Change In Oxidation State Research Articles

Redox proteomic analysis of H2O2 -treated Jurkat cells and effects of bicarbonate and knockout of peroxiredoxins 1 and 2

Oxidation of thiol proteins and redox signaling occurs in cells exposed to H2O2 but mechanisms are unclear. We used redox proteomics to seek evidence of oxidation of specific proteins either by a mechanism involving reaction of H2O2 with CO2/bicarbonate to give the more reactive peroxymonocarbonate, or via a relay involving peroxiredoxins (Prdxs). Changes in oxidation state of specific Cys-SH residues on treating Jurkat T lymphoma cells with H2O2 were measured by isotopically labeling reduced thiols and analysis by mass spectrometry. The effects of bicarbonate and of knocking out either Prdx1 or Prdx2 were examined. Approximately 14,000 Cys-peptides were detected, of which ∼ 1% underwent 2-10 fold loss in thiol content with H2O2. Those showing the most oxidation were not affected by the presence of bicarbonate or knockout of either Prdx. Consistent with previous evidence that bicarbonate potentiates inactivation of glyceraldehyde-3-phosphate dehydrogenase, the GAPDH active site Cys residues were significantly more sensitive to H2O2 when bicarbonate was present. Several other proteins were identified as promising candidates for further investigation. Although we identified some potential protein candidates for Prdx- dependent oxidation, most of the significant differences between KO and WT cells were seen in proteins for which H2O2 unexpectedly increased their CysSH content over untreated cells. We conclude that facilitation of protein oxidation by bicarbonate or Prdx-mediated relays is restricted to a small number of proteins and is insufficient to explain the majority of the oxidation of cell thiols that occurs in response to H2O2.

Deciphering the Ce3+to Ce4+Evolution: Insight from X-ray Raman Scattering Spectroscopy at Ce N4,5Edges.

Cerium oxide, or ceria, (CeO2) is one of the most studied materials for its wide range of applications in heterogeneous catalysis and energy conversion technologies. The key feature of ceria is the remarkable oxygen storage capacity linked to the switch between Ce4+ and Ce3+ states, in turn creating oxygen vacancies. Changes in the electronic structure occur with oxygen removal from the lattice. Accordingly, the two valence electrons can be accommodated by the reduction of support cations where the electrons can be localized in empty f states of Ce4+ ions nearby.Quantifying the different oxidation states in situ is crucial to understand and model the reaction mechanism. Beside the different techniques to quantify Ce3+ and Ce4+ states, we discuss the use of X-ray Raman Scattering (XRS) spectroscopy as an alternative method. In particular, we show that XRS can observe the oxidation state changes of cerium directly in the bulk of the materials under realistic environmental conditions. The Hilbert++ code is used to simulate the XRS spectra and quantify accurately the Ce3+ and Ce4+ content. These results are compared to those obtained from in situ X-ray Diffraction (XRD) collected in parallel and the differences arising from the two different probes are discussed.

Long-term effects of transition milk feeding on feed intake, growth performance, feeding behavior, and oxidative status of Holstein calves

This study investigated the long-term effects of feeding 5-d transition milk (TRANS) compared with milk replacer (MR) on parameters, including intake, growth, feeding behavior and oxidative stress. Fifty Holstein calves (30 females and 20 males) were fed either 12 L/day TRANS or MR for the first 5 d after an initial colostrum feeding of 3.5 L. Thereafter, all calves were fed with 12 L of MR/d (140 g/L) and were gradually weaned starting in wk 8 until wk 14. Throughout the 14 wk the calves had unrestricted access to concentrate (up to 9.8 kg/calf/day), hay, and water. After weaning all heifers were fed a total mixed ration for young cows. Oxidative status was assessed in blood samples from birth to first insemination. Parameters assessed included the ferric reducing ability of plasma (FRAP) for antioxidant capacity and the concentration of reactive oxygen metabolites by the dROM (detection of reactive oxygen metabolites) assay. In addition, the activity of glutathione peroxidase (GSH-Px), oxidative damage in the form of lipid peroxidation as thiobarbituric acid reactive substances (TBARS) and as advanced oxidation protein products (AOPP) were measured. An oxidative stress index (OSi) was calculated: dROM/FRAP x 100. Total protein (TP) concentration was also quantified via the Bradford assay. The only significant difference in feeding behavior between the 2 treatment groups was a higher concentrate intake by the TRANS calves during the weaning phase. Body weight and ADG did not differ significantly between the TRANS and MR groups. TRANS calves showed a trend for fewer cases of health disorders. Markers of oxidative status, including TBARS, AOPP, GSHPx, FRAP and ROM, showed no treatment effects but varied significantly over time. Of note, the oxidative stress index as ratio between pro- and antioxidants in both groups peaked during weaning and then returned to baseline, suggesting an effective response to this transition phase Overall, the results indicate that feeding TRANS during the first 5 d of life had no long-term effect on the parameters studied as compared with MR feeding under the present rearing conditions. These results provide insight into the changes of oxidative status with age and confirm that the relatively high milk feeding level, slow and late weaning enables calves to adapt well to solely solid feed.

