Zn-based aqueous batteries have attracted widespread research attention, while the lack of nucleation theory for electrochemical interactions at the Zn-water interface constrains efforts to suppress the thermodynamically spontaneous hydrogen evolution reaction and dendrite formation, thereby stalling practical development. Elucidating Zn electrodeposition in aqueous media requires Zn-specific nucleation theory and a descriptor to regulate interfacial electrochemistry. Conventional Li-based spherical nucleation models disregard Zn's crystallography and the interfacial resistance that governs nucleation, thereby focusing on polarization variations. In this work, we reformulate the classical spherical nucleation theory derived by Li for the hexagonal close-packed structure of Zn and establish a dimensionless descriptor (Wf) to quantitatively rationalize interfacial electrochemistry. Wf synthesizes the polarization driving force and interfacial resistance into a stability metric. Higher Wf values facilitate uniform Zn deposition, as evidenced by the literature. Accordingly, we develop a high-Wf electrolyte to inhibit dendrites and side reactions, achieving over 700 h at 100% depth of discharge and 7660 cycles at 10 A g-1 in a Zn||NaV3O8 cell. This work provides a fundamental nucleation theory and a generally applicable quantitative metric for the rational design of Zn-based aqueous batteries.
Cyclobutenes serve as highly valuable synthetic targets in organic chemistry. However, the efficient construction of the cyclobutene scaffold has long posed a significant challenge, particularly in the synthesis of sulfonyl-substituted cyclobutenes, which remain difficult to access via conventional methods, including transition-metal catalysis, organocatalysis, and photocatalysis. In this work, we developed an electrochemistry-driven strain-release strategy for bicyclo[1.1.0]butanes functionalization by using selenium sulfonates. This unique transformation proceeds via a radical addition/tandem oxidation-elimination process, enabling the synthesis of diverse cyclobutenes under transition metal-free and chemical oxidant-free conditions. Importantly, bifunctional addition products are also achievable under inert atmosphere, which can be further transformed into the corresponding cyclobutenes under given electrochemical conditions. Mechanistic investigations and theoretical density functional theory calculations suggest the involvement of radical intermediates, providing insight into the chemical selectivity of the reaction.
Fused filament fabrication (FFF) has rapidly evolved from a prototyping tool into a powerful platform for electrochemical device innovation. Its accessibility, design freedom, and compatibility with diverse polymers have enabled breakthroughs in sensor architectures, energy storage components, and wearable systems. However, works using currently available commercial filament lack the required conductivity or functionality to create impactful devices. Recent advances in conductive composites, surface functionalization strategies, and multimaterial printing have transformed FFF from a low-resolution technique into a versatile manufacturing approach capable of integrating complex geometries with tailored electrochemical properties with the potential to of achieve real impact. While challenges remain in realizing microscale resolution and consistentency in conductivity between filament batches and in printing across different devices, emerging solutions are pushing the boundaries of what is possible. This review highlights the progress that has positioned FFF at the forefront of additive manufacturing for electrochemistry and outlines the innovations that will drive the next generation of scalable, high-performance devices.
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Vibrio parahaemolyticus is a major foodborne pathogen widely distributed in aquatic environments and seafood supply chains, necessitating rapid and ultrasensitive detection strategies adaptable to diverse testing scenarios. Here, we present a glycine/ PVP- and tetrahedron-integrated one-pot CRISPR sensing platform (termed GPT-CRISPR) for robust and ultrasensitive nucleic acid detection. The platform introduces chemical regulation into a multienzyme one-pot RAA-CRISPR/Cas13a network, where glycine may help reduce nonspecific Cas13a background activity, possibly through weak competitive interactions, while polyvinylpyrrolidone (PVP) may enhance reaction compatibility through macromolecular crowding and spatial shielding. This coordinated microenvironment enables stable amplification and CRISPR activation within a single closed vessel while minimizing background interference. Upon target recognition, activated Cas13a cleaves uracil-containing, surface-immobilized DNA tetrahedra, translating molecular recognition into amplified electrochemical signals. This transduction strategy enables quantitative detection with a linear dynamic range of 1.5 to 3 × 103 copies μL-1 and a limit of detection of 0.38 copies μL-1. The same chemically regulated one-pot CRISPR framework remains compatible with fluorescence and lateral flow readouts. The assay operates under isothermal conditions and delivers results within 30 min without complex sample preparation. Validation across real-world samples demonstrates robustness in complex matrices. Collectively, GPT-CRISPR integrates chemical stabilization of a one-pot CRISPR framework with electrochemical transduction, defining a robust sensing architecture with adaptable readout capability.
