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Abstract This work presents the synthesis and evaluation of Pd-Ni aerogels toward the urea oxidation reaction (UOR). The incorporation of Ni led to a 0.13 V reduction in the energy required for the oxidation and reduction of PdO compared to monometallic Pd, both in alkaline medium with and without urea. Varying the Ni ratios in Pd (Pd-Ni 4:1, Pd-Ni 1:1, and Pd-Ni 1:4) led to significant changes in the electrochemical behaviour. In alkaline medium without urea, PdNi 4:1 showed the formation of NiOOH at 1.35 V, which promoted oxygen diffusion on the electrode surface and increased the current density, confirming the increase in the active sites of NiOOH and NiPdOOH and enabling urea-based electrolysis at these sites. While palladium aerogels alone are ineffective for UOR, the presence of nickel plays a key role in enhancing the UOR efficiency. On the other hand, physicochemical characterisation revealed that PdNi 4:1 has a crystal size of 4.37 nm and a larger shift in the 2θ positions of the (111) and (200) planes, which favours electronic changes that were investigated by XPS. These changes affected the electrocatalytic activity, which is primarily related to electronic effects. The results of SEM and TEM studies and nitrogen adsorption-desorption isotherm confirmed that the aerogels are highly porous and have an effective surface area and abundant active sites for reactions that allow efficient mass transfer and low diffusion resistance. TEM observations revealed interconnected nanochains indicating optimal electrocatalytic activity for both ORR and UOR due to high mass transfer. These interconnected networks are crucial for improving electrocatalytic activity in the urea oxidation reaction.

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.

This systematic review presents the current state of research in the last five years on contaminants in soils, especially in leachates from solid waste landfills, with emphasis on biological remediation. In this work, the pollutants that can be treated by microorganisms and the results obtained worldwide were studied. All the data obtained were compiled, integrated, and analyzed by soil type, pollutant type, bacterial type, and the countries where these studies were carried out. This review provides reliable data on the contamination of soils worldwide, especially soils contaminated by leachate from municipal landfills. The extent of contamination, treatment objectives, site characteristics, cost, type of microorganisms to be used, and time must be considered when selecting a viable remediation strategy. The results of this study can help develop innovative and applicable methods for evaluating the overall contamination of soil with different contaminants and soil types. These findings can help develop innovative, applicable, and economically feasible methods for the sustainable management of contaminated soils, whether from landfill leachate or other soil types, to reduce or eliminate risk to the environment and human health, and to achieve greater greenery and functionality on the planet.

The aim of this work is the evaluation of a Sulfonated Poly Ether-Ether Ketone (S-PEEK) polymer modified by the addition of pure Santa Barbara Amorphous-15 (SBA-15, mesoporous silica) and SBA-15 previously impregnated with phosphotungstic acid (PWA) fillers (PWA/SBA-15) in order to prepare composite membranes as an alternative to conventional Nafion® membranes. This component is intended to be used as an electrolyte in electrochemical energy systems such as hydrogen and methanol Proton Exchange Membrane Fuel Cell (PEMFC) and Electrochemical Hydrogen Pumping (EHP). The common requirements for all the applications are high proton conductivity, thermomechanical stability, and fuel and oxidant impermeability. The morphology of the composite membranes was investigated by Scanning Electron Microscopy- Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis. Water Uptake (Wup), Ion Exchange Capacity (IEC), proton conductivity, methanol permeability and other physicochemical properties were evaluated. In PEMFC tests, the S-PEEK membrane with a 10 wt.% SBA-15 loading showed the highest performance. For EHP, the inclusion of inorganic materials led to a back-diffusion, limiting the compression capacity. Concerning methanol permeability, the lowest methanol crossover corresponded to the composites containing 5 wt.% and 10 wt.% SBA-15.