Microplastics originated from Plasmix-based materials caused biochemical and behavioral adverse effects on Daphnia magna

The implementation of advanced recycling techniques represents a key strategy for mitigating the mismanagement and the environmental impact of plastic waste. A limited array of plastic polymers can be efficiently recycled, while a notable portion of plastic waste remains unrecyclable. In Italy, this residual, heterogeneous fraction is referred to as Plasmix. Because of its complexity and non-homogeneous composition, Plasmix is primarily directed towards low-value applications. However, recent developments in laboratory-scale mechanical recycling have enabled the creation of new plastic materials from Plasmix. Prior to their application, these materials must undergo rigorous eco-safety evaluation. The present study aims to assess the potential toxicity of microplastics (MPs) from Plasmix-based materials on the freshwater crustacean Daphnia magna. Specifically, this study investigated sub-individual and individual effects induced by a 21-day exposure to different concentrations of MPs generated from the grinding of naïve and Additivated Plasmix-based materials (hereafter referred to as Px-MPs and APx-MPs, respectively). Sub-individual endpoints focused on changes in oxidative status, including the modulation of antioxidant and detoxifying enzyme activities, as well as oxidative damage, such as lipid peroxidation. Individual level endpoints included alterations in survival and reproduction. Microscopy analyses confirmed the ingestion of both Px-MPs and APx-MPs by D. magna individuals. An oxidative stress condition raised in organisms exposed to Px-MPs, whereas no effect was observed in individuals exposed to APx-MPs. Although survival was not affected, a significant impairment in reproductive output was detected at the end of exposure to all the concentrations of both MP types. These findings suggest that even low concentrations of Px-MPs and APx-MPs could negatively affect the health status of D. magna, underscoring the need for further research to complete the risk assessment of Plasmix-based materials prior to their use in consumer products.

Durable electrocatalysts based on barium niobates doped with Ca, Fe, and Y: Enhancing catalytic activity and selectivity for oxidative coupling of methane

Effective conversion of methane into value added products such as olefins, is a major research area for the past 40 years. Electrochemical oxidative coupling of methane (E-OCM) is recently gaining attention due to its ability to control the product selectivity by oxide ion flux and applied potential. We report a new series of catalysts, Ca, Fe, and Y co-doped barium niobate perovskites (BCNFY) for E-OCM application. BCNFY perovskites show chemical stability under 4 % H2, CH4, and high CH4-O2 mixtures at high temperatures up to 900 °C. Under reducing conditions, BCNFY perovskites form excess oxygen vacancies that is supported by Nb4+/5+ oxidation state changes that help retain the crystal structure. Temperature programmed reaction (TPR) measurements under 95 % CH4:5% O2 reveal methane activation properties from 600 °C with a high C2+ selectivity of 82 % at 850 °C. TPR measurements further reveal the nature of active sites for methane activation. Cyclic voltammetry measurements show a unique relationship between product selectivity and applied potential as at applied biases close to open circuit potential, CO and H2 are the major products while at high applied biases ethylene and CO2 are the major products. Our results show the advantages of E-OCM over conventional OCM although improvements in terms of electronic conductivity of the electrode and overall current densities are required for commercial viability for these perovskite electrodes.

Effects of In-Air Post Deposition Annealing Process on the Oxygen Vacancy Content in Sputtered GDC Thin Films Probed via Operando XAS and Raman Spectroscopy.

