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Background: Electrochemiluminescence (ECL) is an electrochemically induced process in which radicals generated at the electrode surface undergo exergonic electron transfer reaction to form excited states and luminesce. ECL, with high sensitivity and superior spatiotemporal control, has been widely applied in bioanalysis and light-emitting devices. The ECL signal of rubrene (Rub) was observed in Rub/TPrA oil-in-water (o/w) emulsions, which was inconsistent with the theory of ion-transfer coupled electron-transfer in Rub emulsion droplets, and the conventional ECL mechanism in Rub/TPrA system couldn't explain this phenomenon., Results: Choosing the toluene oil-in-water emulsion droplets as reactors, we put forward and verified a new ECL mechanism of Rub in aqueous solution on the basis of cyclic voltammograms, single-entity electrochemistry, ECL detection techniques and COMSOL finite element simulation. The new mechanism involved that Rub was reduced to Rub •- by the highly reducing species TPrA • , Rub •- was then oxidized to the excited state Rub∗ by the stable intermediate TPrA •+ , and finally Rub∗ was inactivated by emitting photons. In simulation, the standard oxidation rate constant of TPrA in the emulsion droplets was deduced as 1.5 × 10 -4  cm/s, and the deprotonation rate of TPrA •+ was about 200 s -1 . Besides, emulsion droplets colliding on Au ultramicroelectrode (UME) were found to be able to amplify ECL signals., Significance: The newly proposed ECL mechanism of Rub/TPrA emulsion reactors broke the solubility problem of Rub in an aqueous, promoting the research and application of the organic luminophore Rub in bioanalysis. With the ECL signals amplification capability, the o/w emulsion reactors are promising to future design of ECL biosensors with higher sensitivity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: The integration of paper-based analytical devices with lab-on-a-chip technology has opened up new possibilities for miniaturized, rapid, low cost and portable diagnostic testing in resource limited settings. This work introduces an integrated lab-on-a-chip platform coupling paper-based analytical devices (LOC-PADs) for dual usage: electrochemically controlled solid-phase microextraction (EC-SPME) and determination of naproxen (NAP) by potentiometric ion-selective electrode (ISE) in biological samples., Results: Conductive papers were successfully fabricated by a chemical procedure. Thereupon, a conducting molecularly imprinted polymer (CMIP) film based on PPy and an anionic model drug (NAP) as a template were applied to the conductive paper substrate via electrochemical methods. A microfluidic chip device was employed to assess the analytical performance of the fabricated paper-based CMIP. The designed chip is divided into two parts with a microfluidic channel between them. The first chamber is an extraction zone for EC-SPME of NAP by using the CMIP paper as a selective sorbent. The second chamber is the detection zone and consists of a paper-based NAP ion selective sensor for potentiometric detection of drug. The analytical process was investigated and optimized for each chamber. Remarkable selectivity towards NAP was achieved in the concentration range from 4.0 × 10 -7 to 1.0 × 10 -2  mol L -1 with determination coefficient (R 2  = 0.99) and the limit of detection (LOD) was 2.0 × 10 -7  mol L -1 . Anionic Nernstian compliance was gained -58.5 ± 0.5 mV decade -1 , and response time in the detection step was 7s for ISE. Satisfactory spiking recovery values within the acceptable range of 90-110 % with RSDs ≤7 % were achieved for the analysis of real samples with fully portable LOC device., Significance: The LOC-PADs were favorably used for selective extraction and determination of NAP in serum and saliva samples, respectively. EC-SPME caused sample clean-up, reduced or eliminated different interferences and enhanced selective response of ISE as detection zone of device. Integration of EC-SPME and ISE in a single chip enabled easy and fast determination of trace amounts of NAP in limited real sample volumes, and fully portable advantages., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Using molecular simulation and continuum dielectric theory, we consider how electrochemical kinetics are modulated by the twist angle in bilayer graphene electrodes. By establishing a connection between the twist angle and the screening length of charge carriers within the electrode, we investigate how tunable metallicity modifies the statistics of the electron transfer energy gap. Constant potential molecular simulations show that the activation free energy for electron transfer increases with screening length, leading to a non-monotonic dependence on the twist angle. The twist angle alters the density of states, tuning the number of thermally accessible channels for electron transfer and the reorganization energy by affecting the stability of the vertically excited state through attenuated image charge interactions. Understanding these effects allows us to express the Marcus rate of interfacial electron transfer as a function of the twist angle in a manner consistent with experimental observations.

