Nanoporous Cauliflower-like Pd-Loaded Functionalized Carbon Nanotubes as an Enzyme-Free Electrocatalyst for Glucose Sensing at Neutral pH: Mechanism Study.

In this work, we propose a novel functionalized carbon nanotube (f-CNT) supporting nanoporous cauliflower-like Pd nanostructures (PdNS) as an enzyme-free interface for glucose electrooxidation reaction (GOR) in a neutral medium (pH 7.4). The novelty resides in preparing the PdNS/f-CNT biomimetic nanocatalyst using a cost-effective and straightforward method, which consists of drop-casting well-dispersed f-CNTs over the Screen-printed carbon electrode (SPCE) surface, followed by the electrodeposition of PdNS. Several parameters affecting the morphology, structure, and catalytic properties toward the GOR of the PdNS catalyst, such as the PdCl2 precursor concentration and electrodeposition conditions, were investigated during this work. The electrochemical behavior of the PdNS/f-CNT/SPCE toward GOR was investigated through Cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), and amperometry. There was also a good correlation between the morphology, structure, and electrocatalytic activity of the PdNS electrocatalyst. Furthermore, the LSV response and potential-pH diagram for the palladium-water system have enabled the proposal for a mechanism of this GOR. The proposed mechanism would be beneficial, as the basis, to achieve the highest catalytic activity by selecting the suitable potential range. Under the optimal conditions, the PdNS/f-CNT/SPCE-based biomimetic sensor presented a wide linear range (1-41 mM) with a sensitivity of 9.3 µA cm-2 mM-1 and a detection limit of 95 µM (S/N = 3) toward glucose at a detection potential of +300 mV vs. a saturated calomel electrode. Furthermore, because of the fascinating features such as fast response, low cost, reusability, and poison-free characteristics, the as-proposed electrocatalyst could be of great interest in both detection systems (glucose sensors) and direct glucose fuel cells.

Effect of Contact Area and Shape of Anode Current Collectors on Bacterial Community Structure in Microbial Fuel Cells.

Low electrical conductivity of carbon materials is a source of potential loss for large carbonaceous electrode surfaces of MFCs due to the long distance traveled by electrons to the collector. In this paper, different configurations of titanium current collectors were used to connect large surfaces of carbon cloth anodes. The current collectors had different distances and contact areas to the anode. For the same anode surface (490 cm2), increasing the contact area from 28 cm2 to 70 cm2 enhanced power output from 58 mW·m-2 to 107 mW·m-2. For the same contact area (28 cm2), decreasing the maximal distance of current collectors to anodes from 16.5 cm to 7.75 cm slightly increased power output from 50 mW·m-2 to 58 mW·m-2. Molecular biology characterization (qPCR and 16S rRNA gene sequencing) of anodic bacterial communities indicated that the Geobacter number was not correlated with power. Moreover, Geobacter and Desulfuromonas abundance increased with the drop in potential on the anode and with the presence of fermentative microorganisms. Electrochemical impedance spectroscopy (EIS) showed that biofilm resistance decreased with the abundance of electroactive bacteria. All these results showed that the electrical gradient arising from collectors shapes microbial communities. Consequently, current collectors influence the performance of carbon-based anodes for full-scale MFC applications.

Galvano-Fenton Engineering Solution with Spontaneous Catalyst's Generation from Waste: Experimental Efficiency, Parametric Analysis and Modeling Interpretation Applied to a Clean Technology for Dyes Degradation in Water.

In this paper, the degradation of the diazo dye naphthol blue black (NBB) using the Galvano-Fenton process is studied experimentally and numerically. The simulations are carried out based on the anodic, cathodic, and 34 elementary reactions evolving in the electrolyte, in addition to the oxidative attack of NBB by HO• at a constant rate of 3.35×107 mol-1·m3·s-1 during the initiation stage of the chain reactions. The selection of the operating conditions including the pH of the electrolyte, the stirring speed, and the electrodes disposition is performed by assessing the kinetics of NBB degradation; these parameters are set to 3, 350 rpm and a parallel disposition with a 3 cm inter-electrode distance, respectively. The kinetics of Fe(III) in the electrolyte were monitored using the principles of Fricke dosimetry and simulated numerically. The model showed more than a 96% correlation with the experimental results in both the blank test and the presence of the dye. The effects of H2O2 and NBB concentrations on the degradation of the dye were examined jointly with the evolution of the simulated H2O2, Fe2+, and HO• concentrations in the electrolyte. The model demonstrated a good correlation with the experimental results in terms of the initial degradation rates, with correlation coefficients exceeding 98%.

