Search Results (977)

This work introduces a novel approach to enhancing the performance of zinc anodes in zinc–air batteries through a photopolymerizable organic–inorganic hybrid coating. Electrochemical tests were conducted in a neutral NaCl electrolyte, selected to minimize electrolyte carbonation, anode corrosion, and zinc dendrite formation. The behavior of bare and coated zinc electrodes was investigated using linear sweep voltammetry, electrochemical impedance spectroscopy (EIS), potentiostatic measurements, galvanostatic discharge tests, and charge-discharge tests, while morphological and structural characterizations were carried out by Atomic Force Microscopy (AFM), Raman spectroscopy, and X-ray Diffraction (XRD). The results confirmed that the hybrid coating acts as a corrosion-resistant barrier, enhancing the reversibility and stability of zinc electrodes through a barrier mechanism. Charge–discharge tests further confirmed the improved performance of the coated electrode, obtaining at a current density of 1 mA/cm², a coulombic efficiency of 92.61% and a capacity retention of 90.18%, respectively, after 16 cycles. These findings highlight the effectiveness of the photopolymerizable hybrid coating in improving the durability and rechargeability of zinc–air batteries. Full article

This paper presents a novel batch Forward Osmosis (FO) process for hydropower generation. It focuses on analyzing the parameters needed to make the proposed osmotic power plant implementable with currently available technology. Starting from the solution–diffusion model and using flow and mass balance equations, the equations that describe the behavior of the system over time are obtained. Membrane orientation, concentration polarization, reverse solute flux, and membrane fouling are not considered. The equations for calculating the operation time for the charging and discharging stages are obtained. Also, an equation for calculating the required membrane area to make the duration of the two stages the same is obtained. The results indicate that a volume of approximately $30.4 {\mathrm{m}}^3$ discharging through a $0.84 \mathrm{i}\mathrm{n}\mathrm{c}\mathrm{h}$ diameter outflow jet towards a turbine could generate an energy of $25 \mathrm{k}\mathrm{w}·\mathrm{h}.$ The discharging stage would take $12 \mathrm{h}$, and with a membrane with a water permeability constant $A_m=1.763·{10}^{-12} \mathrm{m}/(\mathrm{s}·\mathrm{P}\mathrm{a})$, the charging stage would require a membrane superficial area ${Ar}_m=1·{10}^4 {\mathrm{m}}^2$ to have the same duration. The proposed osmotic power plant, whose working principle is based on volume change over time, contrary to pressure retarded osmosis, whose working principle requires expending energy to extract energy from the salinity gradient, could deliver greater net produced energy with comparatively lower operational costs as it does not require high-pressure pumps or energy recovery devices as are required in pressure-retarded osmosis. The use of several tanks that charge and discharge alternatively can make the system generate energy as if it were a continuous process. Full article

The replacement of polyvinylidene fluoride (PVDF) with environmentally friendly binders offers potential advantages in the development of aqueous lithium-ion batteries (ALIBs) and flow batteries (FBs) incorporating solid charge carriers (so-called solid boosters). This study investigates the electrochemical stability of ethyl cellulose and cross-linked gluten as substitutes for PVDF in LiMn₂O₄ (LMO) cathodes for aqueous Li-ion battery electrodes and solid boosters for FBs. The millimetre-scaled solid booster beads must be easily produced on a large scale, and at the same time, their charging and discharging must be reversible over long durations under electrolyte tank conditions. The binders were tested under standardized conditions for discharge capacity and cycling stability. Our results demonstrate that ethyl cellulose and cross-linked gluten can rival the electrochemical stability of PVDF, maintaining initial discharge capacities near 100 mAh g⁻¹ at 0.2 C for LMO cathodes and exhibiting reasonable capacity retention over hundreds of cycles. This work supports the feasibility of sustainable electrode processing, provides promising directions for scalable, eco-friendly electrode fabrication methods, and highlights promising binder candidates for use in aqueous energy storage systems. Full article