Currently, the ethanol electro-oxidation reaction has attracted considerable attention in fuel cells because of new green ethanol synthetic methods based on biomass processes that have emerged. In this study, PtFe/C and Pt/C nanoparticles were synthesized by a chemical reduction method and tested in the ethanol electro-oxidation reaction. Furthermore, the electrocatalytic effect of the PtFe bimetallic catalyst was analyzed by in situ surface-enhanced Raman spectroscopy (SERS) coupled to an electrochemical cell. X-ray diffractograms showed typical face-centered cubic structures with crystallite sizes of 3.31 and 3.94 for Pt/C and PtFe/C, respectively. TEM micrographs revealed nanoparticle sizes of 2 ± 0.4 nm and 3 ± 0.6 nm for Pt/C and PtFe/C respectively. PtFe/C exhibited a Pt90Fe10 composition by both X-ray fluorescence and energy-dispersive X-ray spectroscopy. A better electrocatalytic activity as function of concentration was obtained through the incorporation of a small amount of Fe into the Pt lattice and the presence of Fe2+/Fe3+ (observed by X-ray photoelectron spectroscopy). According to SERS experiments, the presence of these iron species promotes the chemisorption of ethanol, the formation of formic acid as main product and renewal of the catalytic sites, resulting in current densities that were at least three fold higher than the values obtained for the Pt/C nanocatalyst.

The new concept of a hook-and-loop tape-based membraneless device constructed on adhesive polyester film, which is fabricated using non-sophisticated and inexpensive fabrication techniques at room temperature, is presented. This concept overcomes the concerns about the reliability, versatility, weight, cost, lifetime and high performance of microfluidic fuel cell devices to satisfy the needs of portable energy applications. Current densities from 150 to 600 mA cm−2 and power densities from 40 to 132 mW cm−2 were achieved by varying the formic acid concentration, flow rates and by using air and dissolved oxygen as an oxidant. [ABSTRACT FROM AUTHOR]

Nowadays, hydrogen has a preponderant position among the potentially sustainable energy sources. Due to its power density, its storage is of main concern when considering a broad use in practical applications. Carbon nanotubes constitute promising candidates for the design and construction of hydrogen storage devices. This work explores the use of some procedures involving electrochemistry, aimed to bond atomic Ti on the outer surface of MWNTs. Each titanium atom has the potential of hosting two hydrogen molecules and relinquishing them by heating. Nevertheless, nanotubes are difficult to handle due to electrostatic charge and agglomeration, and in this context, two routes were tested as procedures to spread and stick nanotubes on an electrode: (1) a functionalization capable of attaching gold was tested in two forms, as either using 4 nm particles or a flat gold electrode. The fixation of Au particles was confirmed by HRTEM. (2) A simpler route that consisted on drying a CH2Cl2/nanotubes solution previously spread on a glassy carbon flat electrode. CH2Cl2 was selected as the medium and TiCl4 as the precursor for attaching atomic Ti to the nanotubes. The results revealed that hydrogen adsorption, estimated from voltamperometry, was five times higher on Ti-MWNTs than on bare nanotubes.

This work presents the modification of glassy carbon electrodes (GCE) by using a dispersion resulting from the non-covalent functionalization of multi-walled carbon nanotubes (MWCNT) with polyarginine (polyArg). MWCNT-polyArg is used for the quantification of ascorbic acid (AA) in the presence of acetaminophen (APAP) and viceversa. Since ascorbic acid and acetaminophen are strongly absorbed on GCE/MWCNT-polyArg, they can be detected in the presence of 4.0×10 -5 M acetaminophen (and 3.0×10 -5 M ascorbic acid) by using adsorptive stripping with media exchange and differential pulse voltammetry. Using water as the solvent for the MWCNT dispersion, the result was Z-potential of 0.053 ± 0.006 V. The developed sensor showed excellent specificity, sensitivity, stability and reproducibility compared to previously published sensors. The GCE/MWCNT-polyArg sensor shows a fast response time of ∼5 minutes, low limits of detection and quantification for AA (0.95 and 2.9 μM respectively) and APAP (0.27 and 0.82μM, respectively), high sensitivity of 0.0616 μA/M for AA or APAP 0.240μA/M. It was used to test its practicability by determining the concentration of AA or APAP (AA and APAP) in pharmaceutical samples. Finally, the simultaneous measurement of ascorbic acid and acetaminophen in pharmaceuticals showed a good correlation, with a maximum error and RSD of 4.5 and 5.1 %, respectively., Competing Interests: Declaration of Competing Interest The authors declare no competing interests, (Copyright © 2024 Elsevier B.V. All rights reserved.)