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The development of high-energy-density sodium-ion batteries places stringent requirements on cathode materials to simultaneously achieve high operating voltages, rapid Na+ ions transport, and long-term structural and interfacial stability. Polyanionic NASICON-type frameworks have emerged as a compelling cathode platform due to their robust three-dimensional Na+ ions diffusion networks, strong inductive effects, and excellent thermal stability. Within this materials family, fluorophosphate NASICON cathodes offer elevated redox potentials, while targeted anion chemistry modulation provides an effective strategy to tune electronic structure, ion migration, and interfacial reactivity. Representative vanadium-based fluorophosphate cathodes, Na3V2(PO4)2F3 (NVPF) and Na3V2O2(PO4)2F (NVOPF), exhibit closely related crystal frameworks yet display distinct sodium storage behavior and degradation characteristics under high-voltage operation. In NVOPF, partial substitution of F- by O2- enhances electronic conductivity and Na+ ions transport kinetics, while NVPF maintains a higher redox potential associated with the V3+/V4+ couple. This review critically compares NVPF- and NVOPF-based cathodes in terms of crystal structure, sodium storage mechanism, synthesis and modification strategies, and high-voltage cathode/electrolyte interfacial stability. By correlating structural chemistry with electrochemical and interfacial evolution, this work provides general insights and design guidelines for high-voltage NASICON-type cathodes in sodium-ion batteries.
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Given the distinct pharmacological activities and toxicological profiles of fluoxetine enantiomers, highly selective analytical tools are essential to ensure medication safety and advance the accuracy of chiral recognition. The hydrogen-bonded organic framework HOF-101 possesses well defined porous channels, abundant directional hydrogen-bonding sites, and intrinsic fluorescence, and can achieve chiral recognition through differential cavity confinement and stereospecific hydrogen-bonding interactions. Based on this, we have developed a multimodal chiral fluorescent probe based on HOF-101 to identify the enantiomers of fluoxetine. By leveraging the ordered porous structure and abundant active sites of HOF-101, we effectively identified the enantiomers of fluoxetine using a combination of colorimetric, fluorescent, and electrochemical detection methods. We investigated the probe's performance across three orthogonal detection modalities: visual colorimetry response, fluorescence turn-on (λem blue-shift from 550.0 nm to 450.0 nm; PLQY increase from 7.38% to 87.77%), and electrochemistry response. The limits of detection (LODs) were 0.464 nM (fluorescence) and 0.0303 nM (electrochemistry), respectively, the probe achieved sub-nanomolar sensitivity. The selective recognition mechanism involves competitive hydrogen bonding, wherein S-FLX enters the cavity of HOF-101, inducing a structural collapse that elicits pronounced photophysical and electrochemical responses. In contrast, the R-enantiomer is excluded due to steric incompatibility, resulting in negligible signal changes. These results highlight that cross validation across all three modes confirms result reproducibility and eliminates modality specific artifacts. This study provides a new technical solution for the rapid recognition and high sensitivity detection of chiral drugs.
Electrochemistry involving superconcentrated electrolytes has rapidly gained attention as a transformative approach in electrochemical processes. Superconcentrated electrolytes have emerged as a groundbreaking solution in electrochemical applications, recognized for their nonflammable nature, ecofriendly composition, and expanded electrochemical stability window compared to conventional dilute aqueous electrolytes. The electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are fundamental processes in energy conversion and storage technologies. This study investigates the electrochemical activity of platinum electrodes in lithium-based electrolytes for understanding the electrochemical characteristics from low to high concentration. The HER and OER kinetics in superconcentrated electrolytes were performed to address challenges related to stability and efficiency in high-concentration ionic environments. Highly concentrated electrolytes characterized by their unique solvation structure and extended electrochemical stability potential window offer promising avenues for enhancing energy storage and conversion applications. Through cyclic voltammetry and linear sweep voltammetry, we analyze key parameters such as redox reactions, overpotentials, and kinetic reactions. This study explores the interaction between platinum and highly concentrated aqueous electrolytes to elucidate its influence on catalytic performance. The results provide insights into optimizing platinum-based electrocatalysis for next-generation sustainable energy solutions, highlighting the role of electrolyte composition in dictating reaction kinetics, potential window, and overall electrochemical performance.