Viologens are promising candidates for next-generation electrochromic devices due to their reversible color changes, low operating voltages, and structural tunability. However, their practical performance is often constrained by limited color range, stability issues, and poor charge delocalization. In this study, we present a detailed density functional theory (DFT) and time-dependent DFT (TD-DFT) investigation of asymmetric viologens based on the Benzyl-4,4′-dipyridyl-R (BnV-R) framework. A series of electron-donating and electron-withdrawing substituents (CN, COOH, PO₃H₂, CH₃, OH, NH₂) were introduced via either benzyl or phenyl linkers. Geometry optimizations for neutral, radical cationic, and dicationic states were performed at the CAM-B3LYP/6-31+G(d,p) level with C-PCM solvent modeling. Electronic structure, frontier orbital distributions, and redox potentials were correlated with substituent type and linkage mode. Natural Bond Orbital analysis showed that electron-withdrawing groups stabilize reduced states, while electron-donating groups enhance intramolecular charge transfer and switching kinetics. TD-DFT calculations revealed significant bathochromic and hyperchromic shifts dependent on substitution patterns, with phenyl linkers promoting extended conjugation and benzyl spacers minimizing aggregation. Radical cation stability, quantified via ΔE_red and comproportionation constants, highlighted cyano- and amine-substituted systems as particularly promising. These insights provide predictive design guidelines for tuning optical contrast, coloration efficiency, and electrochemical durability in advanced electrochromic applications. Full article

The narrow operating temperature window of commercial V-W/TiO₂ catalysts severely limits NO_x removal efficiency, especially during low-load boiler operations. To achieve broad-temperature NO_x abatement, we developed Ce-M/Ti (M = Co, Fe, Mn, Mo) catalysts via a dual-site strategy. The temperatures required for 80% NO conversion (T₈₀) were 302 °C for Ce-Mo/Ti, 372 °C for Ce-Fe/Ti, 393 °C for Ce-Mn/Ti, and 415 °C for Ce-Co/Ti. Among them, Ce-Mo/Ti exhibited the most favorable low-temperature activity, outperforming a commercial catalyst (324 °C). Its turnover frequency (3.12 × 10⁻³ s⁻¹) was 1.29 times higher. Combined physicochemical characterization and density functional theory (DFT) calculations further reveal the mechanism behind the enhanced dual-site synergy in Ce-Mo/Ti. In the Ce-Co, Ce-Fe, and Ce-Mn sites, weak orbital hybridization leads to limited charge transfer. In contrast, Ce-Mo/Ti exhibits stronger hybridization between the Ce 4f/5d and Mo 4d orbitals, which breaks the inherent limitation of the Ce-based (Ce³⁺/Ce⁴⁺) redox capability and enables reverse electron transfer from Mo to Ce. This distinctive electron transfer direction creates a unique electronic environment, activating an efficient redox cycle between Mo⁶⁺/Mo⁵⁺ and Ce⁴⁺/Ce³⁺. This work offers a promising design strategy for dual-site catalysts with high NO_x removal efficiency over a wide temperature range. Full article

Cellulose, the most abundant polysaccharide on earth, possesses desirable properties such as biodegradability, low cost, and low toxicity, making it suitable for a wide range of applications. Being a non-conductive material, the structure of the nanocellulose can be modified or incorporated with conductive filler to facilitate charge transport between the polymer matrix and conductive components. Recently, cellulose-based ion exchange membranes (IEMs) have gained strong attention as alternatives to environmentally burdening synthetic polymers in electrochemical energy systems, owing to their renewable nature and versatile chemical structure. This article provides a comprehensive review of the structures, fabrication aspects and properties of various cellulose-based membranes for fuel cells and water electrolyzers, batteries, supercapacitors, and reverse electrodialysis (RED) applications. The scope includes an overview of various cellulose-based membrane fabrication methods, different forms of cellulose, and their applications in energy conversion and energy storage systems. The review also discusses the fundamentals of electrochemical energy systems, the role of IEMs, and recent advancements in the cellulose-based membranes’ research and development. Finally, it highlights current challenges to their performance and sustainability, along with recommendations for future research directions. Full article

Adenosine triphosphate (ATP) varies from nanomolar to millimolar levels across the physiological landscapes in which it serves as an energy carrier, phosphate donor, and purinergic signaling molecule. To measure these vastly different concentrations, genetically encoded sensors with different affinities are needed to match the particular ATP range and application. To this end, we mutagenized two key arginine residues in the ATP-binding domain of the ATeam family of sensors to explore how charge neutralization and charge reversal affect ATP affinity. As a result, we generated an extended family of affinity mutants with apparent dissociation constants ranging from sub-micromolar to millimolar. We then carried out live-cell imaging to demonstrate the utility of different affinity mutants in detecting mild versus extreme metabolic inhibition. Overall, these sensors add to the toolbox for understanding ATP dynamics in and around cells. Full article