Lead (Pb), cadmium (Cd) and arsenic (As) contamination in soils show a growing environmental concern. However, owing to the significant differences in chemical characteristics, remediating heavy metal(loid)s of Pb, Cd and As is challenging. Herein, anionic surfactant-activated electrochemical approach was proposed to realize efficient immobilization of As, Cd and Pb heavy metal(loid)s from contaminated soils. In this innovative method, calcium lignosulfonate (CL) as anionic surfactant was used to activate Cd and Pb from contaminated soils into solution, afterwards anodically generated Fe (II) ions by the electrochemical process react with Pb and Cd to form precipitates. Meanwhile, owing to the strong binding capacities of Fe (II) ions, As contaminations were remediated. Moreover, via various characterizations and cyclic voltammetric method, the reaction kinetics and phase transformation process during the electrochemical process were analyzed in detail. These findings show great potential in optimizing the design of electrochemical treatment, which will be applied in remediating multi-component heavy metal(loid) polluted soils., Competing Interests: Declaration of competing interest The authors declared that they have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Understanding the nature of intermediates/active species in reactions is a major challenge in chemistry. This is because spectator species typically dominate the experimentally derived data and consequently active phase contributions are masked. Transient methods offer a means to bypass this difficulty. In particular, modulation excitation with phase-sensitive detection (ME-PSD) provides a mechanism to distinguish between spectator and reacting species. Herein, modulation excitation (ME) time-resolved (energy dispersive) X-ray absorption spectroscopy, assisted by phase sensitive detection (PSD) analysis, has been applied to the study of a liquid phase process; in this case the classic ferrocyanide/ferricyanide redox couple. Periodic switches of the electrical potential (anodic/cathodic) enabled the use of the ME approach. Structural changes at fractions as low as 2 % of the total number of electroactive species were detected within the X-ray beam probe volume containing ~30 pmol of Fe(II)/Fe(III)., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Molecularly imprinted polymers (MIPs) are artificial receptors equipped with selective recognition sites for target molecules. One of the most promising strategies for protein MIPs relies on the exploitation of short surface-exposed protein fragments, termed epitopes, as templates to imprint binding sites in a polymer scaffold for a desired protein. However, the lack of high-resolution structural data of flexible surface-exposed regions challenges the selection of suitable epitopes. Here, we addressed this drawback by developing a polyscopoletin-based MIP that recognizes recombinant proteins via imprinting of the widely used Strep-tag II affinity peptide (Strep-MIP). Electrochemistry, surface-sensitive IR spectroscopy, and molecular dynamics simulations were employed to ensure an utmost control of the Strep-MIP electrosynthesis. The functionality of this novel platform was verified with two Strep-tagged enzymes: an O 2 -tolerant [NiFe]-hydrogenase, and an alkaline phosphatase. The enzymes preserved their biocatalytic activities after multiple utilization confirming the efficiency of Strep-MIP as a general biocompatible platform to confine recombinant proteins for exploitation in biotechnology., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Electron transfers in multinuclear metal complexes are the origin of their unique functionalities both in natural and artificial systems. However, electron transfers in multinuclear metal complexes are generally complicated, and predicting and controlling these electron transfers is extremely difficult. Herein, we report the precise manipulation of the electron transfers in multinuclear metal complexes. The development of a rational synthetic strategy afforded a series of pentanuclear metal complexes which composed of metal ions and 3,5-bis(2-pyridyl)pyrazole (Hbpp) as a platform to probe the phenomena. Electrochemical and spectroscopic investigations clarified overall picture of the electron transfers in the pentanuclear complexes. In addition, unique electron transfer behaviors, in which the reduction of a metal center occurs during the oxidation of the overall complex, were identified. We also elucidated the two dominant factors that determine the manner of the electron transfers. Our results provide comprehensive guidelines for interpreting the complicated electron transfers in multinuclear metal complexes., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The advent of wearable sensing platforms capable of continuously monitoring physiological parameters indicative of health status have resulted in a paradigm shift for clinical medicine. The accessibility and adaptability of such portable, unobtrusive devices enables proactive, personalized care based on real-time physiological insights. While wearable sensing platforms exhibit powerful capabilities for continuously monitoring physiological parameters, device fabrication often requires specialized facilities and technical expertise, restricting deployment opportunities and innovation potential. The recent emergence of rapid prototyping approaches to sensor fabrication, such as laser-induced graphene (LIG), provides a pathway for circumventing these barriers through low-cost, scalable fabrication. However, inherent limitations in laser processing restrict the spatial resolution of LIG-based flexible electronic devices to the minimum laser spot size. For a CO 2 laser-a commonly reported laser for device production-this corresponds to a feature size of ∼120 μm. Here, we demonstrate a facile, low-cost stencil-masking technique to reduce the minimum resolvable feature size of a LIG-based device from 120 ± 20 μm to 45 ± 3 μm when fabricated by CO 2 laser. Characterization of device performance reveals this stencil-masked LIG (s-LIG) method yields a concomitant improvement in electrical properties, which we hypothesize is the result of changes in macrostructure of the patterned LIG. We showcase the performance of this fabrication method via production of common sensors including temperature and multi-electrode electrochemical sensors. We fabricate fine-line microarray electrodes not typically achievable via native CO 2 laser processing, demonstrating the potential of the expanded design capabilities. Comparing microarray sensors made with and without the stencil to traditional macro LIG electrodes reveals the s-LIG sensors have significantly reduced capacitance for similar electroactive surface areas. Beyond improving sensor performance, the increased resolution enabled by this metal stencil technique expands capabilities for scalable fabrication of high-performance wearable sensors in low-resource settings without reliance on traditional fabrication pathways., Competing Interests: Declaration of competing interest The authors declare the following competing financial interest(s): T.R.R. is an inventor on patents and patent applications related to epidermal microfluidics and has a consulting and advisory relationship with Epicore Biosystems., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Nickel-rich cobalt-free LiNi0.9Mn0.05Al0.05O2 (NMA955) is considered a promising cathode material to address the scarcity and soaring cost of cobalt. Particle size and elemental composition significantly impact the electrochemical performance of NMA955 cathodes. However, differences in precipitation rates among metal ions coveys a challenge in obtaining cathode materials with the desired particle size and composition via hydroxide co-precipitation synthesis. Utilizing complexing agents like ammonia offers an effective strategy to tackle these issues. Here, we investigate the optimal ammonia concentration to achieve moderate particle size and precise material composition. Although ammonia only forms complex coordination with transition metals, its concentration also affects the final product's precipitation and composition, including aluminum. This study shows that ammonia serves a dual function in NMA synthesis via hydroxide co-precipitation, i.e., regulating particle size and adjusting elemental composition. It was found that an ammonia concentration of 1.2 M achieved optimal particle size and composition, resulting in superior electrochemical performance. NMA955 synthesized in 1.2 M ammonia demonstrated a high specific capacity of 188.12 mAh g-1 at 0.1C, retained 71.16% of its capacity after 200 cycles at 0.2C, and delivered 110.30 mAh g-1 at 5C. These results suggest tuning ammonia concentration is crucial for producing high-performance cathode materials., (© 2024 Wiley‐VCH GmbH.)

A widely used method to obtain tetrazoles is through the azide and nitrile [3+2] cycloaddition. However, this process often involves using non-recyclable transition metals or Lewis acid catalysts and stoichiometric amounts of oxidants and additives, which reduces atom efficiency. We have discovered a convergent paired electrochemical reaction to perform this cycloaddition reaction, without the need for metal catalysts or oxidants. This tetrazolation strategy uses azidotrimethylsilane (TMSN 3 ) and N-heterocycles in an undivided cell at a constant current. We use a mixture of CH 3 CN and equivalent amounts of H 2 O as co-solvent at room temperature. It is crucial to produce a stoichiometric amount of active hydroxyl ions through the cathodic reduction of water. Cyclic voltammetry (CV) studies and control experiments confirm that the cycloaddition reaction is specific to the electrode electron transfer process, eliminating the need for a mediator to shuttle electrons. This metal- and oxidant-free strategy is highly compatible with different functional groups and produces products with moderate to good yields. We have successfully tetrazolated bioactive compounds at a late stage, scaled up batches efficiently, and synthesized free amino-containing N-heterocycles via denitrogenation of tetrazoles., (© 2024 Wiley-VCH GmbH.)

Exploring cathode materials with excellent electrochemical performance is crucial for developing rechargeable aqueous zinc ion batteries (RAZIBs). Zinc hexacyanoferrate (ZnHCF), a promising candidate of cathode materials for RAZIBs, suffers from severe electrochemical instability issues. This work reports using low contents of alkaline metal cations as electrolyte additives to improve the cycle performance of ZnHCF. The cations with large sizes, particularly Cs + , changes the intercalation chemistry of ZnHCF in RAZIBs. During cycling, Cs + cations co-inserted into ZnHCF stabilize the host structure. Meanwhile, a stable phase of CsZn[Fe(CN) 6 ] forms on the ZnHCF cathode, suppressing the loss of active materials through dissolution. ZnHCF gradually converts to an electrochemically inert Zn-rich phase during long-term cycling in aqueous electrolyte, leading to irreversible capacity loss. Introducing Cs + in the electrolyte inhibits this conversion reaction, resulting in the extended lifespan. Owing to these advantages, the capacity retention rate of ZnHCF/Zn full batteries increases from the original 7.0 % to a high value of 54.6 % in the electrolyte containing 0.03 M of Cs 2 SO 4 after 300 cycles at 0.25 A ⋅ g -1 . This research provides an in-depth understanding of the electrochemical behavior of ZnHCF in aqueous zinc electrolyte, beneficial for further optimizing ZnHCF and other metal hexacyanoferrates., (© 2024 Wiley-VCH GmbH.)

