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At least 775 records · Page 43

A facile one-step synthesis of Mn{sub 3}O{sub 4} nanoparticles-decorated TiO{sub 2} nanotube arrays as high performance electrode for supercapacitors

Via a facile one-step chemical bath deposition route, homogeneously dispersed Mn{sub 3}O{sub 4} nanoparticles have been successfully deposited onto the inner surface of TiO{sub 2} nanotube arrays (TNAs). The content and size of Mn{sub 3}O{sub 4} can be controlled by changing the deposition time. Field emission scanning electron microscopy and transmission electron microscopy analysis reveal the morphologies structures of Mn{sub 3}O{sub 4}/TNAs composites. The crystal-line structures are characterized by the X-ray diffraction patterns and Raman spectra. X-ray photoelectron spectroscopy further confirms the valence states of the sample elements. The electrochemical properties of Mn{sub 3}O{sub 4}/TNAs electrodes are systematically investigated by the combine use of cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. The resulting Mn{sub 3}O{sub 4}/TNAs electrode prepared by deposition time of 3 h shows the highest specific capacitance of 570 F g{sup −1} at a current density of 1 A g{sup −1}. And it also shows an excellent long-term cycling stability at a current density of 5 A g{sup −1}, which remaining 91.8% of the initial capacitance after 2000 cycles. Thus this kind of Mn{sub 3}O{sub 4} nanoparticles decorated TNAs may be considered as an alternative promising candidate for high performance supercapacitor electrodes. - Graphical abstract: Mn{sub 3}O{sub 4} nanoparticles have been uniformly deposited onto the inner surfaces of TiO{sub 2} nanotube arrays through a facile one-step chemical bath deposition method. As electrodes for supercapacitors, they exhibit a relatively high specific capacity and excellent cycling stability. - Highlights: • Mn{sub 3}O{sub 4} nanoparticles have been deposited onto TiO{sub 2} nanotube arrays by chemical bath deposition. • The Mn{sub 3}O{sub 4}/TNAs exhibits a highest specific capacitance of 570 F g{sup –1} at a current density of 1 A g{sup –1}. • The Mn{sub 3}O{sub 4}/TNAs electrode shows an excellent cycling stability of 91.8% after 2000 cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation of CuInS{sub 2}/TiO{sub 2} nanotube heterojunction arrays electrode and investigation of its photoelectrochemical properties

Graphical abstract: Schematic illustration of the synthesis steps of CuInS{sub 2}/TiO{sub 2} heterojunction arrays electrode. - Highlights: • CuInS{sub 2}/TiO{sub 2} nanotube heterojunction arrays electrode was successfully fabricated via a modified SILAR method. • Morphology, chemical compositions and the photoelectrochemical properties were studied. • The formed heterojunction structure is demonstrated as n–n type heterojunction. - Abstract: CuInS{sub 2}/TiO{sub 2} nanotube heterojunction arrays electrode was synthesized via a modified successive ionic layer adsorption and reaction (SILAR) method. The morphology, crystalline structure and chemical composition of the composite electrode were characterized with field-emission scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS), respectively. The optical properties were investigated by UV–vis diffusion reflection spectra (DRS) and photoluminescence (PL) spectra as well as the photoelectrochemical measurements. Significantly enhanced photoelectrochemical properties of CuInS{sub 2}/TiO{sub 2} NTs electrode were observed under visible light irradiation, which could be attributed to the high absorption coefficient of CuInS{sub 2} in visible region and the heterostructure formed between CuInS{sub 2} and TiO{sub 2}.

36 MATERIALS SCIENCE↗

A novel rapid synthesis of Fe{sub 2}O{sub 3}/graphene nanocomposite using ferrate(VI) and its application as a new kind of nanocomposite modified electrode as electrochemical sensor