Alkaptonuria (AKU) is a rare metabolic disorder caused by homogentisate 1,2-dioxygenase (HGD) deficiency, leading to homogentisic acid (HGA) accumulation and ochronotic pigment deposition, which drug therapy cannot reverse. The process of pigment formation and deposition is still unclear. This study offers molecular insights into the polymeric structure, with the goal of developing future adjuvant strategies that can inhibit or reverse pigment formation, thereby complementing drug therapy in AKU. HGA polymerisation was examined under physiological, acidic, and alkaline conditions using liquid and solid phase nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and polyacrylamide gel electrophoresis. At physiological pH, HGA polymerised slowly, while alkaline catalysis accelerated pigment formation while retaining the HGA aromatic scaffold. During the process, EPR detected a semiquinone radical intermediate, consistent with an oxidative coupling mechanism. Reactivity profiling showed the diphenol ring was essential for polymerisation, while –CH₂COOH modifications did not impair reactivity. Pigments displayed a polydisperse molecular weight range (11–50 kDa) and a strong negative charge. Solid-state NMR has revealed the presence of phenolic ether and biphenyl linkages. Collectively, these identified structural motifs can serve as a foundation for future molecular targeting related to pigment formation. Full article

Thick active layers are crucial for scalable production of organic photodetectors (OPDs). However, most OPDs with active layers thicker than 200 nm typically exhibit decreased photocurrents and responsivities due to exciton diffusion and prolonged charge transport pathways. To address these limitations, we designed and synthesized PFBDT-8ttTPD, a fluorinated polymer donor. The strategic incorporation of fluorine effectively enhanced the charge carrier mobility, enabling more efficient charge transport, even in thicker films. OPDs combining PFBDT−8ttTPD with IT−4F or Y6 non-fullerene acceptors showed a substantially lower dark current density (J_d) for active layer thicknesses of 250−450 nm. Notably, J_d in the IT-4F-based devices declined from 8.74 × 10⁻⁹ to 4.08 × 10⁻¹⁰ A cm⁻² under a reverse bias of −2 V, resulting in a maximum specific detectivity of 3.78 × 10¹³ Jones. Meanwhile, Y6 integration provided near-infrared sensitivity, with the devices achieving responsivity above 0.48 A W⁻¹ at 850 nm and detectivity over 10¹³ Jones up to 900 nm, supporting broadband imaging. Importantly, high-quality thick films (≥400 nm) free of pinholes or defects were fabricated, enabling scalable production without performance loss. This advancement ensures robust photodetection in thick uniform layers and marks a significant step toward the development of industrially viable OPDs. Full article

The global transition toward renewable energy sources has intensified in response to escalating environmental challenges. Nevertheless, the inherent intermittency and instability of renewable energy necessitate the development of reliable energy storage technologies. Supercapacitors are particularly notable for their high specific capacitance, rapid charge and discharge capability, and exceptional cycling stability. Concurrently, the increasing demand for efficient and sustainable energy storage systems has stimulated interest in multifunctional electrode materials that integrate electrocatalytic activity with electrochemical energy storage. Two-dimensional transition metal dichalcogenides (TMDs), owing to their distinctive layered structures, large surface areas, phase state, energy band structure, and intrinsic electrocatalytic properties, have emerged as promising candidates to achieve dual functionality in electrocatalysis and electrochemical energy storage for asymmetric supercapacitors (ASCs). Specifically, their unique electronic properties and catalytic characteristics promote reversible Faradaic reactions and accelerate charge transfer kinetics, thus markedly enhancing charge storage efficiency and energy density. This review highlights recent advances in TMD-based multifunctional electrodes. It elucidates mechanistic correlations between intrinsic electronic properties and electrocatalytic reactions that influence charge storage processes, guiding the rational design of high-performance ASC systems. Full article

We report combined scanning probe microscopy and electrical measurements to investigate local electronic transport in reduced graphene oxide (rGO) devices. We demonstrate that quantum transport in these materials can be significantly tuned by the electrostatic potential applied with a conducting atomic force microscope (AFM) tip. Scanning gate microscopy (SGM) reveals a clear p-type response in which local gating modulates the source–drain current, while scanning impedance microscopy (SIM) indicates corresponding shifts of the Fermi level under different gating conditions. The observed transport behavior arises from the combined effects of AFM tip-induced Fermi-level shifts and defect-mediated scattering. These results show that resonant scattering associated with impurities or structural defects plays a central role and highlight the strong influence of local electrostatic potentials on rGO conduction. Consistent with this electrostatic control, the device also exhibits chemical gating and sensing: during exposure to electron-withdrawing molecules (acetone), the source–drain current increases reversibly and returns to baseline upon purging with air. Repeated cycles over 15 min show reproducible amplitudes and recovery. Using a simple transport model, we estimate an increase of about $40\%$ in carrier density during exposure, consistent with p-type doping by electron-accepting analytes. These findings link nanoscale electrostatic control to macroscopic sensing performance, advancing the understanding of charge transport in rGO and underscoring its promise for nanoscale electronics, flexible chemical sensors, and tunable optoelectronic devices. Full article