Broadening the scope of functionalities that can be covalently bound to single-walled carbon nanotubes (SWCNTs) is crucial for enhancing the versatility of this promising nanomaterial class in applied settings. Here we report the covalent linkage of triphenylphosphine oxide [Ph 3 P(O)] to SWCNTs, a hitherto overlooked surface functionality. We detail the synthesis and structural characterization of a new family of phosphine oxide-functionalized diaryliodonium salts that can facilitate direct Ph 3 P(O) transfer and afford novel SWCNTs with tunable Ph 3 P(O) content (SWCNT-P). The molecularly-distributed and robust nature of the covalent Ph 3 P(O) attachment in SWCNT-P was supported by a combination of characterization methods including Raman, infrared, UV/Vis-NIR and X-ray photoelectron spectroscopies coupled with thermogravimetric analysis. Electron microscopy further revealed the effectiveness of the Ph 3 P(O) moiety for de-bundling SWCNTs to yield SWCNT-P with superior dispersibility and processability. Finally, electrochemical studies established that SWCNT-P is sensitive to the presence of Li + , Na + and K + wherein the Gutmann-Beckett Lewis acidity parameters of the ions were quantitatively transduced by Ph 3 P(O) to electrochemical responses. This work hence presents a synthetic, structural, spectroscopic and electrochemical foundation for a new phosphorus-enriched responsive nanomaterial platform featuring the Ph 3 P(O) functionality., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Rechargeable magnesium batteries are promising for future energy storage. However, among other challenges, their practical application is hindered by low coulombic efficiencies of magnesium plating and stripping. Fundamental processes such as the formation, structure, and stability of passivation layers and the influence of different electrolyte components on them are still not fully understood. In this work, we gain unique insights into the initial Mg plating and stripping cycles by comparing magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2 )- and magnesium tetrakis(hexafluoroisopropyloxy)borate (Mg[B(hfip) 4 ] 2 )-based electrolytes, each with and without MgCl 2 , on gold electrodes by highly sensitive operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) applying hydrodynamic spectroscopy. With the stable Mg[B(hfip) 4 ] 2 -based electrolytes, highly efficient and interphase-free cycling is possible and passivation layers are attributed to electrolyte contaminants. These are forming and degrading during the so-called initial conditioning process. With the more reactive Mg(TFSI) 2 -based electrolyte, thick passivation layers with small pores are growing during cycling. We demonstrate that the addition of chloride lowers the amount of passivated Mg deposits in these electrolytes and accelerates the currentless dissolution of the passivation layer. This has a positive effect since we observe the most efficient cycling and uniform deposition when no interphase is present on the electrode., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

beta-(Trifluoromethyl)styrenes are potentially useful building blocks for the synthesis of organofluorine compounds because their electron-deficient C=C double bonds can undergo diverse transformations. One of the most practical methods for preparing b-(trifluoromethyl)styrenes is the decarboxylative trifluoromethylation of readily available cinnamic acid derivatives using the Langlois reagent as a less expensive trifluoromethyl source. We revisited the electrochemical decarboxylative trifluoromethylation of cinnamic acid derivatives to identify modified conditions that reduce the loading of the Langlois reagent without additional additives. The reaction mechanism was computationally investigated to gain insight into the dependence of the product yields on the aryl terminal groups. The synthetic utility of the obtained b-(trifluoromethyl)styrenes was demonstrated by their transformation into 4-aryl-3-(trifluoromethyl)pyrrolidines., (© 2024 Wiley‐VCH GmbH.)

Replacing petrochemicals with refined waste biomass as a sustainable chemical source has become an attractive option to lower global carbon emissions. Popular methods of refining lignocellulosic waste biomass use thermochemical processes, which have significant environmental downsides. Using electrochemistry instead would overcome many of these downsides, directly driving chemical reactions with renewable electricity and revolutionizing the way many chemicals are produced today. This review mainly focuses on two furanic platform chemicals that are produced from the dehydration of cellulose, 5-hydroxymethylfurfural and furfural, which can be electrochemically reduced or oxidized to replace fuels and monomers that today are obtained from petrochemicals. Critical parameters such as electrode materials and electrolyte pH are discussed in relation to their influence on conversion efficiency and product distribution.This article is part of the discussion meeting issue 'Green carbon for the chemical industry of the future'.

Two novel BODIPY dyes, BOC3 and BC12, were synthesized with variable alkyl chains at terminal amide functional units. BC12, featuring a longer alkyl chain (-C12H25), formed a gel compared to BOC3, which has a shorter alkyl chain (-CH2OCH3), due to supra molecular self-assembly in film. Both dyes exhibited absorption peaks around 530 nm in the visible region, with a red shift of about 30 nm in the film state, essential for organic electronic applications. Concentration variation studies revealed π-π stacking/aggregates in the solid state causing red shifts in absorption and emission. BC12 exhibited more significant red shifts in film compared to its solution state due to supra molecular self-assembly. Electronic structure analysis using density functional theories (BMK and O3LYP) showed better correlation with absorption using the O3LYP method. Both dyes displayed quasi-irreversible oxidation and reduction couples with suitable HOMO (5.46 eV) and LUMO (3.32 eV) energy levels for organic electronic applications. Transient photoluminescence studies indicated a longer lifetime for BC12 (5.28 ns) than BOC3 (4.50 ns), suggesting π-π aggregation and supra molecular self-assembly. BC12's gelation, attributed to its long alkyl chain and two-dimensional motifs of the BODIPY core, forms spherical-shaped nano networks., (© 2024 Wiley‐VCH GmbH.)

Knowing the exact location of the semiconductor band-edges is key for mechanistic insights into their use for water and CO 2 photo/electrocatalysis. In this regard, a reliable strategy for nano-semiconductors did not exist yet. We demonstrate the use of reversible redox probes on nano-semiconductor electrodes to determine their band-edge locations in aqueous solutions. Rectifying current-potential (i-U) characteristics with the high work function (i.e. more positive formal potential) Fe(CN) 6 3- /Fe(CN) 6 4- redox couple yielded the exact flatband potential at various pH whereas the reversible i-U characteristics with the low work function (i.e. more negative formal potential) Ru(NH 3 ) 6 3+ /Ru(NH 3 ) 6 2+ redox couple provided the conduction band-edge location and dopant concentration for a 30 nm thin-film n-TiO 2 . The methodology can be extended to other nano-semiconductors and serves as an alternative to and goes beyond the capabilities of the Mott-Schottky procedure for bulk semiconductor electrodes., (© 2024 Wiley-VCH GmbH.)