Highlights: • A novel rapid synthesis of rGO–Fe{sub 2}O{sub 3} nanocomposite was developed using Fe(VI). • Fe(VI) as an environmentally friendly oxidant was introduced for GO synthesis. • Synthesized rGO–Fe{sub 2}O{sub 3} nanocomposite was applied as electrochemical sensor. • A non-enzymatic sensor was developed for H{sub 2}O{sub 2}. - Abstract: In this study, a novel, simple and sensitive non-enzymatic hydrogen peroxide electrochemical sensor was developed using reduced graphene oxide/Fe{sub 2}O{sub 3} nanocomposite modified glassy carbon electrode. This nanocomposite was synthesized by reaction of sodium ferrate with graphene in alkaline media. This reaction completed in 5 min and the products were stable and its deposition on the surface of electrode is investigated. It has been found the apparent charge transfer rate constant (ks) is 0.52 and transfer coefficient (α) is 0.61 for electron transfer between the modifier and glassy carbon electrode. Electrochemical behavior of this electrode and its ability to catalyze the electro-reduction of H{sub 2}O{sub 2} has been studied by cyclic voltammetry and chronoamperometry at different experimental conditions. The analytical parameters showed the good ability of electrode as a sensor for H{sub 2}O{sub 2} amperometric reduction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A reversible perovskite air electrode for active and durable oxygen reduction and evolution reactions via the A-site entropy engineering

The performance of reversible solid oxide electrochemical cells (R-SOECs) is largely hindered by the insufficient electroactivity and poor durability of the bifunctional air electrodes, where the oxygen reduction and evolution reactions (ORR and OER) occur. Here, we report our findings in boosting the electrochemical activity and durability of an air electrode with Pr 0.2 Ba 0.2 Sr 0.2 La 0.2 Ca 0.2 CoO 3-δ (PBSLCC) via an A-site entropy engineering. The PBSLCC electrode shows enhanced oxygen reaction activity and excellent durability compared to binary and ternary double perovskites (PrBaCo 2 O 5+δ and Pr 0.8 Ba 0.8 Ca 0.4 Co 2 O 5+δ , respectively). A low and nearly unchanged area-specific resistance of 0.042Ωcm 2 is achieved at 750 °C during the 225-h stability test. La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ electrolyte-supported cells with the PBSLCC air electrode show remarkable performance at 800 °C, demonstrating a peak power density of 1.2Wcm -2 in the fuel cell mode, and a current density of -1.1 Acm -2 at 1.3 V in the electrolysis mode while maintaining the excellent cycling durability of 228 h at ±0.5 Acm -2 under humidified H 2 (10% H 2 O). A bulk oxygen p-band center model is applied to verify that tailoring of the A-site entropy strongly influences the surface exchange coefficients (k* chem ), leading to higher oxygen reaction activity of PBSLCC than the binary and ternary perovskites. Finally, this study opens a new class of high-entropy perovskites for the rational design of air electrodes for R-SOECs with high activity and durability.

30 DIRECT ENERGY CONVERSION↗

Electrochemical Detection of Oxycodone and Its Main Metabolites with Nafion-Coated Single-Walled Carbon Nanotube Electrodes

Oxycodone is a strong opioid frequently used as an analgesic. Although proven efficacious in the management of moderate to severe acute pain and cancer pain, use of oxycodone imposes a risk of adverse effects such as addiction, overdose, and death. Fast and accurate determination of oxycodone blood concentration would enable personalized dosing and monitoring of the analgesic as well as quick diagnostics of possible overdose in emergency care. However, in addition to the parent drug, several metabolites are always present in the blood after a dose of oxycodone, and to date, there is no electrochemical data available on any of these metabolites. In this paper, a single-walled carbon nanotube (SWCNT) electrode and a Nafion-coated SWCNT electrode were used, for the first time, to study the electrochemical behavior of oxycodone and its two main metabolites, noroxycodone and oxymorphone. Both electrode types could selectively detect oxycodone in the presence of noroxycodone and oxymorphone. However, we have previously shown that addition of a Nafion coating on top of the SWCNT electrode is essential for direct measurements in complex biological matrices. Therefore, in this work, the Nafion/SWCNT electrode was further characterized and used for measuring clinically relevant concentrations of oxycodone in buffer solution. The limit of detection for oxycodone with the Nafion/SWCNT sensor was 85 nM, and the linear range was 0.5–10 μM in buffer solution. Furthermore, this study shows that the fabricated Nafion/SWCNT sensor has potential to be applied in clinical concentration measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Free-Standing Boron-Doped Diamond Grid Electrode for Fundamental Spectroelectrochemistry