Bioengineering of bimetallic oxides is a significant requirement for both social and environmental applications. In this work, bimetal oxide nanomaterials, Zinc orthotitanate Zn2TiO4 was produced using a green process which utilizes natural extract of Hibiscus sabdariffa. More accurately, natural extract/phyto-compounds of Hibiscus sabdariffa was validated as an effective chelating agent at room temperature and atmospheric pressure. A variety of techniques were applied to analyse their physicochemical properties and verify the production of the Zn2TiO4 nanoparticles. The XRD analysis illustrated the crystalline structure of the Zn2TiO4 nanocomposites. The SEM analysis showed the morphology of the compounds Zn2TiO4 to be highly porous. The EDS analysis validated the presence of elements such as Ti, and Zn while FTIR analysis indicated the existence of multiple functional groups, including O-H, C-H, C=O, Ti-O, and Zn-O bonds in the compound. The PL peaks identified at 240 and 450 nm are attributed to the charge transfer characteristics present in the surface state of the resulting product. The single phase crystals of the bio-engineered Zn2TiO4 were found to be within the nanoscale while exhibiting a significantly elevated photocatalytic efficacy in decomposing Methylene Blue reaching a threshold of about 94.1% efficacy at about 120 min. From the electrochemistry viewpoint, the bioengineered Zn2TiO4 nanomaterial demonstrated enhanced redox activity and stability, exhibiting 94.2% current retention after 20 cycles. Cyclic voltammetry (CV) studies confirmed a diffusion-controlled process, while electrochemical impedance spectroscopy (EIS) revealed a 10-fold reduction in charge transfer resistance ®ct), from 5.48 to 0.53 KΩ. This significant acceleration in electron transfer kinetics is corroborated by a nearly 2-fold increase in interfacial admittance (Yo), indicating an expanded electroactive surface area. These results demonstrate the applicability and potential for Zn2TiO4 nanomaterial in advanced electrochemical applications. From the antibacterial perspective, Zn₂TiO₄ nanomaterial showed limited activity in the agar-disc diffusion assay, with no meaningful inhibition against most tested Gram-positive and Gram-negative strains and only a marginal response against K. pneumoniae. These results suggest that any antibacterial potential of the Zn₂TiO₄ nanomaterial may likely to be strongly dependent on assay format, nanoparticle dispersion, contact conditions, and possible light-driven ROS generation.
We report on the synthesis of the palladium(IV)-containing hexatungstate [PdIVW6O24]8- (PdW6) with a central 6-coordinated PdIV ion, which is surrounded by a ring of six edge-shared WO6 octahedra. The sodium salt of PdW6 was structurally characterized in the solid state by multiple techniques, and the solution redox chemistry was investigated by electrochemistry. The catalytic hydrogenation of o-xylene using supported PdW6 as a precatalyst was also studied.
The detection of chloramphenicol residues in food is critical to consumer health. To achieve efficient and sensitive detection, this study proposes a biosensor based on covalent organic framework@Au nano-flower (COF@Au NFs) and DNAzyme cascade amplification. Owing to their excellent biocompatibility, high electrical conductivity, and strong surface-enhanced Raman scattering (SERS) enhancement, COF@Au NFs serve as an efficient substrate for both electrochemistry (EC) and SERS detection. The biosensor achieves sensitive dual-mode EC and SERS detection at femtomole levels. In the sensing system, chloramphenicol specifically activates a DNAzyme, triggering a cascade amplification reaction and releasing single-stranded DNA (S1), S1 subsequently induces the self-assembly of the sequence-specific DNA fragment EAD2 into a G-quadruplex bipedal structure capable of binding methylene blue (MB). This bipedal design enhances MB binding, thereby significantly improving both the EC and SERS responses. Experimental results demonstrate that the method exhibits an excellent linear response over the range of 1.0 × 10-13 M to 0.1 × 10-7 M, with an EC detection limit of 6.0070 × 10-14 M and a SERS detection limit of 2.3472 × 10-14 M. This dual-mode detection method, with its high sensitivity and selectivity, holds promise for rapid and reliable chloramphenicol residue detection, providing robust technical support for food safety monitoring and further safeguarding consumer health.