Electrochemical pH-swing strategies offer a promising avenue for cost-effective and energy-efficient carbon dioxide (CO 2 ) capture, surpassing the traditional thermally activated processes and humidity-sensitive techniques. The concept of elevating seawater's alkalinity for scalable CO 2 capture without introducing additional chemical as reactant is particularly intriguing due to its minimal environmental impact. However, current commercial plants like chlor-alkali process or water electrolysis demand high thermodynamic voltages of 2.2 V and 1.23 V, respectively, for the production of sodium hydroxide (NaOH) from seawater. These high voltages are attributed to the asymmetric electrochemical reactions, where two completely different reactions take place at the anode and cathode. Here, we developed a symmetric electrochemical system for seawater alkalization based on a highly reversible and identical reaction taking place at the anode and cathode. We utilize hydrogen evolution reaction at the cathode, where the generated hydrogen is looped to the anode for hydrogen oxidation reaction. Theoretical calculations indicate an impressively low energy requirement ranging from 0.07 to 0.53 kWh/kg NaOH for established pH differences of 1.7 to 13.4. Experimentally, we achieved the alkalization with an energy consumption of 0.63 kWh/kg NaOH, which is only 38% of the theoretical energy requirements of the chlor-alkali process (1.64 kWh/kg NaOH). Further tests demonstrated the system's potential of enduring high current densities (~20 mA/cm 2 ) and operating stability over an extended period (>110 h), showing its potential for future applications. Notably, the CO 2 adsorption tests performed with alkalized seawater exhibited remarkably improved CO 2 capture dictated by the production of hydroxide compared to the pristine seawater., Competing Interests: Competing interests statement:The authors declare no competing interest.

Iron-bearing smectite clay minerals can act as electron sources and sinks in the environment. Previous studies using mediated electrochemical analyses to determine the reduction potential ( E H ) values of smectites observed that the relationship between the structural Fe 2+ (s) /Fe Total ratio in the smectite and E H varied based on the redox history of the smectite. We hypothesize that this behavior, referred to as redox hysteresis, results from the smectite particles not equilibrating with the applied E H over the course of the experiment (∼30 min). To test this hypothesis, we developed a model incorporating interfacial electron transfer kinetics and charge redistribution within the particle to simulate the mediated electrochemical experiments from previous studies. The simulated redox curves accurately matched the previously reported experimental redox curves of the smectite SWa-1, demonstrating that longer equilibration periods led to a decrease in redox hysteresis. We validated this experimentally by measuring the redox curve of SWa-1 after an equilibration period of at least 12 h. Furthermore, we extended the simulations to three other smectites (NAu-1, NAu-2, and SWy-2) and extracted their respective thermodynamic and kinetic parameters. This work offers a framework for interpreting and modeling redox reactions on clay surfaces, along with key parameters for four commonly studied smectites.

The high-rate electrochemical dissolution of copper in nitrate electrolytes is investigated primarily via polarization curves, while varying parameters such as the electrolyte flow velocity, the electrolyte resistance, the anode geometry, and the temperature. This study focuses on the re-rise in current at high voltages after the limiting current plateau. As a result of the studies, a change in the complexation mechanism from hydration to "solvo-nitration" is proposed, which requires an additional potential drop within the electrochemical double layer., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In almost all electrochemical systems for electrochemiluminescence (ECL) analysis, electrodes are connected with an external power source, either directly or via wireless energy transfer circuit. That is inconvenient and makes some applications impossible. Herein, we use galvanized iron with two different metals as both power source and electrodes to achieve a self-powered ECL and exploit ECL for the imaging of the corrosion of protective coating of widely used metal (e.g. galvanized iron) for the first time. The self-powered ECL enables the visualization of the deterioration of galvanic coating on iron using a smartphone and the detection of ascorbic acid with a linear range of 0.5-100 μM and a limit of detection of 0.31 μM. The devices based on self-powered approach do not require external power supply, thus effectively reducing their volume and cost. The self-powered ECL holds great promise for metal corrosion imaging and analytical applications., (© 2024 Wiley-VCH GmbH.)

Early detection of disease remains a crucial challenge in medicine. Delayed diagnosis often leads to limited treatment options, increased disease progression, and unfortunately, even death in some cases. To address this, the need for rapid, cost-effective, and noninvasive diagnostic tools is paramount. In recent years, electrochemical nanosensor-based point-of-care diagnostic tools have emerged as promising tools for various fields, with significant interest in their biological and chemical applications. These tiny sensors, utilizing nanoparticles and chemical agents, can detect and monitor physical components like disease biomarkers at the nanoscale, offering a unique advantage rarely found in other diagnostic methods. This unprecedented sensitivity has made them highly sought-after tools for biological applications, particularly in disease diagnosis. This review focuses specifically on electrochemical nanosensors and their potential as diagnostic tools in medicine. We will delve into their properties, applications, current advancements, and existing limitations., (© 2024 Wiley Periodicals LLC.)

The metabolism research of bioactive phenolic acids  widely found in natural products is of great significance for elucidating pharmacologic mechanisms and screening lead compounds. However, it is time-consuming and vulnerable to interference to conduct the traditional metabolism approach by applying organisms or biomaterials. Herein, a bionic technology was established by combining online electrochemistry-mass spectrometry (EC-MS) with offline electrochemistry-liquid chromatography-mass spectrometry (EC-LC-MS) to investigate the oxidative transformation and metabolic processes of the active phenolic acids (including salvianolic acid A, caffeic acid, 3, 5-O-dicaffeoylquinic acid, ferulic acid, salvianic acid A, and protocatechuic acid). Phase I metabolism of the phenolic acids were simulated by applying a three-electrode controlled potential electrochemical reactor with a boron-doped diamond electrode, with glutathione mixed into the oxidative products simultaneously for obtaining the phase II metabolites. Finally, structural characterization of the simulated metabolites of the phenolic acids was achieved successfully, including hydroxylation, methylation, demethylation, decarboxylation, etc. It was revealed that the simulated metabolism process based on an electrochemical system was effective in yielding a wide variety of metabolites for these compounds, which was also compared with the metabolism results applying rat liver microsomes. Consequently, this bionic technology is expected to be a powerful tool to investigate the material basis for the efficacy of active ingredients of natural products., (© 2024 Wiley‐VCH GmbH.)

Mycotoxin contamination poses serious threats to human and animal health. Food and environmental systems are often simultaneously contaminated with multiple mycotoxins, a problem that is further exacerbated by the synergistic toxicological effects of these co-occurring mycotoxins. Consequently, the development of rapid detection methods capable of simultaneously identifying multiple mycotoxins in agricultural products is essential to prevent their entry into the food chain. Compared to standard detection methods, optical and electrochemical (EC) sensing methods have distinct advantages for the rapid detection of mycotoxins. This review comprehensively summarizes the latest advancements in the field of simultaneous detection of multiple mycotoxins using optical and EC sensing methods over the last 6 years (2018-2024). First, the review introduces the classification and relevant principles of optical and EC sensing methods. Thereafter, it emphasizes innovative simultaneous detection strategies within these approaches. Finally, it discusses current challenges and offers a reference for further research. Currently, the main challenge lies in the mutual interference among targets, making the development of an interference-free detection platform essential. Furthermore, the ongoing development of integrated technology is expected to aid regulatory authorities in improving the quality of agricultural products for field applications., (© 2024 Institute of Food Technologists®.)

