Redox Potential Research Articles

Redox-mediated changes in the release dynamics of lead and bacterial community composition in a biochar amended soil contaminated with metal halide perovskite solar panel waste.

This study explored the redox-mediated changes in a lead (Pb) contaminated soil (900 mg/kg) due to the addition of solar cell powder (SC) and investigated the impact of biochar derived from soft wood pellet (SWP) and oil seed rape straw (OSR) (5% w/w) on Pb immobilization using an automated biogeochemical microcosm system. The redox potential (Eh) of the untreated (control; SC) and biochar treated soils (SC + SWP and SC + OSR) ranged from -151 mV to +493 mV. In SC, the dissolved Pb concentrations were higher under oxic (up to 2.29 mg L-1) conditions than reducing (0.13 mg L-1) conditions. The addition of SWP and OSR to soil immobilized Pb, decreased dissolved concentration, which could be possibly due to the increase of pH, co-precipitation of Pb with FeMn (hydro)oxides and pyromorphite, and complexation with biochar surface functional groups. The ability and efficiency of OSR for Pb immobilization were higher than SWP, owing to the higher pH and density of surface functional groups of OSR than SWP. Biochar enhanced the relative abundance of Proteobacteria irrespective of Eh changes, while the relative abundance of Bacterioidota increased under oxidizing conditions. Overall, we found that both OSR and SWP immobilized Pb in solar panel waste contaminated soil under both oxidizing and reducing redox conditions which may mitigate the potential risk of Pb contamination.

Stable anode/separator interface enabled by graft modification of polypropylene separator via electron beam irradiation technique toward high-performance sodium metal batteries

Sodium metal batteries (SMBs) are considered as strong alternatives to lithium-ion batteries (LIBs), due to the inherent merits of sodium metal anodes (SMAs) including low redox potential (−2.71 V vs. SHE), high theoretical capacity (1166 mAh g−1), and abundant resources. However, the uncontrollable Na dendrite growth has significantly impeded the practical deployment of SMBs. Separator modification has emerged as an effective strategy for substantially enhancing the performance of SMAs. Herein, for the first time, we present the successful grafting polyacrylic acid (PAA) onto polypropylene (PP) separators (denoted as PP-g-PAA) using highly efficient electron beam (EB) irradiation to improve the cyclability of SMAs. The polar carboxyl groups of PAA can facilitate the electrolyte wetting and provide ample mechanical strength to resist dendrite penetration. Consequently, the regulation of Na+ ion flux enables uniform Na+ deposition with dendrite-free morphology, facilitated by the favorable anode/separator interface. The PP-g-PAA separator significantly enhances the cyclability of fabricated cells. Notably, the lifespan of Na||Na symmetric cells can be extended up to 5519 h at 1 mA cm−2 and 1 mAh cm−2. The stable design of the anode/separator interface achieved through polyolefin separator modification presented in this study holds promise for the further advancement of next-generation advanced battery systems.

Heavy Metal Exposure-Induced Cardiovascular Diseases: Molecular Mechanisms and Therapeutic Role of Antioxidants.

Globally, cardiovascular diseases (CVDs) are the main cause of mortality every year worldwide. CVD health is influenced by various health factors, such as blood pressure, cholesterol levels, and glucose control. The main risk factors include smoking, physical activity, food intake, and body mass index. Around 90% of CVDs could be prevented by controlling these risk factors. Heavy metals are indigenous to the environment of the earth. However, modern lifestyles have led to the exploitation of our environment by unconstrained use of heavy metals. Though heavy metals are essential components, they are hazardous to humans and living systems due to their persistent and non-degradable nature. The mainpurpose of this study is to provide a literature review on the mechanisms of heavy metals, particularly arsenic, lead, and cadmium, that cause cardiovascular diseases. The major mechanism by which heavy metals result in various modalities of cardiovascular disease is the generation of reactive species and the depletionof the antioxidant reserves inside the biological system. The generation of reactive species gradually leads to the activation of various signaling pathways, resulting in either apoptosis or unrestricted cell growth. These unfavorable conditions result in a state when there is an imbalance between reactive species generation and antioxidant activity. Both endogenously present antioxidants and dietary antioxidants are very much essential in regulating the redox potential of the body. They help in the detoxification and excretion of heavy metals and their metabolites in the biological system. Therefore, recognizing the role of heavy metals in cardiovascular health is crucial for developing preventive strategies and interventions aimed at mitigating their adverse effects on human health.