The vibration properties of materials play a role in their conduction of electric charges. Ionic conductors such as electrodes and solid electrolytes are also relevant in this respect. The vibration properties are typically assessed with infrared and Raman spectroscopy, and inelastic neutron scattering, which all allow for the derivation of the phonon density of states (PDOS) in part of a full portion of the Brioullin zone. Nuclear resonant vibration spectroscopy (NRVS) is a novel method that produces the element-specific PDOS from Mössbauer-active isotopes in a compound. We employed NRVS operando on a pouch cell battery containing a Li⁵⁷FePO₄ electrode, and thus could derive the PDOS of the ⁵⁷Fe in the electrode during charging and discharging. The spectra reveal reversible vibrational changes associated with the two-phase conversion between LiFePO₄ and FePO₄, as well as signatures of metastable intermediate states. We demonstrate how the NRVS data can be used to tune the atomistic simulations to accurately reconstruct the full vibration structures of the battery materials in operando conditions. Unlike optical techniques, NRVS provides bulk-sensitive, element-specific access to the full phonon spectrum under realistic operando conditions. These results establish NRVS as a powerful method to probe lattice dynamics in working batteries and to advance the understanding of ion transport and phase transformation mechanisms in electrode materials. Full article

Given the pivotal role of coumarins as tunable nonlinear optical (NLO) materials for advanced photonics, this study aims to decipher the regulatory mechanisms governing their excited-state dynamics and nonlinear absorption. In this study, two amino-coumarin dyes (102 and 153) differing in electron-withdrawing groups are synthesized to probe the impact of intramolecular charge transfer (ICT) on transient dynamics and nonlinear absorption. Frontier orbital and natural transition orbital analyses reveal subtle alterations in the ICT characteristics of amino-coumarin molecules. These minor modifications induce a significant red shift in the stimulated emission band within transient absorption spectroscopy, ultimately triggering a transition from reverse saturable absorption (RSA) to saturable absorption (SA) at 515 nm. Our findings demonstrate that, with straightforward molecular modifications, coumarins emerge as promising dual-function materials for saturable absorption and optical limiting. Full article

The potential of silicon carbide (SiC) as a promising high-capacity and stable anode material is hindered by poor electronic conductivity and slow lithium diffusion kinetics. Here, we report a one-step laser chemical vapor deposition (LCVD) process to directly synthesize porous graphene@SiC heterostructures on carbon fiber substrates. This in situ method yields an integral, binder-free electrode architecture that enhances mechanical robustness against pulverization. A critical feature of this heterostructure is the built-in electric field at the graphene–SiC interface, which is revealed by theoretical calculations to significantly accelerate charge transport and lithium-ion diffusion. The resulting anode delivers a high reversible capacity of 668 mAh·g⁻¹ after 100 cycles at 0.1 A·g⁻¹. More remarkably, a unique multi-stage activation mechanism is discovered, leading to an unprecedented capacity rebound to 735 mAh·g⁻¹ after cycling at rates up to 5 A·g⁻¹. This activation process is observed to accelerate with increasing current density in the 0.1–2 A·g⁻¹ range. Furthermore, post-cycling analysis via XRD, TEM, and XPS confirms both the structural durability of the electrode and a reversible lithium intercalation mechanism, providing a critical foundation for the future design of high-performance LIB anodes. Full article

This work focuses on the synthesis and the comprehensive characterization of polydianiline (PDANI) polymer, obtained via oxidative polymerization of dianiline, a low-toxicity and more environmentally friendly starting monomer for polyaniline (PANI) formation. Despite the structural similarity to PANI, PDANI remains underexplored, especially regarding the effect of different synthesis conditions. Here, we investigate how chloride, sulfate, and camphor sulfonate dopants, combined with green solvents such as water and DMSO, modulate the final properties of PDANI in the emeraldine salt configuration. The produced materials were extensively characterized using a multi-technique approach. FTIR, Raman, EPR, and UV-Vis spectroscopies provided insights into chemical structure, molecular order, and polaron population. Electrical conductivity was disclosed via current-voltage (I-V) measurements, while cyclic voltammetry (CV) and coulovoltammetry (QV) were employed to evaluate redox activity and charge reversibility. The resulting PDANI displays structural and functional features comparable to those of PANI synthesized under similar conditions. Notably, the nature of the dopant and acidic medium was found to crucially govern the oxidation level, molecular organization, and electrochemical performance, boosting PDANI as a tunable and sustainable alternative for applications ranging from electronics to energy storage. Full article