We investigate the ionic mobility in room-temperature RF-sputtered gadolinium doped ceria (GDC) thin films grown on industrial solid oxide fuel cell substrates as a function of the air-annealing at 800 and 1000 °C. The combination of X-ray diffraction, X-ray photoelectron spectroscopy, operando X-ray absorption spectroscopy, and Raman spectroscopy allows us to study the different Ce3+/ Ce4+ ratios induced by the post growth annealing procedure, together with the Ce valence changes induced by different gas atmosphere exposure. Our results give evidence of different kinetics as a function of the annealing temperature, with the sample annealed at 800 °C showing marked changes of the Ce oxidation state when exposed to both reducing and oxidizing gas atmospheres at moderate temperature (300 °C), while the Ce valence is weakly affected for the 1000 °C annealed sample. Raman spectra measurements allow us to trace the responses of the investigated samples to different gas atmospheres on the basis of the presence of different Gd-O bond strengths inside the lattice. These findings provide insight into the microscopic origin of the best performances already observed in SOFCs with a sputtered GDC barrier layer annealed at 800 °C and are fundamental to further improve sputtered GDC thin film performance in energy devices.

In Situ X-ray Absorption Spectroscopy Study of the Deactivation Mechanism of a Ni-SrTiO3 Photocatalyst Slurry Active in Water Splitting.

We used in situ X-ray absorption spectroscopy (XAS) to investigate the composition-performance correlation of Ni-SrTiO3 photocatalysts active for water splitting. After preparation and exposure to ambient conditions, the Ni particles on SrTiO3 consist of Ni(0) and Ni(II) phases, with a 4:1 at % ratio, in a metal/oxide core/shell configuration, as confirmed by XPS and TEM-EDX. In situ XAS experiments using an aqueous slurry of the Ni-SrTiO3 photocatalyst and simultaneous continuous exposure to 365 nm light with a power density of 100 mW cm-2 and the X-rays do not reveal significant changes in oxidation state of the Ni particles. Contrarily, when the X-rays are discontinuously applied, UV excitation leads to oxidation of a significant fraction of Ni(0) to Ni(II), specifically to NiO and Ni(OH)2 phases, along with cocatalyst restructuring. Ni dissolution or oxidation to higher valence states (e.g., Ni(III)) was not observed. The UV light-induced oxidation of Ni(0) causes the hydrogen evolution rate to drop to similar rates as observed for pristine SrTiO3, suggesting that Ni(0) is the active phase for H2 generation. Our results underscore the importance of assessing the effects of (continuous) X-ray exposure to (photo)catalyst-containing aqueous slurries during in situ XAS experiments, which can significantly influence the observation of compositional and structural changes in the (photo)catalysts. We ascribe this to X-ray induced water photolysis and formation of free electrons, which in this study quench SrTiO3 photoholes and prevent Ni oxidation.

PSVI-14 Effects of poor maternal nutrition during gestation on first generation offspring oxidative status in skeletal muscle

Abstract Poor maternal nutrition (restricted- and over-nutrition) during gestation negatively impacts offspring pre- and post-natal growth. Previous work has identified decreased muscle mass and increased adiposity, leading to poor quantity and quality of animal protein products. Alterations in oxidative status, such as the imbalance of antioxidant activity and the production of free radicals, can result in oxidative stress damaging lipid membranes, proteins, and DNA. Changes in oxidative status may contribute to the poor growth outcomes observed in offspring from poorly nourished dams. Therefore, the objective of this research was to determine the effects of poor maternal nutrition during gestation on the oxidative status in offspring skeletal muscle in sheep. We hypothesized that offspring of restricted- and over-fed ewes would have decreased antioxidant activity and increased products of oxidative stress in skeletal muscle. To test this hypothesis, multiparous Dorset ewes (n = 46) pregnant with twins were fed 100% (CON), 60% (RES), or 140% (OVER) of total nutrient requirements (NRC) from d 30 of gestation until parturition. Following parturition, ewes were fed a control diet throughout lactation. At d 282 of age semitendinosus (STN) samples were collected from rams at necropsy, and at d 284 of age muscle biopsies from STN were collected from ewes. Data were analyzed in SAS using PROC MIXED with fixed effects of maternal diet and offspring sex. Data were considered significant at P ≤ 0.05. The activity of the endogenous antioxidant superoxide dismutase (SOD) was decreased by 45% and 33% in RES and OVER offspring, respectively, compared with CON (P ≤ 0.01). Offspring sex did not alter STN SOD activity (P = 0.35). Muscle glutathione peroxidase (GPx) activity was decreased in RES offspring by 20% compared with CON (P ≤ 0.04), but neither differed from OVER offspring (P ≥ 0.24). Ewes had 34% greater GPx activity compared with rams (P < 0.0001). Offspring from RES and OVER ewes had 77% and 87% greater concentrations of malondialdehyde (MDA), a marker of lipid peroxidation, when compared with CON (P < 0.0001). Ewes had 29% greater MDA concentrations compared with rams (P = 0.05). Protein carbonyl (PC), a marker of protein oxidation, concentrations were 36% and 38% greater in RES and OVER offspring, respectively, compared with CON (P ≤ 0.01). The decrease in antioxidant activities and increase in products of protein and lipid oxidation in offspring from poorly nourished dams suggests dysregulation in skeletal muscle oxidative status that may contribute to the negative consequences observed in offspring. Future work should focus on determining the mechanistic role of skeletal muscle oxidative stress in the decreased quantity and quality of animal protein products and identifying potential strategies to mitigate alterations in oxidative status as a result of poor maternal nutrition during gestation.

