Oxidation Potential Research Articles

Association between time of day and carbonaceous PM2.5 and oxidative potential in summer and winter in the Suncheon industrial area, Republic of Korea

Association between time of day and carbonaceous PM2.5 and oxidative potential in summer and winter in the Suncheon industrial area, Republic of Korea

External Short-Circuit Scenarios under Different Mechanical Pressures Applied to Lithium-Ion Cells with Silicon-Dominant Anodes

Abstract The safety behavior of lithium-ion cells using high contents of silicon as new anode active material was barely investigated. This work investigates the short-circuit behavior of self-manufactured single-layered pouch cells using 70%wt microscale silicon and NCA cathodes in a novel dual reference cell setup consisting of a gold wire and a lithium metal reference electrode. Six cells were externally shortened at three different compression levels using a novel developed quasi-isothermal calorimetric shortcircuit test bench. The same current plateaus and transition zones were observed for all pressure settings, as reported in the literature for graphite-containing anodes. In addition, a direct dependency of the short-circuit intensity and the heat generation is measured for the differently compressed cells. This higher short-circuit intensity was quantitatively explained by the decreasing impedance at increased pressure levels. The built-in reference electrodes allow for monitoring of the negative terminal voltage, revealing potentials of up to 3:508 V versus Li+/Li and thus explaining the measured over-discharge in the range of ≈25% SoC. The post-mortem analysis reveals copper deposition on both electrodes and the separator, confirming the electrochemically measured over-discharge. Linear scans and potential trajectories reveal 3.379 V versus Li+/Li as oxidation potential for copper dissolution using copper||lithium-metal coin cells.

Modulation for Redox States of Single-Walled Carbon Nanotubes: Effect of Wrapping Conjugated Polymers.

Controlling the redox states of single-walled carbon nanotubes (SWNTs) is important for the optimization of their real performances in various fields. By means of in situ photoluminescence (PL) spectroelectrochemical measurements, we report a successful modulation for the redox parameters (redox potentials and electrochemical band gap) of (6,5) and (7,5)SWNTs with a simple change in conjugated polymers (CPs) non-covalently wrapped on the nanotubes. The large shift in the band gap (187 meV for (6,5)SWNTs and 101 meV for (7,5)SWNTs) was connected to the prominent difference in the interactions between the CPs and SWNTs as suggested by molecular dynamics (MD) simulations, while a striking difference in the 𝜋-electrons states of CP/SWNTs enabled the tuning of SWNTs' electronic states. Asymmetrical modulation for the reduction potential (LUMO) and oxidation potential (HOMO) of the SWNTs was observed as well. Our results can be promising for a simple but precise control of the electric states of SWNTs.

Activating Oxygen via the 3‐Electron Pathway to Hydroxyl Radical by La‐O4 Single‐atom on WO3 for Water Purification

Shifting photocatalytic oxygen activation towards 3‐electron (e‐) pathway to hydroxyl radicals, instead of the normal 1 e‐ to superoxide radicals, becomes increasingly important for pollution degradation since hydroxyl radicals possess a high oxidation potential (2.80 V). Here, we demonstrate a selective oxygen activation to hydroxyl radicals via 3 e‐ pathway using single atomically dispersed La based on WO3 fabricated with oxygen vacancies to weaken La‐O coordination strength (denoted as LaO4‐WOv). Unsaturated‐state La overcomes the rate‐limited step of 2 e‐ oxygen reduction reaction towards to hydrogen peroxide via tuning binding free energy of key reaction intermediate *OOH, stepped by easy generation of hydroxyl radicals via 1 e‐. This strategy alters the activation of oxygen process from 1 e‐ to 3 e‐. Hydrogen peroxide and hydroxyl radicals over LaO4‐WOv produces 3.8 and 3.3 mmol L‐1 h‐1, 35 and 8 times that of detected over WO3, respectively. Rapid and complete removal of tetracycline realizes over LaO4‐WOv with 0.077 min‐1 of rate constant, 38 times that of WO3. Degradation efficiencies keep greater than 98% following five repeats, revealing a practical‐utilization‐level robust stability. This work builds an unsaturated‐state transition metal site for manipulating oxygen activation towards an effective water purification as a representative application.

