate three-dimensional (3D) hollow nanosphere electrocatalysts for CO2 conversion into formate with excellent H-Cell performance and industrially-relevant current density in a 25 cm2 membrane electrode assembly electrolyzer device. Varying calcination temperature maximized formate production via optimizing the crystallinity and particle size of the constituent SnO2 nanoparticles. The best performing SnO2 nanosphere catalysts contained ~ 7.5 nm nanocrystals and produced 71–81% formate Faradaic efficiency (FE) between −0.9 V and −1.3 V vs. the reversible hydrogen electrode (RHE) at a maximum formate partial current density of 73 ± 2 mA cmgeo−2 at −1.3 V vs. RHE. The higher performance of nanosphere catalysts over SnO2 nanoparticles and commercially-available catalyst could be ascribed to their initial structure providing higher electrochemical surface area and preventing extensive nanocrystal growth during CO2 reduction. Our results are among the highest performance reported for SnO2 electrocatalysts in aqueous H-cells. We observed an average 68 ± 8% FE over 35 h of operation with multiple on/off cycles. In situ Raman and time-dependent X-ray diffraction measurements identified metallic Sn as electrocatalytic active sites during long-term operation. Further evaluation in a 25 cm2 electrolyzer cell demonstrated impressive performance with a sustained current density of 500 mA cmgeo−2 and an average 75 ± 6% formate FE over 24 h of operation. Our results provide additional design concepts for boosting the performance of formate-producing catalysts. [ABSTRACT FROM AUTHOR]

Herein, we report high electrocatalytic activity of monoclinic VO2 (M1 phase) for the oxygen evolution reaction (OER) for the first time. The single-phase VO2 (M1) nanoparticles are prepared in the form of uniformly covering the surface of individual carbon fibers constituting a carbon fiber paper (CFP). The VO2 nanoparticles reveal the metal-insulator phase transition at ca. 65 °C (heating) and 62 °C (cooling) with low thermal hysteresis, indicating a high concentration of structural defect which is considered a grain boundary among VO2 nanoparticles with some particle coalescence. Consequently, the VO2/CFP shows a high electrocatalytic OER activity with the lowest η10 (350 mV) and Tafel slope (46 mV/dec) values in a 1 M aqueous solution of KOH as compared to those of the vacuum annealed V2O5 and the hydrothermally grown VO2 (M1), α-V2O5, and γ′-V2O5. The catalytically active site is considered V4+ components and V4+/5+ redox couples in VO2. The oxidation state of V4+ is revealed to be more favorable to the OER catalysis compared to that of V5+ in vanadium oxide through comparative studies. Furthermore, the amount of V5+ component is found to be increased on the surface of VO2 catalyst during the OER, giving rise to the performance degradation. This work suggests V4+ and its redox couple as a novel active component for the OER in metal-oxide electrocatalysts. [ABSTRACT FROM AUTHOR]

Lateral flow assays (LFAs) are the best-performing and best-known point-of-care tests worldwide. Over the last decade, they have experienced an increasing interest by researchers towards improving their analytical performance while maintaining their robust assay platform. Commercially, visual and optical detection strategies dominate, but it is especially the research on integrating electrochemical (EC) approaches that may have a chance to significantly improve an LFA's performance that is needed in order to detect analytes reliably at lower concentrations than currently possible. In fact, EC-LFAs offer advantages in terms of quantitative determination, low-cost, high sensitivity, and even simple, label-free strategies. Here, the various configurations of EC-LFAs published are summarized and critically evaluated. In short, most of them rely on applying conventional transducers, e.g., screen-printed electrode, to ensure reliability of the assay, and additional advances are afforded by the beneficial features of nanomaterials. It is predicted that these will be further implemented in EC-LFAs as high-performance transducers. Considering the low cost of point-of-care devices, it becomes even more important to also identify strategies that efficiently integrate nanomaterials into EC-LFAs in a high-throughput manner while maintaining their favorable analytical performance. [ABSTRACT FROM AUTHOR]

B arising from b Z. Weng et al. I Nature Communications i https://doi.org/10.1038/s41467-018-02819-7 (2018) Metal phthalocyanines and porphyrins are among the most popular molecular catalysts for the electrochemical reduction of CO SB 2 sb . More recently, I operando i X-ray Absorption Spectroscopy studies revealed that under cathodic conditions, small copper nanoparticles were forming from complex demetallation and were responsible for the catalysis[2]. In the following work, the same catalyst along with Cu phthalocyanine ( B CuPc b ), Cu cyclam, and a copper-based metal-organic framework was investigated with I operando i X-ray Absorption Spectroscopy[2]. [Extracted from the article]