Natural modulation of redox status throughout the ontogeny of Amazon frog Physalaemus ephippifer (Anura, Leptodactylidae)

During their development, amphibians undergo various physiological processes that may affect their susceptibility to environmental pollutants. Naturally occurring fluctuations caused by developmental events are often overlooked in ecotoxicological studies. Our aim is to investigate how biomarkers of oxidative stress are modulated at different stages of larval development in the Amazonian amphibian species, Physalaemus ephippifer. The premetamorphosis, prometamorphosis and metamorphic climax stages were used to analyze total antioxidant capacity (ACAP), glutathione S-transferase (GST) activity, lipid peroxidation (LPO) levels and the expression of genes nrf2, gst, gsr (glutathione reductase) and gclc (glycine-cysteine ligase, catalytic subunit). Although there was no difference in ACAP and the genes expression among the studied stages, individuals from the premetamorphosis and prometamorphosis showed higher GST activity than ones under the climax. LPO levels were highest in individuals from the metamorphic climax. The present study suggests that the oxidative status changes during ontogeny of P. ephippifer tadpoles, especially during the metamorphic climax, the most demanding developmental phase. Variations in the redox balance at different developmental stages may lead to a divergent response to pollution. Therefore, we recommend that studies using anuran larvae as biomonitors consider possible physiological differences during ontogeny in their respective analyses.

Insights into the Phases Transformation of Copper and Nickel Catalysts during Partial Oxidation and Steam Reforming of Methane

AbstractThe paper shows the structural changes of copper and nickel catalysts in the presence of strong (O2) and weak (H2O) oxidizing agents and their influence on the course of methane conversion. The changes in oxidation states of investigated catalysts were studied during partial oxidation and steam reforming of methane using an X‐ray reactor chamber (XRD) coupled with an online mass spectrometer. Also, the susceptibility of these catalysts to oxidation and reduction by individual reaction components was investigated using TPR, TPO, and in situ XPS techniques. The obtained results indicated the distinct catalytic behavior of copper and nickel catalysts depending on their oxidation state and the importance of coke formation in the activation of the partial oxidation process. The mechanism of re‐reduction of catalysts under reaction conditions and a method to increase the activity of nickel catalysts are proposed.

Uncovering quantum characteristics of incipient evolutions at the photosynthetic oxygen evolving complex

Water oxidation of photosynthesis at the oxygen evolving complex (OEC) is driven by the polarization field induced by the photoelectric hole. By highlighting the role of the polarization field in reshaping the spin and orbit potentials, we reveal in this work the characteristics and underlying mechanism in the relatively simpler OEC evolutions within the states S0–S2 prior to the water oxidation. The characteristic shifts of the density of states (DOS) of the electron donor Mn atom are observed in the vicinity of the Fermi surface to occur with the spin flips of Mn atoms and the change in the Mn oxidation states during the electron transfer. Notably, the spin flips of Mn atoms point to the resulting spin configuration of the next states. It is found that the electron transfer tends to stabilize the catalyst OEC itself, whereas the proton transfer pushes the evolution forward by preparing a new electron donor, demonstrating the proton-coupled electron transfer. Meanwhile, it shows that the Mn–O bonds around the candidate Mn atom of the electron donor undergo characteristic changes in the bond lengths during the electron transfer. These concomitant phenomena uncovered in first-principle calculations characterize the essential equilibrium of the OEC between the state evolution and stability that forms the groundwork of the dynamic OEC cycles. In particular, the characteristic undulation of the DOS around the Fermi level occurring at the proton-coupled electron transfer can be used to reveal crucial processes in a wide range of realistic systems.

Cyanide Linkage Isomerization Induced by Cobalt Oxidation-State Changes at a Co-Fe Prussian-Blue Analogue/ZnO Interface.