Electrochemical CO 2 reduction reaction (eCO 2 RR) has been explored extensively for mitigation of noxious CO 2 gas generating C 1 and C 2+ hydrocarbons and oxygenates as value-added fuels and chemicals with remarkable selectivity. The source of CO 2 being a pure CO 2 feed, it does not fully satisfy the real-time digestion of industrial exhausts. Besides the detrimental effect of noxious gas mixture leading to global warming, there is a huge capital investment in purifying the flue gas mixtures from industries. The presence of other impurity gases affects the eCO 2 RR mechanism and its activity and selectivity toward C 2+ products dwindle drastically. Impurities like NO x , SO x , O 2 , N 2 , and halide ions present in flue gas mixture reduce the conversion and selectivity of eCO 2 RR significantly. Instead of wiping out these impurities via separation processes, new strategies from material chemistry and electrochemistry can open new avenues for turning foes to friends! In this perspective, the co-electroreduction will vividly discussed and supporting role of different heteroatom-containing impurity gases with CO 2 , generating highly stable C─N, C─S, C─X bonds, and highlight the existing limitations and providing probable solutions for attaining further success in this field and translating this to industrial exhaust streams., (© 2024 Wiley‐VCH GmbH.)

Biomolecular condensation is a key mechanism for organizing cellular processes in a spatiotemporal manner. The phase-transition nature of this process defines a density transition of the whole solution system. However, the physicochemical features and the electrochemical functions brought about by condensate formation are largely unexplored. We here illustrate the fundamental principles of how the formation of condensates generates distinct electrochemical features in the dilute phase, the dense phase and the interfacial region. We discuss the principles by which these distinct chemical and electrochemical environments can modulate biomolecular functions through the effects brought about by water, ions and electric fields. We delineate the potential impacts on cellular behaviors due to the modulation of chemical and electrochemical environments through condensate formation. This Perspective is intended to serve as a general road map to conceptualize condensates as electrochemically active entities and to assess their functions from a physical chemistry aspect., (© 2024. Springer Nature America, Inc.)

Fluorinated organic compounds (FOCs) represent a class of synthetic chemicals distinguished by their resilient carbon-fluorine bonds, which demonstrate an ability to withstand environmental degradation over an extended period. The integration of FOCs into cutting-edge applications, including lithium-ion batteries (LiBs), presents considerable potential for environmental harm that has not yet been sufficiently addressed. This study focuses on the environmental fate of two fluorinated aromatics, tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), given their important role in improving the performance of LiBs. To achieve this, laboratory simulation methods including total oxidizable precursor assay, electrochemistry (EC), Fenton reaction, UV-C irradiation, and hydrolysis were employed. Liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry were used for identification of transformation products (TPs) and prediction of their molecular formulae. Despite the structural similarity between TPFPB and TPFPP, distinct differences in electrochemical behavior and degradation pathways were observed. TPFPB readily underwent hydroxylation and hydrolysis, resulting in a wide range of 49 TPs. A total of 28 TPs were newly identified, including oligomers and highly toxic dioxins. In contrast, TPFPP degraded exclusively under harsh conditions, requiring the development of innovative conditioning protocols for EC. In total, the simulation experiments yielded nine structurally different compounds, including seven previously undescribed, partially defluorinated TPs. This study highlights the potential risks associated with the use of FOCs in LiBs and provides insight into the complex environmental behavior of FOCs., (© 2024. The Author(s).)