Activating Oxygen via the 3-Electron Pathway to Hydroxyl Radical by La-O4 Single-atom on WO3 for Water Purification.

Shifting photocatalytic oxygen activation towards 3-electron (e-) pathway to hydroxyl radicals, instead of the normal 1 e- to superoxide radicals, becomes increasingly important for pollution degradation since hydroxyl radicals possess a high oxidation potential (2.80 V). Here, we demonstrate a selective oxygen activation to hydroxyl radicals via 3 e- pathway using single atomically dispersed La based on WO3 fabricated with oxygen vacancies to weaken La-O coordination strength (denoted as LaO4-WOv). Unsaturated-state La overcomes the rate-limited step of 2 e- oxygen reduction reaction towards to hydrogen peroxide via tuning binding free energy of key reaction intermediate *OOH, stepped by easy generation of hydroxyl radicals via 1 e-. This strategy alters the activation of oxygen process from 1 e- to 3 e-. Hydrogen peroxide and hydroxyl radicals over LaO4-WOv produces 3.8 and 3.3 mmol L-1 h-1, 35 and 8 times that of detected over WO3, respectively. Rapid and complete removal of tetracycline realizes over LaO4-WOv with 0.077 min-1 of rate constant, 38 times that of WO3. Degradation efficiencies keep greater than 98% following five repeats, revealing a practical-utilization-level robust stability. This work builds an unsaturated-state transition metal site for manipulating oxygen activation towards an effective water purification as a representative application.

First‐Principles Study on Electronic and Optical Properties of Novel Potential Photocatalytic Water‐Splitting Material: Blue‐P/Hf2CO2 vdW Heterostructure

ABSTRACTIn this work, we set a series of blue‐P/Hf2CO2 vdW heterostructures by stacking blue‐P and Hf2CO2 monolayers together. Then the most stable structure, the AD‐stacking blue‐P/Hf2CO2 vdW structure (the HS), is selected out for further investigation. The electronic and optical properties of the HS are studied for exploring its potential applications. Result of its electronic structure investigation indicates that the HS is a type‐I band arrangement. By applying different biaxial strains parallel to the stacking direction to the HS, we regulate its band gap and band edge positions. Results show a suitable strain not only can adjust the band alignment type of the HS change from type‐I to type‐II but also regulate the band structure to a suitable band edge positions for photocatalytic water splitting. The band edge position of HS (2%) across the oxidation and reduction potential indicates that it is a potential photocatalyst of water splitting at pH = 7. By calculating the absorption coefficient, we found the HS (2%) has a good light‐harvesting ability in visible light and UV region, which further proves it has the potential as the sunlight‐driven photocatalyst for water splitting.

Engineering Stable Decomposition Products on Cathode Surfaces to Enable High Voltage All‐Solid‐State Batteries

Sulfide solid electrolytes such as Li6PS5Cl hold high promise for solid state batteries due to their high ionic conductivity; however, their oxidation potential of ~2.5 V is not compatible with high voltage Ni‐rich cathodes such as LiNixCoyMn1−x−yO2 (x≥0.8). Here, we devise an effective, conformal and thin coating on the cathode active material guided by density functional theory, which suppresses the oxidative decomposition of Li6PS5Cl as shown by experiment. The nanometric coating on nickel‐rich NMC85 enabled capacity retention of 82% after 200 cycles (2.8‐4.3 V vs Li+/Li) using Li6PS5Cl as the solid electrolyte. In comparison, cells with an uncoated CAM only displayed 56% capacity retention. The coated‐NCM85 cells also demonstrate much better rate performance and higher capacity. The enhanced performance is due to the formation of a stable amorphous cathode‐electrolyte interphase accruing from the decomposition products of the LiPO2F2 precursor (as predicted by DFT), which protect the sulfide electrolyte from oxidation. The coating fabricated in this cost‐effective process showed superior performance to state‐of‐the‐art coatings such as LiNbO3. This work highlights the importance of rationally designing stable coating materials based on their potential decomposition products and confirms the suitability of a low‐cost and conformal coating to enable sulfide electrolyte‐based all‐solid‐state batteries.