Understanding the interfacial composition in heterostructures is crucial for tailoring heterogenous electrochemical and photoelectrochemical processes. This work aims to elucidate the structure of a series of Co-Fe Prussian blue analogue modified ZnO (PBA/ZnO) electrodes with interface-sensitive vibrational sum frequency generation (VSFG) spectroscopy. Our measurements revealed, for the first time, a cyanide linkage isomerism at the PBA/ZnO interface, when the composite is fabricated at elevated temperatures. In situ VSFG spectro-electrochemistry measurements correlate the CoII➝CoIII oxidation with the flip of the bridging CN ligand from Co-NC-Fe coordination mode to a Co-CN-Fe one. Photoluminescence measurements and X-ray photoelectron spectroscopy reveal that this unprecedented linkage isomerism originates from surface defects, which act as oxidation sites for the PBA. The presence of such surface defects is correlated with the fabrication temperature for PBA/ZnO. Thus, this contribution identifies the interplay between the surface states of the ZnO substrates and the chemical composition of PBA at the ZnO surface, suggesting an easily accessible approach to control the chemical composition of the interface.

(Invited) Extended Hubbard Functionals for Accurate Modeling of Li-Ion Battery Cathode Materials

Designing novel cathode materials for Li-ion batteries necessitates accurate first-principles predictions of their properties. Density-functional theory (DFT) employing standard (semi-)local functionals encounters challenges due to pronounced self-interaction errors within the partially filled d shells of transition-metal (TM) elements. Here, we demonstrate the efficacy of DFT with extended Hubbard functionals in accurately predicting the "digital" change in oxidation states of TM ions for mixed-valence phases at intermediate Li concentrations in phospho-olivine and spinel cathode materials. The resulting voltages exhibit remarkable agreement with experimental data [1,2].Our approach involves the use of onsite U and intersite V Hubbard parameters computed from density-functional perturbation theory with Lowdin-orthogonalized atomic orbitals, thus circumventing empirical factors [3,4]. Notably, the incorporation of intersite Hubbard V interactions proves indispensable for the precise prediction of thermodynamic quantities, particularly when electronic localization occurs amid inter-atomic orbital hybridization.Extending our investigation to vibrational spectroscopy, we calculate Raman spectra for these materials and find very good agreement with available experimental data [5]. Leveraging the robust and accurate computational framework based on extended Hubbard functionals, we embark on a high-throughput screening of Li-containing compounds, aiming to unveil novel and promising candidates for cathodes [6]. Our findings underscore the pivotal role of advanced DFT methodologies in advancing the discovery and design of high-performance battery materials.[1] I. Timrov, F. Aquilante, M. Cococcioni, N. Marzari, PRX Energy 1, 033003 (2022).[2] I. Timrov, M. Kotiuga, N. Marzari, Phys. Chem. Chem. Phys. 25, 9061 (2023).[3] I. Timrov, N. Marzari, M. Cococcioni, Phys. Rev. B 98, 045141 (2021).[4] I. Timrov, N. Marzari, M. Cococcioni, Phys. Rev. B 103, 085127 (2018).[5] L. Bastonero, N. Marzari, I. Timrov, in preparation.[6] C. Malica, L. Bastonero, M. Bercx, N. Marzari, I. Timrov, in preparation.

Operando and Ex-Situ Studies of Columbite Electrode Materials

Storing and utilising electricity from renewable sources is of growing importance as we move away from our reliance on fossil fuels. Batteries and supercapacitors are becoming ever more present in our day to day lives; in order to improve the next generation of batteries and supercapacitors, we must understand on an atomic scale what happens to electrode materials upon charge and discharge. In order to do this, we must combine structural and electrochemical studies, using techniques which use both different length scales and different timescales. These experiments are known as operando experiments and are a valuable tool in analysing new materials for energy storage.Transition metal niobates of the columbite structure (MNb2O6, M = transition or alkali earth metal) have previously been studied for their photocatalytic and magnetic properties but recently have garnered interest as negative electrode materials for batteries and supercapacitors.1 In this study, a series of columbite materials have been studied using a range of operando and ex-situ techniques. Samples were prepared using both solid-state synthesis2 and solution methods. Ex-situ X-ray diffraction and scanning electron microscopy were used to characterise the columbites prior to electrochemical testing. Operando X-ray absorption spectroscopy and operando Raman studies have been used to probe the changes in oxidation state of the transition metals and local structure upon charge/discharge. References Yang, X. Zhao, F. Liao, Q. Cheng, L. Mao, H. Fa and L. Chen, Sustain. Energy Fuels, 2021, 5, 3039Garía Alvarado, A. Orera, J. Canales-Vázquez, and J. T. S. Irvine, Chem. Mater., 2006, 18, 3827-3834 Figure 1