Herein, the study reports the first electrochemical nickel-catalyzed enantioselective hydro-arylation/alkenylation of enones in an undivided cell with low-cost electrodes in the absence of external reductants and supporting electrolytes. Aryl bromides/iodides/triflates or alkenyl bromides are employed as electrophiles for the efficient preparation of more than 56 valuable β-arylated/alkenylated ketones in a simple manner (up to 97% yield, 97% ee). With the advantages of electrochemistry, excellent functional group tolerance and late-stage modification of complex natural products and pharmaceuticals made the established protocol greener and more economic. Mechanism investigation suggests that a Ni I /Ni III cycle may be involved in this electro-reductive reaction rather than metal reductant driven Ni 0 /Ni II cycle. Overall, the efficient electrochemical activation and turnover of the nickel catalyst avoid the drawbacks posed by the employment of stoichiometric amount of sensitive metal powder reductants., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The discovery of ferroelectricity in nanoscale hafnia-based oxide films has spurred interest in understanding their emergent properties. Investigation focuses on the size-dependent polarization behavior, which is sensitive to content and movement of oxygen vacancies. Though polarization switching and electrochemical reactions is shown to co-occur, their relationship remains unclear. This study employs X-ray photoelectron spectroscopy with depth sensitivity to examine changes in electrochemical states occurring during polarization switching. Contrasting Hf 0.5 Zr 0.5 O 2 (HZO) with Hf 0.88 La 0.04 Ta 0.08 O 2 (HLTO), a composition with an equivalent structure and comparable average ionic radius, electrochemical states are directly observed for specific polarization directions. Lower-polarization films exhibit more significant electrochemical changes upon switching, suggesting an indirect relationship between polarization and electrochemical state. This research illuminates the complex interplay between polarization and electrochemical dynamics, providing evidence for intrinsic polar states in HfO 2 -based ferroelectrics., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The UV/chlorine (UV/Cl 2 ) process is a developing advanced oxidation process and can efficiently remove antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs). However, the transportation and storage of chlorine solutions limit the application of the UV/Cl 2 process, especially for decentralized water treatment. To overcome the limitation, an electrochemically driven UV/Cl 2 process (E-UV/Cl 2 ) where Cl 2 can be electrochemically produced in situ from anodic oxidation of chloride (Cl - ) ubiquitously present in various water matrices was evaluated in this study. >5-log inactivation of the ARB (E. coli) was achieved within 5 s of the E-UV/Cl 2 process, and no photoreactivation of the ARB was observed after the treatment. In addition to the ARB, intracellular and extracellular ARGs (tetA, sul1, sul2, and ermB) could be effectively degraded (e.g., log(C 0 /C) > 4 for i-ARGs) within 5 min of the E-UV/Cl 2 process. Atomic force microscopy showed that the most of the i-ARGs were interrupted into short fragments (< 30 nm) during the E-UV/Cl 2 process, which can thus effectively prevent the self-repair of i-ARGs and the horizontal gene transfer. Modelling results showed that the abatement efficiencies of i-ARG correlated positively with the exposures of •OH, Cl 2 - •, and ClO• during the E-UV/Cl 2 process. Due to the short treatment time (5 min) required for ARB and ARG removal, insignificant concentrations of trihalomethanes (THMs) were generated during of the E-UV/Cl 2 process, and the energy consumption (E EO ) of ARG removal was ∼0.20‒0.27 kWh/m 3 -log, which is generally comparable to that of the UV/Cl 2 process (0.18-0.23 kWh/m 3 -log). These results demonstrate that the E-UV/Cl 2 process can provide a feasible and attractive alternative to the UV/Cl 2 process for ARB and ARG removal in decentralized water treatment system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The development of cost-effective and highly efficient electrocatalysts is critical to help electrochemical non-enzymatic sensors achieve high performance. Here, a new class of catalyst, Ru single atoms confined on Cu nanotubes as a single-atom alloy (Ru 1 Cu NTs), with a unique electronic structure and property, was developed to construct a novel electrochemical non-enzymatic glucose sensor for the first time. The Ru 1 Cu NTs with a diameter of about 24.0 nm showed a much lower oxidation potential (0.38 V) and 9.0-fold higher response (66.5 μA) current than Cu nanowires (Cu NWs, oxidation potential 0.47 V and current 7.4 μA) for glucose electrocatalysis. Moreover, as an electrochemical non-enzymatic glucose sensor, Ru 1 Cu NTs not only exhibited twofold higher sensitivity (54.9 μA mM -1  cm -2 ) and wider linear range (0.5-8 mM) than Cu NWs, but also showed a low detection limit (5.0 μM), excellent selectivity, and great stability. According to theoretical calculation results, the outstanding catalytic and sensing performance of Ru 1 Cu NTs could be ascribed to the upshift of the d-band center that helped promote glucose adsorption. This work presents a new avenue for developing highly active catalysts for electrochemical non-enzymatic sensors., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Voltage-responsive biosensors capable of monitoring real-time adsorption behavior of biological analytes onto electroactive surfaces offer attractive strategies for disease detection, separations, and other adsorption-dependent analytical techniques. Adsorption of biological analytes onto electrically switchable surfaces can be modelled using neutravidin and biotin. Here, we report self-assembled monolayers formed from voltage-switchable biotinylated molecules on gold surfaces with tunable sensitivity to neutravidin in response to applied voltages. By using electrochemical quartz crystal microbalance (EQCM), we demonstrated real-time switchable behavior of these bio-surfaces and investigate the range of sensitivity by varying the potential of the same surfaces from -400 mV to open circuit potential (+155 mV) to +300 mV. We compared the tunability of the mixed surfaces to bare Au surfaces, voltage inert surfaces, and switchable biotinylated surfaces. Our results indicate that quartz crystal microbalance allows real-time changes in analyte binding behavior, which enabled observing the evolution of neutravidin sensitivity as the applied voltage was shifted. EQCM could in principle be used in kinetic studies or to optimize voltage-switchable surfaces in adsorption-based diagnostics., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Through the utilization of fluorescence spectroscopy, electrochemical, and molecular docking methods, this research investigates the interaction between the antihistamine drug desloratadine and calf thymus double-stranded DNA (ct-dsDNA). Deoxyguanosine (dGuo) and deoxyadenosine (dAdo) oxidation signals were diminished by incubation with varying concentrations of desloratadine, as determined by differential pulse voltammetry (DPV). This change was ascribed to desloratadine's binding mechanism to ct-dsDNA. The binding constant (K b ) between desloratadine and ct-dsDNA was determined to be 2.2 × 10 5  M -1 throughout electrochemical experiments. In order to further develop our comprehension of the interaction mechanism between desloratadine and ct-dsDNA, a series of spectroscopic experiments and molecular docking simulations were conducted. The K b value was found to be 8.85 × 10 4  M -1  at a temperature of 25 °C by the use of fluorescence spectroscopic techniques. In summary, the utilization of electrochemical and spectroscopic techniques, alongside molecular docking investigations, has led to the prediction that desloratadine has the capability to interact with ct-dsDNA by groove binding., Competing Interests: Declaration of competing interest The authors state that none of their known financial conflicts or interpersonal connections could have influenced the work that was published in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Objective: We conducted a multi-institutional observational study to investigate whether maintenance hormone therapy following primary treatment of low-grade advanced-stage ovarian cancer (LGSOC) is associated with an overall survival advantage., Methods: We included patients with histologically confirmed stage III or IV LGSOC diagnosed between Jan 1, 2004, and Dec 31, 2019, treated in Commission on Cancer-accredited cancer programs in the US. Patients who received hormone therapy within six months of diagnosis were matched to controls who did not initiate hormone therapy during this timeframe by risk-set propensity score matching. The primary outcome was the risk of death from any cause within five years of initiation of HT or observation., Results: There were 296 patients who initiated maintenance hormone therapy within six months of diagnosis and 2805 potential controls. Patients who received hormone therapy were more often treated in academic medical centers (55% vs. 44%), diagnosed later in the study period (62% vs. 23% diagnosed in 2018-2019), and frequently received no chemotherapy during initial treatment (45% vs. 17%). After risk set propensity score matching, we identified 225 patients treated with HT and 225 untreated controls who were otherwise similar with respect to measured covariates. In the matched cohort, hormone therapy was associated with a reduction in the risk of death (hazard ratio 0.60; 95% CI 0.38-0.94), corresponding to a 60-month survival of 75% compared with 65%., Conclusions: Following primary management of LGSOC, maintenance hormone therapy was associated with improved overall survival compared with observation., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Nanozymes are a class of nanomaterials with biocatalytic function and enzyme-like activity, whose advantages include high stability, low cost, and mass production. They can catalyze the substrates of natural enzymes based on specific nanostructures and serve as substitutes for natural enzymes. Their applied research involves a wide range of fields such as biomedicine, environmental governance, agriculture, and food. Molecular logic gates are a new cross-disciplinary discipline, which can simulate the function of silicon circuits on a molecular scale, perform single or multiple input logic operations, and generate logic outputs. A molecular logic gate is a binary operation that converts an input signal into an output signal according to the rules of Boolean logic, generating two signals, a high level, and a low level. The high and low levels represent the "true" and "false" values of the logic gates, and their outputs correspond to "l" and "0" of the molecular logic gates, respectively. The combination of nanozymes and logic gates is a novel and attractive research direction, and the cross-application of the two brings new opportunities and ideas for various fields, such as the construction of efficient biocomputers, intelligent drug delivery systems, and the precise diagnosis of diseases. This review describes the application of logic gates based on nanozymes, which is expected to provide a certain theoretical foundation for researchers' subsequent studies., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

The increasingly complex electromagnetic (EM) environment necessitates advanced electrically controllable electromagnetic interference (EMI) shielding materials that can adapt to varying EM conditions. This study develops a flexible electrochemically tunable EMI shielding device based on ultrathin Ti 3 C 2 T x MXene films, exhibiting reversible shielding effectiveness (SE) modulation from 18.9 to 26.2 dB in X band at 0.1 and -1.5 V. Unlike the previously reported mechanism relying on interlayer spacing adjustments, the work leverages transformations of charging state and surface chemistry for tunability during the electrochemical process. The Ti 3 C 2 T x flake size is also evidenced to play a crucial role, with smaller flakes offering higher absorption modulation despite lower SE modulation, enabling the device with high designability. When integrated with Salisbury screen structure, the device achieves adjustable absorption from 93.560% at 0.1 V to 99.996% at -1 V, showing a tunable reflection suppression ratio up to 32 dB with an effective bandwidth of 4.2 GHz. Additionally, incorporating resonant cavity structure enables absorption-dominated (over 90%) microwave-responsive switching at 0.1 and -1.5 V. This work highlights significant potential of adaptive EMI shielding materials for applications in smart electronic protection, EM switch, and radar camouflage., (© 2024 Wiley‐VCH GmbH.)