Hydroxyl and sulfate radicals-based electrochemical advanced oxidation process for treating dye-bearing wastewater – a review

ABSTRACT Dye-bearing wastewater presents a substantial ecological risk. Consequently, there is a critical requirement for efficient treatment strategies. Electrochemical advanced oxidation processes (EAOPs) utilizing hydroxyl and sulfate radicals emerge as viable alternatives to degrade dye pollutants effectively. This review article emphasizes the implementation of EAOPs in the treatment of both synthetic and actual dye-bearing wastewater. The fundamentals, chemistry, and recent developments concerning hydroxyl radicals-based EAOP, including anodic oxidation, electro-Fenton, and sulfate radicals-based EAOP, have been thoroughly reviewed. Furthermore, the article explores the comparative effectiveness of the individual hydroxyl and sulfate radical systems as well as the integrated hydroxyl and sulfate radical systems within a singular electrochemical cell. It has been established that sulfate radicals demonstrate a higher oxidation potential, greater pH adaptability, and a longer half-life in comparison to hydroxyl radicals, making them efficient for dye degradation when assessed against anodic oxidation and electro-Fenton processes. Thus, EAOPs represent a promising technological approach for the remediation of dye-bearing wastewater.

Abstract 4137907: Elevated Plasma Neopterin Levels in Patients with Takotsubo Cardiomyopathy

Background: Takotsubo cardiomyopathy (TC) is characterized by left ventricular apical ballooning and intact coronary arteries. The pathogenesis of this disorder is likely to be catecholamine-mediated myocyte damage, microvascular dysfunction and subsequent oxidative stress; however, a number of possible alternative theories have been suggested. Neopterin is produced by activated macrophages following stimulation by interferon-g produced by T-lymphocytes and is capable of enhancing the oxidative potential of reactive oxygen species. The aim of this study was to compare plasma neopterin levels between TC patients and patients with coronary artery disease. Methods: Plasma neopterin levels were measured on admission in patients with TC (n=37), stable angina pectoris (SAP, n=66), unstable angina pectoris (UAP, n=72) and acute myocardial infarction (AMI, n=67) using HPLC. A frozen myocardium specimen was obtained by biopsy from a patient with TC and stained for neopterin, macrophages, and microvessels using immunohistochemistry. Results: Plasma neopterin levels were significantly higher in TC patients compared with SAP patients ( P <0.0001) or UAP patients ( P <0.05), although they were not significantly different from those in AMI patients. In TC patients, plasma neopterin levels correlated positively with neutrophil count (R=0.47, P<0.05) and serum C-reactive protein levels (R=0.38, P<0.05). Immunohistochemical staining showed abundant neopterin-positive macrophages in the myocardium specimen from the patient with TC. Conclusions: This study demonstrates, for the first time, that plasma neopterin levels are elevated in TC patients compared with those in SAP and UAP patients. These findings suggest that neopterin may play an important role in the pathophysiology of Takotsubo cardiomyopathy.

Engineering Stable Decomposition Products on Cathode Surfaces to Enable High Voltage All-Solid-State Batteries.

Sulfide solid electrolytes such as Li6PS5Cl hold high promise for solid state batteries due to their high ionic conductivity; however, their oxidation potential of ~2.5 V is not compatible with high voltage Ni-rich cathodes such as LiNixCoyMn1-x-yO2 (x≥0.8). Here, we devise an effective, conformal and thin coating on the cathode active material guided by density functional theory, which suppresses the oxidative decomposition of Li6PS5Cl as shown by experiment. The nanometric coating on nickel-rich NMC85 enabled capacity retention of 82% after 200 cycles (2.8-4.3 V vs Li+/Li) using Li6PS5Cl as the solid electrolyte. In comparison, cells with an uncoated CAM only displayed 56% capacity retention. The coated-NCM85 cells also demonstrate much better rate performance and higher capacity. The enhanced performance is due to the formation of a stable amorphous cathode-electrolyte interphase accruing from the decomposition products of the LiPO2F2 precursor (as predicted by DFT), which protect the sulfide electrolyte from oxidation. The coating fabricated in this cost-effective process showed superior performance to state-of-the-art coatings such as LiNbO3. This work highlights the importance of rationally designing stable coating materials based on their potential decomposition products and confirms the suitability of a low-cost and conformal coating to enable sulfide electrolyte-based all-solid-state batteries.