Conventionally, the optimization of glucose biosensors is achieved by varying the concentrations of the individual reagents used to immobilize the enzyme. In this work, the effect and interaction between glucose oxidase enzyme (GOx), ferrocene methanol (Fc), and multi-walled carbon nanotubes (MWCNTs) at different concentrations were investigated by a design of experiments (DoE). For this analysis, a factorial design with three factors and two levels each was used with the software RStudio for statistical analysis. The data were obtained by electrochemical experiments on the immobilization of GOx-Fc/MWCNT at different concentrations. The results showed that the factorial DoE method was confirmed by the non-normality of the residuals and the outliers of the experiment. When examining the effects of the variables, analyzing the half-normal distribution and the effects and contrasts for GOx-Fc/MWCNT, the factors that showed the greatest influence on the electrochemical response were GOx, MWCNT, Fc, and MWCNT:Fc, and there is a high correlation between the factors GOx, MWCNT, Fc, and MWCNT:Fc, as shown by the analysis of homoscedasticity and multicollinearity. With these statistical analyses and experimental designs, it was possible to find the optimal conditions for different factors: 10 mM mL -1 GOx, 2 mg mL -1 Fc, and 15 mg mL -1 MWCNT show a greater amperometric response in the glucose oxidation. This work contributes to advancing enzyme immobilization strategies for glucose biosensor applications. Systematic investigation of DoE leads to optimized immobilization for GOx, enables better performance as a glucose biosensor, and allows the prediction of some outcomes., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

This article provides an overview of the work reported in the past decade in the field of microfluidic fuel cells. To develop appropriate research, the most commonly used electrocatalytic materials were considered and a new classification was proposed based on their nature: abiotic, hybrid, or biological. This classification allowed the authors to discern the information collected. In this sense, the types of electrocatalysts used for the oxidation of the most common fuels in different environments, such as glucose, ethanol, methanol, glycerol, and lactate, were presented. There are several phenomena presented in this article. This information gives an overview of where research is heading in the field of materials for electrocatalysis, regardless of the fuel used in the microfluidic fuel cell: the synthesis of abiotic and biological materials to obtain hybrid materials that allow the use of the best properties of each material., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

This systematic review presents the current state of research in the last five years on contaminants in soils, especially in leachates from solid waste landfills, with emphasis on biological remediation. In this work, the pollutants that can be treated by microorganisms and the results obtained worldwide were studied. All the data obtained were compiled, integrated, and analyzed by soil type, pollutant type, bacterial type, and the countries where these studies were carried out. This review provides reliable data on the contamination of soils worldwide, especially soils contaminated by leachate from municipal landfills. The extent of contamination, treatment objectives, site characteristics, cost, type of microorganisms to be used, and time must be considered when selecting a viable remediation strategy. The results of this study can help develop innovative and applicable methods for evaluating the overall contamination of soil with different contaminants and soil types. These findings can help develop innovative, applicable, and economically feasible methods for the sustainable management of contaminated soils, whether from landfill leachate or other soil types, to reduce or eliminate risk to the environment and human health, and to achieve greater greenery and functionality on the planet.