A Novel Energy-from-Waste Approach for Electrical Energy Production by Galvano-Fenton Process.

A novel approach allowing the production of electrical energy by an advanced oxidation process is proposed to eliminate organic micropollutants (MPs) in wastewaters. This approach is based on associating the Galvano-Fenton process to the generation of electrical power. In the previous studies describing the Galvano-Fenton (GF) process, iron was directly coupled to a metal of more positive potential to ensure degradation of organic pollutants without any possibility of producing electrical energy. In this new approach, the Galvano-Fenton process is constructed as an electrochemical cell with an external circuit allowing recovering electrons exchanged during the process. In this study, Malachite Green (MG) dye was used as a model of organic pollutant. Simultaneous MG degradation and electrical energy production with the GF method were investigated in batch process. The investigation of various design parameters emphasis that utilization of copper as a low-cost cathode material in the galvanic couple, provides the best treatment and electrical production performances. Moreover, these performances are improved by increasing the surface area of the cathode. The present work reveals that the GF process has a potential to provide an electrical power density of about 200 W m-2. These interesting performances indicate that this novel Energy-from-Waste strategy of the GF process could serve as an ecological solution for wastewater treatment.

From bipolar to quadrupolar electrode structures: an application of bond-detach lithography for dielectrophoretic particle assembly.

We describe a new, simple process for fabricating transparent quadrupolar electrode arrays enabling large-scale particle assembly by means of dielectrophoresis. In the first step, interdigitated electrode arrays are made by chemical wet etching of indium tin oxide (ITO). Then, the transition from a bipolar to a quadrupolar electrode arrangement is obtained by covering the electrode surface with a thin poly(dimethylsiloxane) (PDMS) film acting as an electrical insulation layer in which selective openings are formed using bond-detach lithography. The PDMS insulating layer thickness was optimized and controlled by adjusting experimental parameters such as the PDMS viscosity (modulated by the addition of heptane) and the PDMS spin-coating velocity. The insulating character of the PDMS membrane was successfully demonstrated by performing a dielectrophoretic assembly of polystyrene particles using interdigitated electrodes with and without a PDMS layer. The results show that the patterned PDMS film functions properly as an electrical insulation layer and allows the reconfiguration of the electric field cartography. Electric field simulations were performed in both configurations to predict the dielectrophoretic behavior of the particles. The simulation results are in perfect agreement with experiments, in which we demonstrated the formation of concentrated clusters of polystyrene particles and living cells of regular size and shape.

Influence of Hydrodynamic Forces on Electroactive Bacterial Adhesion in Microbial Fuel Cell Anodes.

This investigation examined the role of shear stress on the dynamic development of microbial communities within anodic biofilms in single-chamber microbial fuel cells (MFCs). Bacterial attachment to surfaces, often regarded as a crucial step in biofilm formation, may significantly contribute to the selection of electroactive bacteria (EAB). It is well established that hydrodynamic forces, particularly shear forces, have a profound influence on bacterial adhesion. This study postulates that shear stress could select EAB on the anode during the adhesion phase by detaching non-EAB. To examine this hypothesis, MFC reactors equipped with a shear stress chamber were constructed, creating specific shear stress on the anode. The progression of adhesion under various shear stress conditions (1, 10, and 50 mPa) was compared with a control MFC lacking shear stress. The structure of the microbial community was assessed using 16S rRNA gene (rrs) sequencing, and the percentage of biofilm coverage was analyzed using fluorescence microscopy. The results indicate a significant impact of shear stress on the relative abundance of specific EAB, such as Geobacter, which was higher (up to 30%) under high shear stress than under low shear stress (1%). Furthermore, it was noted that shear stress decreased the percentage of biofilm coverage on the anodic surface, suggesting that the increase in the relative abundance of specific EAB occurs through the detachment of other bacteria. These results offer insights into bacterial competition during biofilm formation and propose that shear stress could be utilized to select specific EAB to enhance the electroactivity of anodic biofilms. However, additional investigations are warranted to further explore the effects of shear stress on mature biofilms.

Metaproteomic and Metagenomic-Coupled Approach to Investigate Microbial Response to Electrochemical Conditions in Microbial Fuel Cells.