Control and surveillance of redox potential for 233Pa dissolution in 2LiF-BeF2 molten salt.

233Pa, the precursor nuclide of 233U in the thorium-uranium conversion is prone to reductive deposition in 2LiF-BeF2 (66 : 34 mol%, FLiBe) molten salt. We explored the adjustment and control of the redox potential of the FLiBe melt to avoid the 233Pa reduction deposition. The experimental data indicated that the deposited 233Pa can be completely dissolved and reentered into the molten salt with the addition of oxidant NiF2, and the distribution and behaviour of uranium, thorium, neptunium, and most fission products did not have any significant change in the NiF2-oxidised FLiBe molten salt, showing the feasibility of this manner to make 233Pa exist stably in the melt. The effects of NiF2-addition on the behaviour of the fission products 95Nb and 131I in the FLiBe molten salt were also investigated. It was found that 131I could be used as a redox indicator to monitor the redox potential of the oxidation-enhanced FLiBe molten salt. All the information drawn from this study could provide significant support for the control and surveillance of the redox potential of the FLiBe molten salt in the upcoming thorium molten salt reactor (TMSR).

Computational Analysis of Low Overpotential Ammonia Oxidation by Metal-Metal Bonded Ruthenium Catalysts, and Predictions for Related Osmium Catalysts.

The catalyzed electrochemical oxidation of ammonia to nitrogen (AOR) is an important fuel-cell half-reaction that underpins a future nitrogen-based energy economy. Our laboratory has reported spontaneous chemical and electrochemical oxidation of ammonia to dinitrogen via reaction of ammonia with the metal-metal bonded diruthenium complex Ru2(chp)4OTf (chp- = 2-chloro-6-hydroxypyridinate, TfO- = trifluoromethanesulfonate). This complex facilitates electrocatalytic ammonia oxidation at mild applied potentials of -255 mV vs ferrocene, which is the [Ru2(chp)4(NH3)]0/+ redox potential. We now report a comprehensive computational investigation of possible mechanisms for this reaction and electronic structure analysis of key intermediates therein. We extend this analysis to proposed second-generation electrocatalysts bearing structurally similar fhp and hmp (2-fluoro-6-hydroxypyridinate and 2-hydroxy-6-methylpyridinate, respectively) equatorial ligands, and we further expand this study from Ru2 to analogous Os2 cores. Predicted M24+/5+ redox potentials, which we expect to correlate with experimental AOR overpotential, depend strongly on the identity of the metal center, and to a lesser degree on the nature of the equatorial supporting ligand. Os2 complexes are easier to oxidize than analogous Ru2 complexes by ∼640 mV, on average. In contrast to mono-Ru catalysts, which oxidize ammonia via a rate-limiting activation of the strong N-H bond, we find lowest-energy reaction pathways for Ru2 and Os2 complexes that involve direct N-N bond formation onto electrophilic intermediates having terminal amido, imido, or nitrido groups. While transition state energies for Os2 complexes are high, those for Ru2 complexes are moderate and notably lower than those for mono-Ru complexes. We attribute these lower barriers to enhanced electrophilicity of the Ru2 intermediates, which is a consequence of their metal-metal bonded structure. Os2 intermediates are found to be, surprisingly, less electrophilic, and we suggest that Os2 complexes may require access to oxidation states higher than Os25+ in order to perform AOR at reasonable reaction rates.

Experimental and Theoretical Predictors for Redox Potentials of Bispyridinylidene Electron Donors.

Bispyridinylidenes are neutral organic molecules capable of two-electron oxidation at a range of redox potentials that are widely tunable by choice of substituent, making them attractive as homogeneous organic reductants and active materials in redox flow batteries. In an effort to readily predict the redox potentials of this important class of compounds, we have developed correlations between the experimental redox potentials and both experimental and theoretical predictors. On the experimental side, we show that multinuclear NMR chemical shifts of related pyridinium ions correlate well with the redox potentials of bispyridinylidenes, with R2 and standard errors (S) reaching 0.9810 and 0.048 V, respectively, when the 13C (N-CH3) and 1H (ortho) chemical shifts are used together. Theoretical studies of the bispyridinylidenes and their doubly oxidized bipyridinium ions gave a range of predictively valuable equations at various levels of computational cost. This ranged from a simple model using only the EHOMO of the bispyridinylidenes (R2 = 0.9689; S = 0.060 V), to a more computationally intensive model which include solvation effects for both redox states which gave the highest predictive value for all methods (R2 = 0.9958; S = 0.022 V). This work will guide further studies of this important class of molecules.