Water-Insoluble Copper Complexes As Electrocatalysts for CO2 Reduction

The electrochemical reduction of carbon dioxide (CO2R) constitutes a promising CO2 utilization technology, allowing the production of valuable fuels and chemicals by using electrical energy from renewable sources. Nevertheless, poor selectivity and high required overpotentials hamper practical applications of the CO2R, which highlights the need for the development of more efficient electrocatalysts. Different copper-based materials have been extensively studied as electrocatalysts for CO2R. Particularly, copper complexes exhibited interesting properties under operational conditions: many of them undergo structural modifications (e.g. changes in oxidation state and/or coordination number), which potentially affect activity, selectivity and stability. Interestingly, some complexes exhibit reversible restructuring under specific conditions, which can be an interesting property to reach higher stability. In this presentation, we will show the results obtained for the electrocatalysis of water-insoluble copper complexes for the CO2R. The activity, selectivity and stability of both [Cu(bzimpy)Cl2] and [Cu(pyrben)2(NO3)]NO3 were investigated in K2SO4 0.1 mol L-1 (CO2 sat.) under different electrochemical conditions. Here, bzimpy and pyrben stand for 2,6-bis(2-benzimidazolyl)pyridine and 2-(2-pyridyl)benzimidazole, respectively. Qualitative EC-MS (Electrochemistry Coupled to Mass Spectrometry) analysis evidenced that both complexes are active for CO2 reduction and that product distribution changes according to the applied potential. Quantitative gas chromatography measurements revealed that, at -1.24 V vs. RHE, [Cu(bzimpy)Cl2] promotes the formation of H2, CO, CH4 and C2H4 with faradaic efficiencies of 26, 3.4, 9.2 and 31%, respectively. On the other hand, [Cu(pyrben)2(NO3)]NO3 shows FE values of 24, 8.8, 15 and 24% for H2, CO, CH4 and C2H4, respectively. After 1.6 h of electrolysis, the former exhibited stable current and FE of ~42% towards ethylene formation.

Material Changes of Bimetallic Ag–Cr, Fe, Co, Ni, Cu, Sn Electrocatalysts during Alkaline Oxygen Reduction in Fundamental Versus Alkaline Membrane Exchange Fuel Cell Conditions

The more apparent challenges of climate change drastically increase the global demand for sustainable fuel production and usage.1 In this context, hydrogen fuel cells (FCs) powered by renewable electricity are among the promising technologies.2 Addressing the sluggish cathode reaction in FCs, the oxygen reduction reaction (ORR), these devices hold immense potential for sustainable energy conversion and storage. An alkaline environment allows for the utilization of more abundant and cost-effective metals in contrast to current platinum-based catalysts. Silver (Ag), for instance, exhibits high selectivity for the ORR, i.e., forming hydroxide instead of peroxide.3 When combined with secondary metals, bimetallic Ag catalysts show enhanced activity, making them viable alternatives to platinum-group materials for ORR.In our highly collaborative research, we investigated the material transformations of bimetallic Ag thin films with chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and tin (Sn) as secondary metals for ORR electrocatalysis in fundamental rotating disk electrode (RDE) setups and the application device, anion-exchange membrane FC (AEMFC). Grazing-incidence X-ray diffraction (GI-XRD) conducted prior to electrochemical testing reveals no evidence of alloying except for the Ag-Sn bimetallic thin film. However, X-ray photoelectron spectroscopy (XPS) indicates a shift of the Ag 3d peaks to higher binding energies for all catalysts, suggesting a hybridization of Ag and the secondary metals. The composition of the metal surface, native oxide formation, ORR performance, and material changes post-RDE testing vary distinctly among the Ag bimetallic catalysts depending on the secondary metal. Intriguingly, performance is either enhanced (Ag-Co, Ag-Sn), maintained with reduced Ag content (Ag-Fe, Ag-Cr), or falls in between the two monometallic materials (Ag-Ni) compared to monometallic Ag thin films. Density functional theory (DFT) calculations offer insights into the catalyst performances and changes in metal oxidation states and surface composition prior and post electrocatalysis. AEMFC tests reveal promising performances under device conditions contradicting our fundamental RDE measurements. The integration of fundamental and application device tests, along with material characterization and DFT calculations, enables a comprehensive exploration of material changes under varying electrochemical conditions. This underscores the complexity of bimetallic catalysts and the importance of testing under device conditions, positioning Ag-bimetallic catalysts as highly promising alternatives to platinum-group metal catalysts for alkaline ORR.