MFCs represent a promising sustainable biotechnology that enables the direct conversion of organic matter from wastewater into electricity using bacterial biofilms as biocatalysts. A crucial aspect of MFCs is how electroactive bacteria (EAB) behave and their associated mechanisms during extracellular electron transfer to the anode. A critical phase in the MFC start-up process is the initial colonization of the anode by EAB. Two MFCs were operated with an external resistance of 1000 ohms, one with an applied electrical voltage of 500 mV during the initial four days of biofilm formation and the other without any additional applied voltage. After stabilization of electricity production, total DNA and protein were extracted and sequenced from both setups. The combined metaproteomic/metagenomic analysis revealed that the application of voltage during the colonization step predominantly increased direct electron transfer via cytochrome c, mediated primarily by Geobacter sp. Conversely, the absence of applied voltage during colonization resulted in a broader diversity of bacteria, including Pseudomonas and Aeromonas, which participated in electricity production via mediated electron transfer involving flavin family members.

Selective Sensing in Microbial Fuel Cell Biosensors: Insights from Toxicity-Adapted and Non-Adapted Biofilms for Pb(II) and Neomycin Sulfate Detection.

This study introduces the utilization of self-powered microbial fuel cell (MFC)-based biosensors for the detection of biotoxicity in wastewater. Current MFC-based biosensors lack specificity in distinguishing between different pollutants. To address this limitation, a novel approach is introduced, capitalizing on the adaptive capabilities of anodic biofilms. By acclimating these biofilms to specific pollutants, an enhancement in the selectivity of MFC biosensors is achieved. Notably, electrochemically active bacteria (EAB) were cultivated on 3D porous carbon felt with and without a model toxicant (target analyte), resulting in the development of toxicant-resistant anodic biofilms. The model toxicants, Pb2+ ions and the antibiotic neomycin sulfate (NS), were deployed at a concentration of 1 mg L-1 during MFC operation. The influence of toxicity on biofilm growth and power production was investigated through polarization and power density curves. Concurrently, the electrochemical activity of both non-adapted and toxicity-adapted biofilms was investigated using cyclic voltammetry. Upon maturation and attainment of peak powers, the MFC reactors were evaluated individually as self-powered biosensors for pollutant detection in fresh wastewater, employing the external resistor (ER) mode. The selected ER, corresponding to the maximum power output, was positioned between the cathode and anode of each MFC, enabling output signal tracking through a data logging system. Subsequent exposure of mature biofilm-based MFC biosensors to various concentrations of the targeted toxicants revealed that non-adapted mature biofilms generated similar current-time profiles for both toxicity models, whereas toxicity-adapted biofilms produced distinctive current-time profiles. Accordingly, these results suggested that merely by adapting the anodic biofilm to the targeted toxicity, distinct and identifiable current-time profiles can be created. Furthermore, these toxicity-adapted and non-adapted biofilms can be employed to selectively detect the pollutant via the differential measurement of electrical signals. This differentiation offers a promising avenue for selective pollutant detection. To the best of our current knowledge, this approach, which harnesses the natural adaptability of biofilms for enhanced sensor selectivity, represents a pioneering effort in the realm of MFC-based biosensing.

Untreated vs. Treated Carbon Felt Anodes: Impacts on Power Generation in Microbial Fuel Cells.

This research sought to enhance the efficiency and biocompatibility of anodes in bioelectrochemical systems (BESs) such as microbial fuel cells (MFCs), with an aim toward large-scale, real-world applications. The study focused on the effects of acid-heat treatment and chemical modification of three-dimensional porous pristine carbon felt (CF) on power generation. Different treatments were applied to the pristine CF, including coating with carbon nanofibers (CNFs) dispersed using dodecylbenzene sulfonate (SDBS) surfactant and biopolymer chitosan (CS). These processes were expected to improve the hydrophilicity, reduce the internal resistance, and increase the electrochemically active surface area of CF anodes. A high-resolution scanning electron microscopy (HR-SEM) analysis confirmed successful CNF coating. An electrochemical analysis showed improved conductivity and charge transfer toward [Fe(CN)6]3-/4- redox probe with treated anodes. When used in an air cathode single-chamber MFC system, the untreated CF facilitated quicker electroactive biofilm growth and reached a maximum power output density of 3.4 W m-2, with an open-circuit potential of 550 mV. Despite a reduction in charge transfer resistance (Rct) with the treated CF anodes, the power densities remained unchanged. These results suggest that untreated CF anodes could be most promising for enhancing power output in BESs, offering a cost-effective solution for large-scale MFC applications.

Cedar Wood-Based Biochar: Properties, Characterization, and Applications as Anodes in Microbial Fuel Cell.