Spectroelectrochemistry (SEC) is a powerful technique that enables a variety of redox properties to be studied, including formal potential (E o ), thermodynamic values (ΔG, ΔH, ΔS), diffusion coefficient (D), electron transfer stoichiometry (n), and others. SEC requires an electrode which light can pass through while maintaining sufficient electrical conductivity. This has been traditionally composed of metal or metal oxide films atop transparent substrates like glass, quartz, or metallic mesh. Robust electrode materials like boron-doped diamond (BDD) could help expand the environments in which SEC can be performed, but most designs are limited to thin films (~100–200 nm) on transparent substrates less resilient than free-standing BDD. Here, this work presents a free-standing BDD grid electrode (G-BDD) for fundamental SEC measurements, using the well-characterized Fe(CN) 6 3–/4– redox couple as proof-of-concept. With a combination of cyclic voltammetry (CV), thin-layer SEC, and chronoabsorptometry, several of the redox properties mentioned above were calculated and compared. For E o' , n, and D, similar results were obtained when comparing the CV [E o' = +0.279 (±0.002) V vs Ag/AgCl; n = 0.97; D = 4.1 × 10 –6 cm 2 ·s –1 ] and SEC [E o' = +0.278 (±0.001) V vs Ag/AgCl; n = 0.91; D = 5.2 × 10 –6 cm 2 ·s –1 ] techniques. Both values align with what has been previously reported. To calculate D from the SEC data, modification of the classical equation used in chronoabsorptometry was required to accommodate the G-BDD electrode geometry. Overall, this work expands on the applicability of SEC techniques and BDD as a versatile electrode material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gastight Hydrodynamic Electrochemistry: Design for a Hermetically Sealed Rotating Disk Electrode Cell

Rotating disk electrodes (RDEs) are widely used in electrochemical characterization to analyze the mechanisms of various electrocatalytic reactions. RDE experiments often make use of or require collection and quantification of gaseous products. The combination of rotating parts and gaseous analytes makes the design of RDE cells that allow for headspace analysis challenging due to gas leaks at the interface of the cell body and the rotator. In this manuscript we describe a new, hermetically sealed electrochemical cell that allows for electrode rotation while simultaneously providing a gastight environment. Electrode rotation in this new cell design is controlled by magnetically coupling the working electrode to a rotating magnetic driver. Calibration of the RDE using a tachometer shows that the rotation speed of the electrode is the same as that of the magnetic driver. To validate the performance of this cell for hydrodynamic measurements, limiting currents from the reduction of a potassium ferrocyanide (K 4 [Fe(CN) 6 ]·3H 2 O) were measured and shown to compare favorably with calculated values from the Levich equation and with data obtained using more typical, nongastight RDE cells. Faradaic efficiencies of ~95% were measured in the gas phase for oxygen evolution in alkaline media at an Inconel 625 alloy electrocatalyst during rotation at 1600 rpm. These data verify that a gastight environment is maintained even during rotation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Functionalization of Electrodes with Tunable [EMIM] x [Cl] x +1 – Ionic Liquid Clusters for Electrochemical Separations

Functionalization of electrodes with clusters of hydrophobic molecules may improve the energy efficiency and selectivity of electrochemical separations by modulating the desolvation process occurring at the interface. Ionic liquids (IL), which have a broad range of compositions and properties, are potential candidates for controlling the transport, desolvation, and adsorption of target ions at electrochemical interfaces. We report a joint experimental and theoretical investigation of the structure, stability, and selective adsorption properties of the IL clusters 1-ethyl-3-methylimidazolium chloride [EMIM] x [Cl] x+1 - (x = 1 – 10) and demonstrate their ability to adsorb and separate ions from solution. The structure and stability of the IL clusters are determined experimentally using high-mass-resolution electrospray ionization mass spectrometry, collision-induced dissociation, and negative ion photoelectron spectroscopy. Global optimization theory and ab initio molecular dynamics simulations provide molecular-level insight into the bonding and structural fluxionality of these species. Ion soft landing is used to selectively functionalize the surface of highly oriented pyrolytic graphite (HOPG) working electrodes with [EMIM] 1 [Cl] 2 - , [EMIM] 3 [Cl] 4 - , and [EMIM] 5 [Cl] 6 - clusters. Kelvin probe microscopy provides insight into the relative stability of the clusters on HOPG and their effect on the work function of IL-functionalized electrodes. Cyclic voltammetry measurements reveal irreversible adsorption of Fe(CN) 6 4-/3- anions during redox cycling, while electrochemical impedance spectroscopy indicates a substantial decrease in the electron transfer resistance of the IL-functionalized electrodes due to adsorption of Fe(CN) 6 4-/3- . Overall, our findings demonstrate that IL clusters with different size and stoichiometry may be used to increase the efficiency of electrochemical separations, opening new horizons in selective electrode functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Continuum Modeling of Porous Electrodes for Electrochemical Synthesis