This work reports on Fe 2 O 3 and ZnO materials for lactate quantification. In the synthesis, the bi-phase γ-/α-Fe 2 O 3 and γ-/α-Fe 2 O 3 /ZnO nanoparticles (NPs) were obtained for their application in a lactate colorimetric sensor. The crystalline phases of the NPs were analyzed by XRD and XPS techniques. S/TEM images showed spheres with an 18 nm average and a needle length from 125 to 330 nm and 18 nm in diameter. The γ-/α-Fe 2 O 3 and γ-/α-Fe 2 O 3 /ZnO were used to evaluate the catalytic activity of peroxidase with the substrate 3,3,5,5-tetramethylbenzidine (TMB), obtaining a linear range of 50 to 1000 μM for both NPs, and a 4.3 μM and 9.4 μM limit of detection (LOD), respectively. Moreover, γ-/α-Fe 2 O 3 and γ-/α-Fe 2 O 3 /ZnO/lactate oxidase with TMB assays in the presence of lactate showed a linear range of 50 to 1000 µM, and both NPs proved to be highly selective in the presence of interferents. Finally, a sample of human serum was also tested, and the results were compared with a commercial lactometer. The use of ZnO with Fe 2 O 3 achieved a greater response toward lactate oxidation reaction, and has implementation in a lactate colorimetric sensor using materials that are economically accessible and easy to synthesize.

Ferrocene-based polymers as redox mediators are considered versatile and important in the study of glucose biosensors. Poly-L-lysine (PLL), as a cationic polymer, possesses good properties including biocompatibility, biodegradation and water solubility. In this work, PLL was modified with ferrocene carboxylate in a very simple way by activating the carboxyl group of Fc, which reacted with the amino groups of the polymer. The resulting product was analysed by FTIR. Performance as a redox mediator (Fc-PLL) with the enzyme glucose oxidase was tested by cyclic voltammetry and showed an increase in the oxidation current in the presence of glucose in PBS pH 7.4. Additionally, performance as a biosensor was evaluated by amperometry and gave a linear range of 0-10 mM, a limit of detection of 23 μM, a sensitivity of 6.55 μA/cm 2 mM and high selectivity. To evaluate the charged regions of Fc-PLL/GOx on the electrode surface, analysis by scanning electrochemical microscopy showed remarkable activity. The Fc-PLL redox polymer as a glucose biosensor has been well accepted as this kind of material, and the results showed remarkable activity as an electron transfer mediator between the redox polymer and the GOx enzyme., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In this work, unsupported Pd aerogel catalysts were synthesized for the very first time by using microwaves as a heating source followed by a lyophilization drying process and used towards formic acid electro-oxidation in a microfluidic fuel cell. Aerogels were also made by heating in a conventional oven to evaluate the microwave effect during the synthesis process of the unsupported Pd aerogels. The performance of the catalysts obtained by means of microwave heating favored the formic acid electro-oxidation with H 2 SO 4 as the electrolyte. The aerogels' performance as anodic catalysts was carried out in a microfluidic fuel cell, giving power densities of up to 14 mW cm -2 when using mass loads of only 0.1 mg on a 0.019 cm 2 electrode surface. The power densities of the aerogels obtained by microwave heating gave a performance superior to the resultant aerogel prepared using conventional heating and even better than a commercial Pd/C catalyst.

In this work, atomically substituted three-dimensionally ordered macroporous (3DOM) spinels based on Co and Mn (MnCo 2 O 4 and CoMn 2 O 4 ) were synthetized and used as cathodic electrocatalysts in a primary Zn-air battery. Scanning/transmission electron microscopy images show a 3DOM structure for both materials. Skeleton sizes of 114.4 and 140.8 nm and surface areas of 65.3 and 74.6 m 2 g -1 were found for MnCo 2 O 4 and CoMn 2 O 4 , respectively. The increase in surface area and higher presence of Mn 3+ and Mn 4+ species in the CoMn 2 O 4 3DOM material improved battery performance with a maximum power density of 101.6 mW cm -2 and a specific capacity of 1440 mA h g -1 , which shows the highest battery performance reported to date using similar spinel materials. The stability performance of the electrocatalyst was evaluated in half-cell and battery cell systems, showing the higher durability of CoMn 2 O 4 , which was related to its better capability to perform the electrocatalytic process as adsorption, electron transfer, and desorption. It was found through density functional theory calculations that the CoMn 2 O 4 spinel has a higher density of states in the Fermi level vicinity and better conductivity. Finally, the unique shape of 3DOM spinels promoted a high interaction between electroactive species and catalytic sites, making them suitable for oxygen reduction reaction applications.