In this study, the relationship between pyrolysis temperature of woody biomass and physicochemical properties of derived biochar was investigated for microbial fuel cell (MFC) application. Physical and chemical properties of biochar were characterized for different pyrolysis temperatures. Results showed that biochar obtained at 400 °C was not conductor, while biochars prepared at 600 °C, 700 °C, and 900 °C exhibited decreased electrical resistivity of (7 ± 6) × 103 Ω.m, (1.8 ± 0.2) Ω.m, and (16 ± 3) × 10-3 Ω.m, respectively. Rising pyrolysis temperature from 400 to 700 °C exhibited honeycomb-like macroporous structures of biochar with an increase in the specific surface area from 310 to 484 m2.g-1. However, the production of biochar at 900 °C reduced its specific surface area to 136 m2.g-1 and caused the loss of the ordered honeycomb structure. MFCs using anodes based on biochar prepared at 900 °C produced maximum power densities ((9.9 ± 0.6) mW.m-2) higher than that obtained with biochar pyrolyzed at 700 °C ((5.8 ± 0.1) mW.m-2) and with conventional carbon felt anodes ((1.9 ± 0.2) mW.m-2). SEM images of biochar-based anodes indicated the clogging of macropores in honeycomb structure of biochar prepared at 700 °C by growth of electroactive biofilms, which might impede the supply of substrate and the removal of metabolites from the inside of the electrode. These findings highlight that electrical conductivity of biochar is the major parameter for ensuring efficient anodes in microbial fuel cell application. Schematic representation of cedar wood-based biochar and its application as anode in MFC.

A membrane-less Glucose/O2 non-enzymatic fuel cell based on bimetallic Pd-Au nanostructure anode and air-breathing cathode: Towards micro-power applications at neutral pH.

Herein, the authors propose a miniaturized glucose/O2 n-EFC based on a new direct electron transfer. The anode is a screen-printed carbon electrode (SPCE) modified with functionalized carbon nanotubes (f-CNTs) and cauliflower-like PdAu nanostructures (PdAuNS). The PdAuNS/f-CNT biomimetic nanocatalyst was prepared using a cost-effective and straightforward method, which consisted of drop-casting well-dispersed f-CNTs over the SPCE surface before PdAuNS electrodeposition. This enzyme-free interface was used for glucose electrooxidation at neutral medium (pH 7.4). The electrochemical behaviour of the PdAuNS/f-CNT/SPCE was investigated using cyclic voltammetry, linear sweep voltammetry, and amperometry. Several parameters were optimized and discussed, including the metal precursor concentration (HAuCl4, PdCl2) and the electrodeposition conditions. The cathode for oxygen electroreduction is an air-cathode which is composed of Pt-coated carbon cloth. The electrochemical performances of the anode and the cathode were evaluated separately for glucose oxidation and oxygen reduction, respectively. Both electrodes were then assembled in a membrane-less single chamber n-EFC with an innovative architecture. Electrical characterization of the n-EFC supplied with a neutral buffered solution containing 20 mM glucose showed a maximal power output of 129 ± 11 µW cm-2, a current density of 600 ± 39 µA cm-2 with a cell voltage of 0.35 V, and an open circuit potential of 0.56 V. The proposed electrocatalyst possesses several advantages such as fast response, low cost, reusability, poison-free characteristics, and good stability. Hence, glucose/O2 n-EFC could be of great interest in direct glucose fuel cell applications (e.g., powering mountable/implantable biomedical micro-devices running at low electrical power supply) or in self-powered biosensing.

Carbon Nano-Fiber/PDMS Composite Used as Corrosion-Resistant Coating for Copper Anodes in Microbial Fuel Cells.

The development of high-performance anode materials is one of the greatest challenges for the practical implementation of Microbial Fuel Cell (MFC) technology. Copper (Cu) has a much higher electrical conductivity than carbon-based materials usually used as anodes in MFCs. However, it is an unsuitable anode material, in raw state, for MFC application due to its corrosion and its toxicity to microorganisms. In this paper, we report the development of a Cu anode material coated with a corrosion-resistant composite made of Polydimethylsiloxane (PDMS) doped with carbon nanofiber (CNF). The surface modification method was optimized for improving the interfacial electron transfer of Cu anodes for use in MFCs. Characterization of CNF-PDMS composites doped at different weight ratios demonstrated that the best electrical conductivity and electrochemical properties are obtained at 8% weight ratio of CNF/PDMS mixture. Electrochemical characterization showed that the corrosion rate of Cu electrode in acidified solution decreased from (17 ± 6) × 103 µm y-1 to 93 ± 23 µm y-1 after CNF-PDMS coating. The performance of Cu anodes coated with different layer thicknesses of CNF-PDMS (250 µm, 500 µm, and 1000 µm), was evaluated in MFC. The highest power density of 70 ± 8 mW m-2 obtained with 500 µm CNF-PDMS was about 8-times higher and more stable than that obtained through galvanic corrosion of unmodified Cu. Consequently, the followed process improves the performance of Cu anode for MFC applications.