Material Dynamics of Nickel (oxy)Hydroxide As an Alcohol Oxidation Electrocatalyst

Electrochemical alcohol oxidation is an attractive reaction for renewable-energy driven production of value-added chemicals, like precursors for acrylic (acrolein from glycerol) and nylon (adipic acid from cyclohexanol). Implementing selective, earth-abundant catalysts for alcohol oxidation can improve electrolyzer efficiency and economics. For example, replacing the energy intensive oxygen evolution reaction (OER) in CO2 electrolyzers with alcohol oxidation can decrease operating voltage by about 0.85 V and reduce electricity requirements up to 53% while also reducing carbon emissions from chemical production.1 Electrochemical alcohol oxidation catalyzed by as synthesized nickel oxyhydroxide (NiOOH) is hypothesized to proceed through two pathways, a chemical, redox pathway preferred by aldehydes (geminal diols in alkaline electrolyte), and a potential dependent pathway preferred by alcohols.2 Many studies have focused on understanding reaction mechanisms and device performance, however, transition metal alcohol oxidation catalysts, such as NiOOH, are known to undergo reduction/oxidation, phase changes, and even dissolution in the same potential window as alcohol oxidation.3 It is still unclear how these processes affect catalyst material stability and electrochemical performance.In this work, we probe the performance stability and material stability of Ni(OH)2 for alcohol oxidation in alkaline media through electrochemical cycling and chronoamperometry. We use a rigorously Fe-free environment to mitigate performance impacts from Fe-contamination common in non-purified alkaline electrochemical studies.4 We show that the rate of change of alcohol oxidation current density (mA cm-2) depends on reaction pathway (redox vs. potential dependent), alcohol concentration, and side chain structure. Using EC-MS and NMR, we also probe changes in performance in yield and selectivity by quantifying oxidation products, including oxygen gas. These changes in performance are correlated to material changes through monitoring dissolution with on-line ICP-MS. Furthermore, to disentangle the role of potential and reactant (e.g. alcohol or water) on stability, we elucidate oxidation state and local structural changes using in situ X-ray Absorption Spectroscopy (XAS). Insights from this rigorous model system are directly translatable to the broader goal of developing efficient, long-lasting catalysts for industrial deployment of electrochemical organic reactions powered by clean energy. References. Verma, Sumit, Shawn Lu, and Paul JA Kenis. Nature Energy 4.6 (2019): 466-474.2.Bender, Michael T., and Kyoung‐Shin Choi. ChemSusChem 15.13 (2022): e202200675.Klaus, Shannon, et al. The Journal of Physical Chemistry C 119.13 (2015): 7243-7254Wei, Lingze, et al. ACS Catalysis 13.7 (2023): 4272-4282.

Structure, Thermodynamics, Chemomechanics, and Kinetics: The Hidden Complexities of LiNiO2