Copper (Cu) catalysis merged with electrochemistry offers efficient transformations under mild conditions, yet in situ generation of active Cu species remains challenging. Here, we introduce a novel source of catalytically active Cu(i) cations that operates without strong additives, oxidants, high concentrations of Cu salts, bases, or elevated temperatures. These Cu(i) species are integrated into a nanoelectrospray ionization (nanoESI)-based electrocatalytic platform, in which a Cu wire replaces the conventional inert electrode. Under applied voltage, anodic corrosion releases Cu(i) directly into the reaction solution inside the emitter, providing (i) in situ generation of active Cu cations, (ii) electrocatalysis under additive-free mild conditions, and (iii) online reaction monitoring by high-resolution mass spectrometry (MS). The Cu electrode serves a dual role: as a sacrificial anode supplying Cu(i) without competing counteranions, enhancing reaction efficiency and minimizing MS signal suppression, and as a voltage source generating a stable electrospray for real-time analysis. Using this platform, we demonstrate efficient Cu-catalyzed (i) C-H amination of arenes, (ii) intermolecular N-N homocoupling of o-phenylenediamine, and (iii) intramolecular dehydrogenative N-N coupling of anthranilamide. The scalability of the electrochemical microreactor concept was demonstrated through the successful translation of the in situ Cu-catalyzed electrochemical C-H amination to a bulk electrochemical cell. This synergistic approach enables rapid reaction screening, discovery of mild conditions, and continuous capture of transient intermediates, providing novel mechanistic insight and advancing sustainable Cu electrocatalysis.
High-temperature platinum (Pt) thin films have been widely used in gas-phase devices such as temperature sensors and microheaters, but little has been done in the field of high-temperature electrochemistry, particularly under hydrothermal conditions. In this work, we explored the chemical and mechanical stability of sapphire-supported tantalum-platinum (sapphire/Ta/Pt) electrodes capped at their edges with a conformal Ta/SiO2 layer in 0.1 M H2SO4 at 200 °C under autogenous pressure. A subset of samples was annealed for 10 min in flowing O2 at 650 °C to gauge the impact of the Ta/SiO2 layer on the overall performance of the Pt electrodes in acidic solutions. The temperature and pressure investigated in this work are well above those reported in previous studies on Ta, Pt, and Pt-alloy thin films, particularly those focused on catalyst materials for energy storage and conversion devices. The electrochemically (or electrochemical) active surface area (ECSA) of the Pt electrodes was measured before and after immersion in H2SO4 at 200 °C and used as the primary durability metric, while X-ray photoelectron spectroscopy (XPS), grazing-incidence X-ray diffraction (GI-XRD), and scanning electron microscopy (SEM) tracked changes in surface chemistry and morphology. Results show that both unannealed and annealed electrodes perform well, retaining more than 80% of their initial ECSA after cycling the potential between 0 and 1.4 V at 500 mV/s in 0.1 M H2SO4 at room temperature, constituting a significant first step toward the development of reusable/low-cost sensors for electrochemical studies in hydrothermal systems.
The movement of a species from the bulk to the electrode surface is a fundamental process vital to many aspects of electrochemistry, including sensing, energy storage, and metal electrodeposition. For diffusion-controlled processes, several well-accepted methods to determine the rate of diffusion are available for conventional solvents; however, in more complex solvents such as ionic liquids (ILs), it is still unclear whether the same methods provide accurate measurements. In this work, we evaluated the accuracy of four electrochemical methods, namely, the Randles-Ševčík equation, the Cottrell equation, the Shoup and Szabo approximation, and the Levich equation, to determine the diffusion coefficient of ferrocene in two widely used ILs, using various working electrodes. The results show that the Randles-Ševčík equation yields reliable and accurate values on a glassy carbon (GC) electrode but lower than expected diffusion coefficients on Pt thin-film electrodes (TFEs). However, the Shoup and Szabo approximation was found to provide accurate values at a Pt micro disk electrode. The Levich method provided highly accurate diffusion coefficients for the two ILs tested; however, bubble formation prevented the diffusion coefficients from being measured in ILs with higher viscosities. The Cottrell equation was shown to generate inaccurate values, which may be due to a combination of slow rearrangement of the ions in the double layer and uncompensated ohmic resistance, leading to inflated currents after a large potential step. From these findings, it is suggested that multiple techniques should be used to confirm diffusion coefficient values in ILs, with the viscosity of the IL and the electrode material considered when choosing the best methods.
Functional patchy particles, distinguishing themselves from isotropic colloids through different discrete surface domains, are critical for advanced applications such as colloidal assembly, catalysis, and biomedical purposes. In this review, we focus on the elaboration of patchy particles, categorizing the different synthesis strategies based on the specific interfacial environments employed to induce asymmetry. Recent advances, as a function of the various interfacial constraints, are reviewed: (1) solid-gas interfaces, which exploit physical shadowing for directional deposition; (2) liquid-gas interfaces, taking advantage of surface tension and wettability to create tunable dynamic masks for selective modification; (3) solid-liquid interfaces, utilizing surface immobilization to restrict chemical access or induce site-selective growth; and (4) liquid-liquid interfaces, where soft boundaries facilitate symmetry breaking via thermodynamic partitioning, confinement induced assembly, and bipolar electrochemistry. By revealing the relationship between interfacial synthesis conditions, the triggered chemical reactions, and the final particle features, this review aims to provide practical insights and design principles for engineering next-generation patchy particles with tailored complexity.