A General Hydrotrifluoromethylation of Unactivated Olefins Enabled by Voltage‐Gated Electrosynthesis

AbstractHere we present the first successful hydrotrifluoromethylation of unactivated olefins under electrochemical conditions. Commercially available trifluoromethyl thianthrenium salt (TT+−CF3BF4−, Ep/2=−0.85 V vs Fc/Fc+) undergoes electrochemical reduction to generate CF3 radicals which add to olefins with exclusive chemoselectivity. The resulting carbon centered radical undergoes a second cathodic reduction, instead of a classical HAT process, to generate a carbanion that can be terminated by protonation from solvent. The use of MgBr2 (+0.20 V onset oxidation potential) plays a key role as an enabling sacrificial reductant for the reaction to operate in an undivided cell. Guided by cyclic voltammetry (CV) studies, fine‐tuning the solvent system, trifluoromethylating reagent's counteranion and careful selection of redox processes, this work led to the development of a voltage‐gated electrosynthesis by pairing two redox processes with a narrow potential difference (ΔE≈1.00 V) allowing the reaction to proceed with two important advances: (a) high reactivity and selectivity towards hydrotrifluoromethylation over undesired dibromination, and (b) an unprecedented functional group tolerance, including aniline, phenols, unprotected alcohol, epoxide, trialkyl amine, and several redox sensitive heterocycles.

Thermodynamic Assessment of Sacrificial Oxidant Potential, H2O/O2 Potential, and Rate-Overpotential Relationship to Examine Catalytic Water Oxidation in Nonaqueous Solvents.

The water oxidation reaction (WOR), which is pivotal to storing energy in chemical bonds, requires a catalyst to overcome its inherent kinetic barrier. In bulk solutions, sacrificial oxidants (SOs) can regenerate the catalysts to ensure that the homogeneous WOR can be operated with long-term consistent performance. To implement this strategy for organic WOR systems, we modified four common SOs with tetra-n-butylammonium ([NBu4]+)─[NBu4]2[Ce(NO3)6], [NBu4][IO4], [NBu4][HSO5], and [NBu4]2[S2O8]─and examined their chemical stability and electrochemical behaviors in various organic solvents. We also derived the organic-solvent-associated redox potential of H2O/O2 in organic media (EH2O/O2(org)) using open-circuit potential measurements of the H+/H2 redox couple and the related thermochemical cycle. Our findings indicate that the EH2O/O2(org) varies with solvent identity and can be adjusted by changing the [H2O], [acid], and [base] levels; thus, the SO should be carefully selected for WOR, because the innate redox potentials of SOs are not always higher than EH2O/O2(org) under the studied conditions. Lastly, we obtained catalyst-performance-related insights via a rate-overpotential free-energy relationship by calculating the overpotentials of previously studied WOR systems in organic media.

Determining plasma dose using equivalent total oxidation potential (ETOP): Concept to practical application via machine learning

Atmospheric pressure nonequilibrium plasma holds significant potential in biomedical applications due to its ability to generate reactive species at low temperatures. However, accurately quantifying and controlling plasma dosage remains challenging. Although equivalent total oxidation potential (ETOP) has been proposed for defining dosage, previous methods required measurement of various reactive oxygen and nitrogen species (RONS) densities, which are impractical in diverse plasma settings. Efficient ETOP prediction across variable conditions is thus essential. To address this, we propose a machine learning-based ETOP modeling method. This study collected RONS density data under various conditions using laser-induced fluorescence and trained an artificial neural network to predict ETOP values based on input parameters like voltage, gas flow rate, oxygen concentration, and humidity. This approach enables efficient ETOP prediction across variable conditions, supporting the standardization and clinical application of plasma medicine.

Data-Based Prediction of Redox Potentials via Introducing Chemical Features into the Transformer Architecture.