The aim of this work is the evaluation of a Sulfonated Poly Ether-Ether Ketone (S-PEEK) polymer modified by the addition of pure Santa Barbara Amorphous-15 (SBA-15, mesoporous silica) and SBA-15 previously impregnated with phosphotungstic acid (PWA) fillers (PWA/SBA-15) in order to prepare composite membranes as an alternative to conventional Nafion ® membranes. This component is intended to be used as an electrolyte in electrochemical energy systems such as hydrogen and methanol Proton Exchange Membrane Fuel Cell (PEMFC) and Electrochemical Hydrogen Pumping (EHP). The common requirements for all the applications are high proton conductivity, thermomechanical stability, and fuel and oxidant impermeability. The morphology of the composite membranes was investigated by Scanning Electron Microscopy- Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis. Water Uptake (Wup), Ion Exchange Capacity (IEC), proton conductivity, methanol permeability and other physicochemical properties were evaluated. In PEMFC tests, the S-PEEK membrane with a 10 wt.% SBA-15 loading showed the highest performance. For EHP, the inclusion of inorganic materials led to a back-diffusion, limiting the compression capacity. Concerning methanol permeability, the lowest methanol crossover corresponded to the composites containing 5 wt.% and 10 wt.% SBA-15.

The demand for hydrophobic polymer-based protective coatings to impart high corrosion resistance has increased recently. The increase of the hydrophobicity in a hybrid coating is a new challenge, for that reason and in order to protect a metallic surface of oxidant agents, a poly (methyl methacrylate) (PMMA) coating with the addition of a different amount of silicon dioxide (SiO 2 ) was developed. The hybrid coating was applied on a sample of stainless steel AISI 304 by the dip-coating method. The characterization of the coatings was determined by electrochemical impedance spectroscopy and with a scanning electrochemical microscopy. The best coatings were PMMA and PMMA + SiO 2 0.01% that exhibits a real impedance in the Nyquist diagram of 760 and 427,800 MΩ⋅cm 2 , respectively, and the modulus of the real impedance in the Bode diagram present values of 2.2 × 10 8 and 3.3 × 10 8 Ω⋅cm 2 . Moreover, the phase angle presents constant values around 75° to 85° and 85° for the PMMA and PMMA + SiO 2 0.01%, respectively. Moreover, the values of the real resistance for the PMMA + SiO 2 0.01% coating present values in the order of Mega-ohms despite the coating exhibits an artificial defect in their surface. The contact angle test showed that the hydrophobicity of the hybrid PMMA + SiO 2 0.01% coating is higher than that of the pure PMMA coatings. The hybrid PMMA + SiO 2 coatings developed in this work are a very interesting and promising area of study in order to develop efficient products to protect metallic surfaces from corrosion phenomenon.

Titanium oxide nanotubes (TNTs) were anodically grown in ethylene glycol electrolyte. The influence of the anodization time on their physicochemical and photoelectrochemical properties was evaluated. Concomitant with the anodization time, the NT length, fluorine content, and capacitance of the space charge region increased, affecting the opto-electronic properties (bandgap, bathochromic shift, band-edge position) and surface hydrophilicity of TiO 2 NTs. These properties are at the origin of the photocatalytic activity (PCA), as proved with the photooxidation of methylene blue.

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 1.035V and power density of 3.154mWcm -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 0.93V of cell voltage and a power density close to 1.237mWcm -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 (0.716mWcm -2 ), demonstrating the feasibility of employing human blood as energy source., (Copyright © 2017 Elsevier B.V. All rights reserved.)