Conventional corrosion protection strategies primarily rely on passive defensive approaches, essentially blocking or consuming corrosive agents. In contrast, we hypothesized that the primary corrosive agent, dissolved O₂, could be strategically repurposed from a destructive species into an active repair resource to enable autonomous self-healing. To validate this, we engineered an intelligent coating system incorporating a bimetallic FeCe metal-organic framework (MOF) capable of executing a precise chemical program upon defect exposure. When the coating is mechanically damaged, the subsequent chemical processes were systematically investigated using simulations (density functional theory) alongside experiments (electrochemistry and material testing). Our findings reveal that the MOF catalyzes the conversion of aggressive dissolved O₂ into highly reactive hydroxyl radicals (OH) with near-zero activation energy. These radicals are immediately consumed in a constructive reaction with metal ions and organic linkers released from the MOF, triggering the in-situ formation of a dense inorganic-organic composite film precisely over the damaged area. This on-demand conversion process effectively transforms the destructive agent into a protective barrier. Consequently, the resulting coating exhibits an order-of-magnitude improvement in corrosion resistance compared to conventional systems. This work establishes a new method in materials chemistry by demonstrating the feasibility of repurposing environmental aggressors into functional components for active, autonomous repair.
Four ferrocene-functionalized chalcone derivatives, (3-oxo-3-phenyl-1-propen-1-yl)-ferrocene (I), [3-(3-bromophenyl)-3-oxo-1-propenyl]-ferrocene (II), [3-Oxo-3-(2-pyridinyl)-2-propen-1-yl]ferrocene (III), and [3-(6-Bromo-2-pyridinyl)-3-oxo-1-propenyl]-ferrocene (IV), incorporating benzene or pyridine acceptor units were synthesized and comprehensively investigated to establish structure-property correlations in ultrafast excited-state dynamics and nonlinear optical (NLO) responses. The compounds were fully characterized by NMR, FTIR, mass spectrometry, electrochemistry, and steady-state absorption spectroscopy. Femtosecond transient absorption (fs-TAS) measurements revealed rapid internal conversion from the S2 state to a stabilized intramolecular charge-transfer (ICT) state within picoseconds, followed by slower recovery to the ground state. Global kinetic analysis confirmed that ICT lifetimes are strongly modulated by the nature of the acceptor moiety. ICT-driven delocalization can have a significant effect in enhancing NLO activity. Open-aperture Z-Scan experiments at 800 and 1060 nm demonstrated pronounced reverse saturable absorption arising from two-photon absorption (TPA). Among the series, the 3-bromophenyl derivative exhibited the highest TPA coefficient (β ∼10- 5 cm/GW), attributed to enhanced ICT stabilization and extended π-conjugation. These results highlight halogen substitution as a critical design principle, with bromine enhancing electronic polarization and amplifying NLO performance. The combined spectroscopic and optical studies establish ferrocene-chalcone hybrids as versatile molecular platforms for rational design of photonic materials, offering valuable guidelines for optical limiting and optoelectronic applications.
Rechargeable aluminum batteries (RABs) are considered promising for long-duration, cost-effective energy storage applications due to their intrinsic safety and potential cost advantages. RABs are nonetheless fundamentally hindered by thermodynamics, which favor formation of a high bandgap, thin aluminum oxide (Al2O3) layer at the aluminum (Al) anode-electrolyte interface-passivating the anode. The electrode-level capacities achieved in the literature reports are also typically lower than expected from the redox reactions at the electrodes. Here, we investigate root causes and report a previously unrecognized, yet dominant degradation mechanism associated with interfacial chemistry at the Al anode. Specifically, we find that strong Lewis acid-base interactions between the passivating oxide layer and chloroaluminate species in electrolytes promote formation and migration of oxochloroaluminate species to the cathode. We report further that these species infiltrate the graphite cathode and impede ion transport, rendering a large fraction of the cathode electrochemically inaccessible at high mass loadings. We propose a single-step chemical etching strategy that eliminates the native oxide layer from conventional Al anodes without compromising electrochemistry and transport in the cathode. The effectiveness of the approach is illustrated in full-cell RABs able to achieve high reversibility (Coulombic efficiency (CE) > 98%) at higher cathode mass loadings (e.g., 13 mg cm-2).