Rapid and accurate prediction of basic physicochemical parameters of molecules will greatly accelerate the target-orientated design of novel reactions and materials but has been long challenging. Herein, a chemical language model-based deep learning method, TransChem, has been developed for the prediction of redox potentials of organic molecules. Embedding an effective molecular characterization (combining spatial and electronic features), a nonlinear molecular messaging approach (Mol-Attention), and a perturbation learning method, TransChem, shows high accuracy in predicting the redox potential of organic radicals comprising over 100,000 data (R2 > 0.97, MAE <0.09 V) and is generalized to the smaller 2,1,3-benzothiadiazole data set (<3000 data points) and electron affinity data set (660 data) with low MAE of 0.07 V and 0.18 eV, respectively. In this context, a self-developed data set, i.e., the oxidation potential (OP) of a full-space disubstituted phenol data set (OPP-data set, total set: 74,529), has been predicted by TransChem with a high-throughput, and active learning strategy. The rapid and reliable prediction of OP could hopefully accelerate the screening of plausible reagents in highly selective cross-coupling of phenol derivatives. This study presents an important attempt to guide language modeling with chemical knowledge, while TransChem demonstrates state-of-the-art (SOTA) predictive performance on redox potential prediction benchmark data sets for its better understanding of molecular design and conformational relationships.

Exploring potential of graphene oxide as an alternative antiviral approach for influenza A H1N1.

Aim: Graphene oxide (GO), known for its distinctive physicochemical properties, shows promise as a nanomaterial capable of combating infectious agents. This study investigates the efficacy of GO nanoparticles in restricting influenza A H1N1 replication in MDCK cells.Methods: GO nanoparticles were synthesized. After evaluating the toxicity of GO nanoparticles, the antiviral activity of the highest nontoxic concentration of GO against influenza A H1N1 in MDCK cells was studied.Results: GO treatments resulted in substantial decreases in virus titers, as shown via hemagglutination assay, TCID50 assay and real-time PCR analysis.Conclusion: This study emphasizes that GO nanoparticles have a high level of effectiveness against influenza A H1N1 viruses, making them an intriguing option for various antiviral uses.

Tracking Water Dissociation on RuO2(110) Using Atomic Force Microscopy and First-Principles Simulations.

The interaction between interfacial water and transition metal oxides is a primary enabling step for the oxygen evolution reaction (OER). RuO2 is a prototypical OER electrocatalyst whose ability to activate interfacial water molecules is essential to its OER activity. We image the dissociation of surface water into OH* and O* on RuO2(110), where * denotes adsorbed species, using atomic force microscopy. Starting from the surface-bound water molecules, which form a one-dimensional network along the rows of Ru surface sites, increasing the oxidative potential strips hydrogen away and transforms the water molecules into OH* and O*. This oxidative step changes the pattern of the adsorbates from one- to two-dimensional. First-principles calculations with interfacial polarization, capacitive charging, and adsorbate interactions attribute this evolution to the cooperative dehydrogenation of adsorbed water and OH* on RuO2. We use these results to map the surface phase diagram of RuO2(110) and provide a quantitative interpretation of its cyclic voltammetry. Our result provides the visualization of the water dissociation on a conductive oxide surface, a critical step in the OER, and demonstrates that the water activation is a collective phenomenon at RuO2(110) electrodes.

Seasonal dynamics of bacterial community structure and function in the surf zone seawater of a recreational beach in Ostend, Belgium.

Despite the importance of bacteria in surf zone water quality, detailed insights into their community composition, functions, and seasonal dynamics at recreational beaches are scarce. This study conducted year-long, weekly monitoring of bacterial communities and environmental factors at a recreational beach in Ostend, Belgium. Using full-length 16S rRNA gene sequencing, we correlated bacterial composition and predicted functions with environmental factors to identify potential drivers. Bacterial communities were significantly affected by seasonal variations in chlorophyll a (Chl a), net primary productivity (NPP), and seawater temperature (SWT), with minimal influence from faecal inputs due to human activities. Spring showed distinct abundances of Planktomarina, Amylibacter, and Sulfitobacter, positively correlated with Chl a and related to sulphur oxidation potential. Summer had higher abundances of Cryomorphaceae, likely enhancing chemoheterotrophy. Beginning in mid to late fall and extending into winter, bacterial communities underwent substantial changes. Fall featured a distinctive enrichment of Thioglobaceae, inversely correlated with Chl a. Winter was dominated by Methylophilaceae (OM43 clade), negatively correlated with Chl a, NPP, and SWT. Both seasons exhibited elevated levels of potentially pathogenic phenotypes and predicted functions related to methanol oxidation and methylotrophy. This study provides a baseline for understanding how surf zone bacterial communities respond to environmental changes and impact health.