Electrochemical synthesis possesses substantial promise to utilize renewable energy sources to power the conversion of abundant feedstocks to value-added commodity chemicals and fuels. Of the potential system architectures for these processes, only systems employing 3-D structured porous electrodes have the capacity to achieve the high rates of conversion necessary for industrial scale. However, the phenomena and environments in these systems are not well understood and are challenging to probe experimentally. Fortunately, continuum modeling is well-suited to rationalize the observed behavior in electrochemical synthesis, as well as to ultimately provide recommendations for guiding the design of next-generation devices and components. In this review, we begin by presenting an historical review of modeling of porous electrode systems, with the aim of showing how past knowledge of macroscale modeling can contribute to the rising challenge of electrochemical synthesis. We then present a detailed overview of the governing physics and assumptions required to simulate porous electrode systems for electrochemical synthesis. Here, leveraging the developed understanding of porous-electrode theory, we survey and discuss the present literature reports on simulating multiscale phenomena in porous electrodes in order to demonstrate their relevance to understanding and improving the performance of devices for electrochemical synthesis. Lastly, we provide our perspectives regarding future directions in the development of models that can most accurately describe and predict the performance of such devices and discuss the best potential applications of future models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Particle Mixing and Gravitational Settling on Charge Transport in Carbon Flow-Electrode Cells

Flowable carbon slurries are actively studied and under development for charge transport in various electrochemical systems including flow capacitors, capacitive deionization cells, semi-solid flow batteries, and lithium extraction. However, much less is known about in operando slurry flow dynamics and their corresponding effect on charge transport. We performed an experimental study of mixing and settling dynamics of slurry electrodes within an electrochemical flow cell during continuous operations. The electrochemical cell consisted of two horizontal co-flowing channels, separated by a cation-exchange membrane (CEM). Here we used high-speed optical imaging of planes parallel to gravity and simultaneous electrochemical measurements. At low flow rates, dense yet dynamic particle beds formed on the bottom electrode in each channel, which unexpectedly yielded the highest currents. This approach enables the operation of the flow cell at low system-average particle concentrations while leveraging gravity-driven particle settling to locally enhance carbon concentrations precisely at the current collector sites. Conversely, high flow rates were characterized by thin particle beds and well-mixed particle flows. In the latter case, the electrodes in closest proximity (located on either side of the CEM) achieved a current higher than the other electrode pairs. The observations have implications for slurry control and electrode designs in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Hybrid Quantum–Classical Study of Ion Adsorption at the Copper Electrode

Here, we present a set of computational studies that surveys the molecular structure and thermodynamics of simple ions at the electrode–electrolyte interface. A hybrid quantum–classical approach is used to obtain free energy profiles and solvent structure as a function of the ion’s position relative to the electrochemical liquid/solid interface and system potential. Model systems consist of a copper electrode and single halide or alkali metal ion in contact with an implicit solvent and reveal new insights into the interplay of forces that drive or resist ion absorption at the electrode/ electrolyte interface. We also expand on subtleties of absorption site preference and describe the complex relationship between the energetic barrier to absorption and the ion–electrode binding energy as a function of electrode potential.

36 MATERIALS SCIENCE↗

Predicting the Pseudocapacitive Windows for MXene Electrodes with Voltage-Dependent Cluster Expansion Models

MXene transition-metal carbides and nitrides are of growing interest for energy storage applications. These compounds are especially promising for use as pseudocapacitive electrodes due to their ability to convert energy electrochemically at fast rates. Using voltage-dependent cluster expansion models, we predict the charge storage performance of MXene pseudocapacitors for a range of electrode compositions. M 3 C 2 O 2 electrodes based on group-VI transition metals have up to 80% larger areal energy densities than prototypical titanium-based (e.g., Ti 3 C 2 O 2 ) MXene electrodes. We attribute this high pseudocapacitance to the Faradaic voltage windows of group-VI MXene electrodes, which are predicted to be 1.2 to 1.8 times larger than those of titanium-based MXenes. The size of the pseudocapacitive voltage window increases with the range of oxidation states that are accessible to the MXene transition metals. Here, by similar mechanisms, the presence of multiple ions in the solvent (Li + and H + ) leads to sharp changes in the transition-metal oxidation states and can significantly increase the charge capacity of MXene pseudocapacitors.