Transition metal-catalyzed cross-coupling reaction between organometallic reagents and electrophiles is a potent method for constructing C(sp 2 )-C(sp 3 ) bonds. Given the characters of organometallic reagents, cross-reductive coupling is emerging as an alternative strategy. The resurgence of electrochemistry offers an ideal method for electrochemical reductive of cross-coupling electrophiles. Inspired by the mechanism of electrochemical metal hydride, our study proposed that Ni-H electrochemically catalyze the hydroarylation coupling of unactivated alkenes with aryl halides. 1,1-Diarylalkanes can be produced effectively. This method have advantages including mild conditions, excellent regioselectivity, and satisfactory yields., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

Galvanic corrosion of lead-tin solder in copper plumbing can be a major contributor to water lead contamination. Here, we report the electrochemical reversal of the copper-solder galvanic couple, in which the normally anodic solder becomes cathodic to copper via a reaction with free chlorine. This reversal occurred after a few months of exposure to continuously circulating water with relatively low pH and low alkalinity, causing dramatically decreased lead release and the formation of a Pb(IV) scale. Chloramine did not similarly inhibit solder corrosion over the 4-9 month test duration, resulting in up to 100 times more lead contamination of the water relative to free chlorine. These findings have major implications for corrosion control and public health and can help explain anomalously low levels of lead contamination in some waters with free chlorine that are normally considered corrosive to solder.

In coordination chemistry, 2,2':6',2″-terpyridine is a versatile and extensively studied tridentate ligand. Terpyridine forms stable complexes with a variety of metal ions through coordination sites provided by the three nitrogen atoms in its pyridine rings. This paper presents an electrochemical study on various bis(terpyridine)osmium(II) complexes, addressing the absence of a systematic investigation into their redox behavior. Additionally, a computational chemistry analysis was conducted on these complexes, as well as on eight previously studied osmium(II)-bipyridine and -phenanthroline complexes, to expand both the experimental and theoretical understanding. The experimental redox potentials, Hammett constants, and DFT-calculated energies show linear correlations due to the electron-donating or electron-withdrawing nature of the substituents, as described by the Hammett constants. These substituent effects cause shifts to lower or higher redox potentials, respectively.

The increasing demand for green hydrogen is driving the development of efficient and durable electrocatalysts for the hydrogen evolution reaction (HER). Nickel-molybdenum (NiMo) alloys are among the best HER electrocatalysts in alkaline electrolytes, and here we report a scalable solution precursor plasma spraying (SPPS) process to produce the highly active Ni 4 Mo electrocatalysts directly onto metallic substrates. The NiMo coating coated onto inexpensive Ni mesh revealed an excellent HER performance with an overpotential of only 26 mV at -10 mA cm -2 with a Tafel slope of 55 mV dec -1 . Excellent operational stability with minimum changes in overpotential were also observed even after extensive 60 hour high-current stability test. In addition, we investigate the influence of different substrates over the catalytic performance and operational stability. We also proposed that a slow, but consistent, dissolution of Mo is the primary degradation mechanism of NiMo-based coatings. This unique SPPS approach enables the scalable production of exceptional NiMo electrocatalysts with remarkable activity and durability, positioning them as ideal cathode materials for practical applications in alkaline water electrolysers., (© 2024 The Authors. ChemistryOpen published by Wiley-VCH GmbH.)

Polyoxometalates (POMs) are ideal components for reversible multi-electron storage in energy technologies. To-date, most redox-applications employ only single, individual POM species, which limits the number of electrons that can be stored within a given potential window. Here, we report that spontaneous redox self-equilibration during cluster synthesis leads to the formation of two structurally related polyoxovanadates which subsequently aggregate into co-crystals. This results in systems with significantly increased redox reactivity. The mixed POM system was formed by non-aqueous self-assembly of a vanadate precursor in the presence of Mg 2+ , resulting in two mixed-valent (V IV/V ) species, [(MgOH)V 13 O 33 Cl] 4- (={MgV 13 }) and the di-vanadium-functionalized species [V 14 O 34 Cl] 4- (={V 14 }), which co-crystallize in a 1 : 1 molar stoichiometry. Experimental data indicate that in the native state, {MgV 13 } is reduced by three electrons, and {V 14 } is reduced by five electrons. Electrochemical studies in solution show, that the system can reversibly undergo up to fourteen redox transitions (tentatively assigned to twelve 1-electron processes and two 2-electron processes) in the potential range between -2.15 V to +1.35 V (vs Fc + /Fc). The study demonstrates how highly redox-active, well-defined molecular mixtures of mixed-valent molecular metal oxides can be accessed by redox-equilibration during synthesis, opening new avenues for molecular energy storage., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Synthetic organic electrochemistry is recognized as one of the most sustainable forms of redox chemistry that can enable a wide variety of useful transformations. In this study, readily prepared pyrolytic carbon electrodes are explored in several powerful rAP transformations as well as C-C and C-N bond forming reactions. Pyrolytic carbon provides an alternative to classic amorphous carbon-based materials that are either expensive or ill-suited to large-scale flow reactions., (© 2024 Wiley-VCH GmbH.)

Hemicelluloses (HCs) are promising sustainable biopolymers with a great natural abundance, excellent biocompatibility, and biodegradability. Yet, their potential sensing applications remain limited due to intrinsic challenges in their heterogeneous chemical composition, structure, and physicochemical properties. Herein, recent advances in the development of HC-based sensors for different chemical analytes and physical stimuli using different transduction mechanisms are reviewed and discussed. HCs can be utilized as carbonaceous precursors, reducing, capping, and stabilizing agents, binders, and active components for sensing applications. In addition, different strategies to develop and improve the sensing capacity of HC-based sensors are also highlighted.

The chlorine evolution reaction (CER) is a crucial anode reaction in the chlor-alkali industrial process. Precious metal-based dimensionally stable anodes (DSA) are commonly used as catalysts for CER but are constrained by their high cost and low selectivity. Herein, a Pt dual singe-atom catalyst (DSAC) dispersed on fluorine-doped carbon nanotubes (F-CNTs) is designed for an efficient and robust CER process. The prepared Pt DSAC demonstrates excellent CER activity with a low overpotential of 21 mV to achieve a current density of 10 mA cm -2 and a remarkable mass activity of 3802.6 A g pt -1 at an overpotential around 30 mV, outperforming those of commercial DSA and Pt single-atom catalyst. The excellent CER performance of Pt DSAC is attributed to the high atomic utilization and improved intrinsic activity. Notably, introducing fluorine atoms on CNTs increases the oxidation and chlorination resistance of Pt DSAC, and reduces the demetalization ratio of Pt atoms, resulting in excellent long-term CER stability. Theoretical calculations reveal that several Pt DSAC configurations with optimized first-shell ligands and interatomic distance display lower energy barriers for Cl intermediates generation and weaker ionic Pt-Cl bond interaction, which are favorable for the CER process., (© 2024 Wiley-VCH GmbH.)