Microbial fuel cell anodic microbial population dynamics during MFC start-up.

In order to optimize energy production in MFCs, a better understanding of anodic communities is essential. Our objective was to determine the taxonomic structure of the bacterial communities present at the surface of the anode during the formation and development of electro-active biofilms in MFCs inoculated with fresh primary clarifier overflow. Quantitative microbial community dynamics were evaluated as a function of time and electrical performance using 16S rRNA gene-based phylogenetic microarrays and flow cytometry. Results show that the bacterial community stabilized partially but not completely when voltage output was stable. Geobacter appeared to be the predominant genus, whose growth was associated with voltage, while some other genus still developed or declined after the voltage stabilization. Flow cytometry revealed that some genus showing a decreasing proportional fluorescence intensity over time were still actively respiring bacteria, and thus, active albeit minor members of the biofilm. Finally, this study shows that anodic biofilm selection and maturation is still occurring after more than 20 days of operation and over ten days after voltage is stabilized.

A new biotinylated tris bipyridinyl iron(II) complex as redox biotin-bridge for the construction of supramolecular biosensing architectures.

The bioaffine immobilization of several avidin layers on an electrode modified by a biotinylated polymer was accomplished by the first biotinylated redox bridge consisted of a tris(bipyridyl)iron(II) complex bearing six pre-oriented biotin groups.

Electrogeneration of a biotinylated poly(pyrrole-ruthenium(II)) film for the construction of photoelectrochemical immunosensor.

A biotinylated photosensitive polymer was electrogenerated from on a ruthenium complex bearing biotin and pyrrole groups; the resulting polypyrrolic film allowed the bioaffine immobilisation of avidin and biotinylated cholera toxin and the photoelectrochemical detection of the corresponding antibody.

Magnetic nanoparticle DNA labeling for individual bacterial cell detection and recovery.

A culture independent approach was developed for recovering individual bacterial cells out of communities from complex environments including soils and sediments where autofluorescent contaminants hinder the use of fluorescence based techniques. For that purpose fifty nanometer sized streptavidin-coated superparamagnetic nanoparticles were used to chemically bond biotin-functionalized plasmid DNA molecules. We show that micromagnets can efficiently trap magnetically labeled transformed Escherichia coli cells after these bacteria were subjected to electro-transformation by these nanoparticle-labeled plasmids. Among other applications, this method could extend the range of approaches developed to study DNA dissemination among environmental bacteria without requiring cultivability of recombinant strains or expression of heterologous genes in the new hosts.

Photoelectrochemical immunosensor for label-free detection and quantification of anti-cholera toxin antibody.

We demonstrate herein a newly developed photoelectrochemical immunosensor for the determination of anti-cholera toxin antibody by using a photosensitive biotinylated polypyrrole film. The latter was generated by electro-oxidation of a biotinylated tris(bipyridyl) ruthenium(II) complex bearing pyrrole groups. The photoexcitation of this modified electrode potentiostated at 0.5 V vs SCE, in the presence of an oxidative quencher, pentaaminechloro cobalt(III) chloride (15 mM), led to a cathodic photocurrent. As a result of the affinity interactions, a layer of biotinylated cholera toxin was firmly bound to the functionalized polypyrrole film via avidin bridges. The resulting modified electrodes were tested as immunosensors for the detection of the corresponding antibody from 0 to 200 microg mL(-)(1). The antibody concentration was measured through the decrease in photocurrent intensity resulting from its specific binding onto the polymeric coating, the detection limit being 0.5 microg mL(-)(1).

Electrogeneration of a poly(pyrrole)-NTA chelator film for a reversible oriented immobilization of histidine-tagged proteins.

This contribution reports, for the first time, the synthesis and electropolymerization of a pyrrole N-substituted by a nitrilotriacetic acid acting as a chelating center of Cu2+. A step-by-step approach for protein immobilization was developed via the successive coordination of Cu2+ and histidine-tagged proteins. The self-assembly of histidine-tagged glucose oxidase led to the formation of a close-packed enzyme monolayer at the poly(pyrrole) surface, and the reversibility and reproducibility of this affinity process were demonstrated.