Enabling Efficient Oxygen Evolution via Anchoring Carbon-Layer-Confined RuOx on a Well-Matched Substrate.

Oxygen evolution reaction (OER) is a multistep proton-coupled four-electron process with sluggish kinetics, which seriously limits the hydrogen production efficiency, thus it is of great importance to develop an efficient and stable OER catalyst. In this study, a two-step differential pyrolysis strategy is employed to design a three-dimensional porous microstructured material consisting of RuOx nanoparticles coated by a thin-layer carbon, where the active particles were isolated in separate chambers and the RuOx nanoparticles mainly existed in the form of a heterogeneous interface between RuO2 and partial metallic Ru. The preparation parameters of the catalysts are optimized via combining transient and steady-state polarization properties, and the target catalyst Cat-500-1.5t shows the best OER catalytic performance after ca. 60 h of a chronopotentiometry test in an acidic medium with a much smaller performance change than other samples. The unique design of adopting a carbon layer to form separate reaction chambers largely mitigates the excessive oxidation loss of the active components under strong oxidation potential. The suitability of the catalyst with the loaded substrate and test media is explored, and in an acidic medium, the carbon paper is much better than the titanium fiber, while in an alkaline medium, the titanium fiber is obviously superior to the carbon paper. On both carbon paper and titanium fiber, the performance in an alkaline medium outperforms that in an acidic medium, and the possible reasons for the performance difference are analyzed. Herein, to obtain the actual electrocatalytic performance, the optimal design of the catalyst structure and matching suitable conductive substrate in a specific medium are quite necessary, which provides a feasible strategy for the acquisition of efficient and stable electrocatalysts and the desirable presentation of performance.

Vertically Expanded Covalent Organic Frameworks for Photocatalytic Water Oxidation into Oxygen

Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π‐stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy for developing vertically expanded frameworks to expose originally inaccessible active sites hidden in layers to catalysis. We designed covalently linked two‐dimensional cobalt(II) porphyrin layers and explored coordination bonds to connect the cobalt(II) porphyrin layers with bidentate ligands via a three‐component one‐pot polymerization. The frameworks expand the interlayer space greatly, where both the up and down faces of each cobalt(II) porphyrin layer are exposed to reactants. Unexpectedly, the vertically expanded frameworks increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity and affinity to water, and facilitate water delivery. Remarkably, these positive effects work collectively in the photocatalysis of water oxidation into oxygen, with an oxygen production rate of 1155 µmol g−1 h−1, a quantum efficiency of 1.24% at 450 nm, and a turnover frequency of 1.39 h−1, which is even 5.1‐fold as high as that of the π‐stacked frameworks and ranks them the most effective photocatalysts. This strategy offers a new platform for designing layer frameworks to build various catalytic systems for chemical transformations.

Vertically Expanded Covalent Organic Frameworks for Photocatalytic Water Oxidation into Oxygen.

Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π-stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy for developing vertically expanded frameworks to expose originally inaccessible active sites hidden in layers to catalysis. We designed covalently linked two-dimensional cobalt(II) porphyrin layers and explored coordination bonds to connect the cobalt(II) porphyrin layers with bidentate ligands via a three-component one-pot polymerization. The frameworks expand the interlayer space greatly, where both the up and down faces of each cobalt(II) porphyrin layer are exposed to reactants. Unexpectedly, the vertically expanded frameworks increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity and affinity to water, and facilitate water delivery. Remarkably, these positive effects work collectively in the photocatalysis of water oxidation into oxygen, with an oxygen production rate of 1155 µmol g-1 h-1, a quantum efficiency of 1.24% at 450 nm, and a turnover frequency of 1.39 h-1, which is even 5.1-fold as high as that of the π-stacked frameworks and ranks them the most effective photocatalysts. This strategy offers a new platform for designing layer frameworks to build various catalytic systems for chemical transformations.