After being abandoned due to mechanical and thermodynamic instabilities, layered transition metal oxides with ultra-high Ni content currently see a revival as promising cathode active material in the effort of further pushing the energy density of lithium ion batteries. Because such materials are in many aspects closely related to the pure LiNiO2, understanding the properties and mechanisms of this model system on an atomic level is vital for the development of more complex materials. Therefore, we have analyzed the structure, thermodynamics, chemomechanics and kinetics of LiNiO2 and its delithiated states including the presence of native defects by making use of atomistic simulations to grasp the peculiarities of this material.What makes the structure and related properties of LiNiO2 especially interesting and challenging is the presence of dynamic Jahn-Teller distortions of the NiO6 octahedra. This leads to local monoclinic distortions and our simulations revealed why the material still appears to be of rhombohedral symmetry on a global scale.[1]Upon delithiation and the concurrent oxidation to Ni4+, the Jahn-Teller distortions start to vanish and particularly stable Li orderings may be observed. In this context, we used a cluster expansion approach and were able to reproduce the experimental phase diagram. Moreover, we included native defects in the analysis because LiNiO2 can hardly be prepared stoichiometric. Instead, many synthesis approaches lead to additional Ni ions occupying the Li layers (NiLi). The introduction of such defects as well as other substitutionals in a surrogate model shows that single phase regions tend to be suppressed and solid-solution behavior is favored. This smooths the voltage curves and gives good agreement with experiments.[2]We then focused on more extended defects in layered transition metal oxides: Stacking faults (observed at low Li content and responsible for stacking changes from O3 to O1-type layering) and dislocations (needed to drive stacking changes through the material). We found that the energetics and gliding barriers of stacking faults in stoichiometric LiNiO2 are similar to LiCoO2 for all degrees of lithiation. However, by acknowledging the presence of NiLi we quantified for the first time how this defect hinders layer gliding: In the fully delithiated material, 2% of NiLi in the Li layer has a similar effect as 11%-15% Li, effectively increasing the gliding barriers. In terms of dislocations, their excess energies in LiNiO2 are much lower than in LiCoO2, which we mostly attribute to the Jahn-Teller distortions that are able to collinearly orient in the vicinity of a dislocation in LiNiO2, effectively taking a part of the strain. Moreover, dislocations are able to attract both Li and O vacancies, potentially affecting the kinetics of the material as well as acting as a precursor for further degradation mechanisms.[3]Lastly, we mention our recent analysis again focusing on NiLi defects. Our simulations show that such Ni ions remain in a +2 oxidation state independent on the degree of lithiation. This contradicts the broad opinion of an oxidation state change to +3 at low Li content, which is believed to lead to a local constriction of the layer that can hardly be relithiated again. Nevertheless, we show that NiLi indeed leads to an attraction of Li vacancies within two lattice sites and the potential to split fast divacancies into two considerably slower single vacancies. These observations together with the fact that any NiLi depicts an obstacle for diffusing Li ions or Li vacancies shed light on the kinetics of non-stoichiometric LiNiO2 and support the development of further optimization schemes.[4][1] Chem. Mater. 2020, 32, 23, 10096–10103[2] J. Mater. Chem. A , 2021,9, 14928-14940[3] Chem. Mater. 2023, 35, 2, 584–594[4] https://doi.org/10.26434/chemrxiv-2023-hkmsn-v3

Decreased vascular contraction and changes in oxidative state in middle–aged Wistar rats after exposure to increased levels of dietary zinc

Both copper and zinc are known to be important for maintaining health, but most research has focused on deficiencies of these elements. Recent studies have shown that high levels of Cu can be toxic, especially to the cardiovascular (CV) system. However, little research has been done on the effects of higher levels of Zn on the CV system. In this study, male Wistar rats aged 12 months were given a diet with twice the recommended daily allowance of zinc (31.8 mg/kg of diet) and compared to a control group (15.9 mg/kg of diet) after 8 weeks. Blood plasma and internal organs of both groups were examined for levels of copper, zinc, selenium and iron, as well as several key enzymes. Aortic rings from both groups were also examined to determine vascular functioning. There were very few changes in the vascular system functioning after chronic exposure to zinc, and only one enzyme, heme oxygenase–1 (HO–1) was elevated, whereas vascular contraction to noradrenaline decreased with no changes in vasodilation to acetylcholine. Of the micronutrients, zinc and selenium were elevated in the blood plasma, while copper decreased. Meanwhile, the total antioxidant status increased. These were not observed in the liver. Therefore, it is proposed that there is a mechanism in place within the vascular system to protect against the overproduction of heme, caused by chronic zinc exposure.

In Situ Characterization of Metastable Pb3O5 and Pb2O3 Phases During Thermal Decomposition of PbO2 to PbO.

Nonstoichiometric lead oxides play a key role in the formation and cycling of the positive electrodes in a lead acid battery. These phases have been linked to the underutilization of the positive active material but also play a key role in the battery's cycle life, providing interparticle adhesion and the connection to the underlying lead grid. Similar phases have previously been identified by mass loss or color change during thermal annealing of PbO2 to PbO, suggesting that at least two intermediate PbOx phases exist. Using multiple, in situ analysis techniques (powder diffraction, X-ray absorption, X-ray photoelectron spectroscopy) and ex situ nuclear magnetic resonance measurements, the structural conversion and changes in the lead oxidation state were identified during this process. Isolation of the PbOx phases enabled confirmation of Pb3O5 and Pb2O3 by diffraction and the first 207Pb NMR measurement of these intermediates. The thermodynamic and kinetic stability of these intermediates and other reported polymorphs were determined by density functional theory, providing key insight into their origins and variation of PbOx structures found in previous studies.