36 MATERIALS SCIENCE↗

Multiscale Characterization of Electrode-Induced Degradation in Perovskite Solar Cells

The stability of metal-halide-perovskite (MHP) solar cells must be understood and improved for the commercial viability of MHP technologies. Here, we apply multiscale characterization methods to study degradation modes, specifically electrode corrosion, for p-i-n MHP partial device stacks and full devices that are stored in the dark under an inert atmosphere. Our multiscale characterization approaches include full-device electro-optical performance using current-voltage (JV) curves and spatial imaging with electroluminescence (EL) and photoluminescence (PL). We further correlate interface properties using cross-sectional Kelvin probe force microscopy, which maps the nanoscale electric field properties, and electron microscopy, which demonstrates structural and chemical features. Devices stored as a full device stack degrade primarily by metal (Ag) electrode diffusion into the absorber, with formation of AgI byproducts and Ag accumulation near the indium tin oxide (ITO) contact. This causes decomposition of the perovskite absorber domains, loss of the potential drop at the electron transport layer (ETL)/perovskite interface near the metal contact, and increased equivalent resistance at the perovskite/hole transport layer (HTL) interface near the ITO contact. The devices stored without metal show a different degradation pathway dominated by corrosion of the ITO, creating voids at the ITO electrode surface with diffusion of In and Sn into the absorber. We conclude that metal electrode-induced degradation is the most severe degradation pathway under dark storage, but that ITO corrosion and absorber instability must also be mitigated. We further demonstrate mitigation of these degradation pathways by changes to the device stack, including a SnO x blocking layer at the ETL side and replacing ITO with FTO at the HTL side. These results provide a useful demonstration of specific dark degradation pathways at each electrode interface, as well as a unique multiscale example that links degradation of chemical, structural, and electrical interface properties to the full-device electro-optical characteristics.

14 SOLAR ENERGY↗

Accurate Prediction of Voltage of Battery Electrode Materials Using Attention-Based Graph Neural Networks

Performing first-principles calculations to discover electrodes’ properties in the large chemical space is a challenging task. While machine learning (ML) has been applied to effectively accelerate those discoveries, most of the applied methods ignore the materials’ spatial information and only use predefined features: based only on chemical compositions. Here, we propose two attention-based graph convolutional neural network techniques to learn the average voltage of electrodes. Our proposed methods, which combine both atomic composition and atomic coordinates in 3D-space, improve the accuracy in voltage prediction significantly when compared to composition-based ML models. The first model directly learns the chemical reaction of electrodes and metal ions to predict their average voltage, whereas the second model combines electrodes’ ML predicted formation energy (E form ) to compute their average voltage. Our E form -based model demonstrates improved accuracy in transferability from our subset of learned Li ions to Na ions. Moreover, we predicted the theoretical voltage of 10 Na x MPO 4 F (M = Ti, Cr, Fe, Cu, Mn, Co, and Ni) fluorophosphate battery frameworks, which are unavailable in the Material Project database. It could be shown that we can expect average voltages higher than 3.1 V from those Na battery frameworks except from the NaTiPO 4 F and TiPO 4 F pair of electrodes, which offer an average voltage of 1.32 V.

25 ENERGY STORAGE↗

Kinetic Analysis of Proton-Coupled Electron Transfer at an Electrode-Immobilized Complex

An alkyne-terminated cobalt complex, [Co(Cp)(dppe ≡H )(Cl)] + (Cp = cyclopentadienyl; dppe ≡H = 1,2-bis-(di-(4-ethynyl-phenyl)phosphino)ethane), (Co ≡H ) was immobilized onto a glassy carbon electrode using two attachment strategies: Cu(I) catalyzed azide–alkyne click chemistry and reductive electropolymerization. The modified electrodes prepared through reductive electropolymerization exhibit current densities and peak resolutions for the electrochemical reduction of the cobalt species, which are amenable to electroanalytical quantification of coupled chemical reactions. Through peak shift analysis of cyclic voltammograms recorded in the presence of 4-chloroanilinium tetrafluoroborate, we quantified the proton transfer rate constant for the stepwise proton-coupled electron transfer reaction that reduces the electrode-immobilized [Co(Cp)(dppe ≡H )(Cl)] + to [H–Co(Cp)(dppe ≡H )] + (k PT app = (9.3 ± 1.8) × 10 5 M –1 s –1 ). In conclusion, the extraction of kinetic parameters for an elementary proton-coupled electron transfer reaction of an electrode-immobilized complex represents the first experimental measurement of its type and lays crucial groundwork for kinetic analyses of hybrid catalyst–electrode architectures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-Tortuosity Thick Electrodes with Active Materials Gradient Design for Enhanced Energy Storage