This work presents the results of a study on the effect of ionic surfactants: cationic hexadecyltriammonium bromide (CTAB) and anionic sodium salt of sulfonic acid (1OSASS) on the Bi(III) electroreduction process in mixed aqueous-organic supporting electrolyte solutions containing methanol. This study showed that the composition of the supporting electrolyte solution, particularly the methanol and surfactant concentrations, significantly affects the mechanism and rate of the Bi(III) ion electroreduction. Analysis of the influence of the indicated factors on the mechanisms and kinetics of metal ion electroreduction can contribute not only to the optimization of industrial electrochemical processes but also to the development of innovative technological solutions, such as advanced electrochemical materials and novel sensors. In these experiments, an innovative electrode made of cyclic renewable liquid silver amalgam (R-AgLAFE) was used as a working electrode, which stands out among classic mercury electrodes (HMDE type) due to the significant reduction in mercury consumption while maintaining similar performance.

Combining intercalation and conversion reactions maximizes the utilization of redox-active elements in electrodes, providing a means for overcoming the current capacity ceiling. However, integrating both mechanisms within a single electrode material presents significant challenges owing to their contrasting structural requirements. Intercalation requires a well-defined host structure for efficient lithium-ion diffusion, whereas conversion reactions entail structural reorganization, which can undermine intercalation capabilities. Based on the previous study that successfully demonstrated reversible intercalation-conversion chemistry in amorphous LiFeSO4F, this study aims to provide an in-depth understanding on how this can be enabled. Experimental and theoretical investigations of a model system based on tavorite-structured LiFeSO4F revealed that amorphization governs the activation and reversibility of the combined reactions. Enhanced reversibility is achieved through the facile migration of transition metals within the amorphous matrix. Unexpectedly, it is found that amorphization also narrowed the voltage gap between the intercalation and conversion reactions. This voltage-gap reduction is explained by the thermodynamic metastability of the amorphous phase. The applicability of the approach to other intercalation hosts is further demonstrated, showing that amorphization enables reversible intercalation and conversion. These findings suggest a new strategy that leverages the full potential of intercalation and conversion reactions, introducing new avenues for cathode design., (© 2024 Wiley‐VCH GmbH.)

Urea contamination in milk poses significant health risks, including kidney failure, urinary tract obstruction, fluid loss, shock, and gastrointestinal bleeding. This highlights the need for sensitive, rapid, and reliable methods to detect traces amount of urea in milk. In this study, we designed an electrochemical transducer for urea detection by utilizing purified watermelon urease (Urs), gold nanoparticles (AuNPs), and graphene oxide (GO). The nanomaterials and biosensor probe were characterized using UV-vis spectroscopy, XPS, TEM, XRD, FTIR, AFM, CV, EIS, and DPV. The engineered probe (GCE/AuNPs/GO/Urs) demonstrated a broad linear detection range of 5 to 90 mg/dL and a low limit of detection (LOD) of 0.037 (±0.012) mg/dL (RSD < 3.7%). The biosensor was tested for potential interferents that may be present in adulterated milk and an exceptionally low coefficient of selectivity (ksel <0.1) was obtained. Evaluation of milk samples from a local dairy farm showed good recovery rates from 93.13% to. 98.79% (RSD < 4.28%, n = 3), indicating reliable detection capabilities. Stability tests confirmed the sensor's reproducibility and consistent performance. Additionally, a comparison study of the system was carried out using the purified watermelon urease and the commercially available urease. Herein, the results obtained using the sensor probe was finally validated with the gold standard method.

Recently, many studies have been published regarding electrochemical oxygen reduction reaction for generating hydrogen peroxide (H 2 O 2 ) using gas diffusion electrodes (GDEs) for various applications. Sodium salts solved in deionized water were usually used as supporting electrolytes. In technical applications, however, tap water-based electrolytes with hardeners are particularly relevant and have only been considered in a few studies to date. In this work, we investigated the influence of hardeners on H 2 O 2 -generation at 150 mA cm -2 and were able to show that scaling occurs predominantly on the GDE-surface and not in its pore structure. With the novel method in electrochemical synthesis by using complexing agents to bind hardeners, we were able to significantly reduce the scaling. Even after 10 h of operation, the reactor still achieves a faradaic efficiency (FE) of above 70 % (>67 mg h -1  cm -2 ), comparable to the experiments without hardeners and complexing agents in the electrolyte. Furthermore, we demonstrate that the complexing agents are not electrochemically converted at the carbon-based GDE and behave inertly. If the cell is operated with complexing agents and rinsed with acidic liquid (anolyte) between batches, scaling can be completely avoided., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The cathodic reduction of pressurized CO 2 (PrCO 2 CR) at suitable cathodes can allow to produce various chemicals, such as formic acid/formate (FA) and carbon monoxide or synthesis gas, with high faradic efficiencies (FEs) and productivities. Here, we have performed the conversion of CO 2 in an undivided pressurized electrochemical reactor using silver cathode in order to determine the optimal values of CO 2 pressure and current density. It was found that the plot FE vs. pressure resulted in a curve with a maximum. Similarly, an optimal value of current density can be selected for the PrCO 2 CR. The competition between the production of carbon monoxide and formic acid/formate is strongly affected by both the pressure and the current density. Eventually the effect of pressure and current density on the economic figures of the process was evaluated., (© 2024 Wiley-VCH GmbH.)

2,5-bis(hydroxymethyl)furan (BHMF) derived from 5-Hydroxymethylfurfural (HMF) through a hydrogenation process has extensive applications in the production of resins, polymers, and artificial fibers. However, screening out the candidate and then modulating the active site to optimize the catalyst for high yield of BHMF are currently insufficient. In this study, Gibbs free energy diagrams of the reduction of HMF on 13 metals were presented, along with the identification of the rate-determining step (RDS) with the highest reaction barrier for each metal. We attempted to construct a volcano plot for HMFRR reaction. Additionally, a strategy was proposed to adjust the reaction barriers of RDS by combining two appropriate metals. Further experiments confirmed that Pb with the lowest energy barrier exhibited the highest HMF conversion (BHMF selectivity) among single metals. The modified catalyst by doping Ag on Pb, further boosted the HMF conversion (BHMF selectivity) from 42.1 % (59.4 %) to 80.8 % (80.9 %), respectively. These results provide an approach to rationally design and construct the catalyst system for efficient conversion of HMF., (© 2024 Wiley-VCH GmbH.)