The ever-growing energy demand of modern society calls for the development of high-loading and high-energy-density batteries, and substantial research efforts are required to optimize electrode microstructures for improved energy storage. Low-tortuosity architecture proves effective in promoting charge transport kinetics in thick electrodes; however, heterogeneous electrochemical mass transport along the depth direction is inevitable, especially at high C-rates. In this work, we create an active material gradient in low-tortuosity electrodes along ion-transport direction to compensate for uneven reaction kinetics and the nonuniform lithiation/delithiation process in thick electrodes. The gradual decrease of active material concentration from the separator to the current collector reduces the integrated ion diffusion distance and accelerates the electrochemical reaction kinetics, leading to improved rate capabilities. Further, the structure advantages combining low-tortuosity pores and active material gradient offer high mass loading (60 mg cm –2 ) and enhanced performance. Comprehensive understanding of the effect of active material gradient architecture on electrode kinetics has been elucidated by electrochemical characterization and simulations, which can be useful for development of batteries with high-energy/power densities.

25 ENERGY STORAGE↗

Geobacter sulfurreducens Immobilized Boron-Doped Diamond Electrodes for Uranium(VI) in Water Electrochemical Bioremediation

The proliferation of nuclear science and technology has resulted in an increase in nuclear waste containing uranium, posing significant risks to both human and environmental health. This study proposes the use of Geobacter sulfurreducens (G. sulfurreducens) modified boron-doped diamond electrodes to facilitate the reduction and removal of uranium(VI) from aqueous media. The bioremediation process involves electrochemically immobilizing the bacteria on a boron-doped diamond electrode (BDD). The immobilization process requires applying reduction potentials ranging from −0.40 to −0.70 V (vs Ag/AgCl (3 M NaCl)), with −0.60 V identified as the optimal potential for effective bacterial modification. The uranium source is provided by a 2.0 mM uranyl acetate solution in G. sulfurreducens growth medium. Scanning electron microscopy (SEM) reveals a highly uniform layer of uranium on the electrode surface. Energy-dispersive X-ray fluorescence spectroscopy (EDS) and cyclic voltammetry (CV) studies confirm the presence of uranium in the system. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) successfully elucidate the reduction process of U(VI) to predominantly U(IV) using a bacteria-electrode coupled system. Additionally, a comparison is made with the electrochemical removal of uranyl ions using the electrodeposition method on unmodified BDD. Results demonstrate the presence of three uranium oxide species (UO 2 , UO 3 , and U 3 O 8 ) on the BDD electrode after experimentation, in contrast to the G. sulfurreducens/BDD assembly, which achieves the predominant reduction of UO 2 2+ to UO 2 with a small quantity of UO 3 as the final species. This study highlights the efficient electrochemical removal of uranyl ions from aqueous media at the G. sulfurreducens/BDD interface through chronoamperometry, presenting a promising approach for remediating sites contaminated with radioactive materials. The findings contribute to the exploration of sustainable alternatives for managing nuclear waste, emphasizing the potential of this electrochemical bioremediation strategy.

Bacteria↗

Charge-Free Mixing Entropy Battery Enabled by Low-Cost Electrode Materials

Salinity gradients are a vast and untapped energy resource. For every cubic meter of freshwater that mixes with seawater, approximately 0.65 kW h of theoretically recoverable energy is lost. For coastal wastewater treatment plants that discharge to the ocean, this energy, if recovered, could power the plant. The mixing entropy battery (MEB) uses battery electrodes to convert salinity gradient energy into electricity in a four-step process: (1) freshwater exchange; (2) charging in freshwater; (3) seawater exchange; and (4) discharging in seawater. Previously, we demonstrated a proof of concept, but with electrode materials that required an energy investment during the charging step. Here, we introduce a charge-free MEB with low-cost electrodes: Prussian Blue (PB) and polypyrrole (PPy). Importantly, this MEB requires no energy investment, and the electrode materials are stable with repeated cycling. The MEB equipped with PB and PPy achieved high voltage ratios (actual voltages obtained divided by the theoretical voltages) of 89.5% in wastewater effluent and 97.6% in seawater, with over 93% capacity retention after 50 cycles of operation and 97–99% over 150 cycles with a polyvinyl alcohol/sulfosuccinic acid (PVA/SSA) coating on the PB electrode.

25 ENERGY STORAGE↗