Redox Properties of Bacillus subtilis Ferredoxin:NADP+ Oxidoreductase: Potentiometric Characteristics and Reactions with Pro-Oxidant Xenobiotics

Bacillus subtilis ferredoxin:NADP+ oxidoreductase (BsFNR) is a thioredoxin reductase-type FNR whose redox properties and reactivity with nonphysiological electron acceptors have been scarcely characterized. On the basis of redox reactions with 3-acetylpyridine adenine dinucleotide phosphate, the two-electron reduction midpoint potential of the flavin adenine dinucleotide (FAD) cofactor was estimated to be −0.240 V. Photoreduction using 5-deazaflavin mononucleotide (5-deazaFMN) as a photosensitizer revealed that the difference in the redox potentials between the first and second single-electron transfer steps was 0.024 V. We examined the mechanisms of the reduction of several different groups of non-physiological electron acceptors catalyzed by BsFNR. The reactivity of quinones and aromatic N-oxides toward BsFNR increased when increasing their single-electron reduction midpoint redox potentials. The reactivity of nitroaromatic compounds was lower due to their lower electron self-exchange rate, but it exhibited the same trend. A mixed single- and two-electron reduction reaction was characteristic of quinones, whereas reactions involving nitroaromatics proceeded exclusively via the one-electron reduction reaction. The oxidation of FADH• to FAD is the rate-limiting step during the oxidation of fully reduced FAD. The calculated electron transfer distances in the reaction with nitroaromatics were close to those of other FNRs including the plant-type enzymes, thus demonstrating their similar active site accessibility to low-molecular-weight oxidants despite the fundamental differences in their structures.

Synergistic Engineering of Energy Band Alignment and Interfacial Electric Field Distribution over Bi-bismuth-Based Hetero-nanofibers for Boosting Visible-Light-Driven Photocatalytic Ammonia Synthesis and Antibiotic Removal.

Synergistic engineering of energy band alignment and interfacial electric field distribution is essential for photocatalyst design but is still challenging because of the limitation on refined regulation in the nanoscale. This study addresses the issue by employing surface modification and thermal-induced phase transformation in Bi2MoO6/BixOyIz hetero-nanofiber frameworks. The energy band alignment switches from a type-II interface to a Z-scheme contact with stronger redox potentials and inhibited electron traps, and the optimized built-in electric field distribution could be reached based on experimental and theoretical investigations. The engineered hetero-nanofibers exhibit outstanding visible-light-driven photocatalytic nitrogen reduction activity (605 μmol/g/h) and tetracycline hydrochloride removal rate (81.5% within 30 min), ranking them among the top-performing bismuth series materials. Furthermore, the photocatalysts show promise in activating advanced oxidants for efficient organic pollutant degradation. Moreover, the Bi2MoO6/Bi5O7I hetero-nanofibers possess good recycling stability owing to their three-dimensional network structure. This research offers valuable insights into heterojunction design for environmental remediation and industrial applications.

Excessive Eutrophication as a Chemical Barrier for Fish Fauna Dispersion: A Case Study in the Emblematic Tietê River (São Paulo, Brazil)

The Tietê River receives most of the effluents and diffuse wastes from the São Paulo metropolis (21.9 million inhabitants). The study aimed to assess the extent to which environmental changes affected the fish fauna. We compared, in rainy and dry seasons, three sites in Tietê and three in tributaries with much better water quality conditions. No physical barriers exist between the sites. Fish were sampled with gillnets (exposed overnight) and the assemblage’s ecological attributes calculated. Water depth, transparency, temperature, electrical conductivity, dissolved oxygen, turbidity, total dissolved solids, pH, redox potential, total phosphorus, total nitrogen, and chlorophyll were simultaneously determined. Low oxygen concentrations (near zero in the rainy period), and the opposite for nutrients and total solids, separated the predominantly hypereutrophic Tietê from the tributaries (PCA). Differences in the fish assemblages were also evidenced (nMDS), including a higher richness per sample in tributaries (11 to 14 spp.) compared to Tietê (3 to 4 spp.). Siluriformes with accessory breathing dominated in Tietê and the highly tolerant detritivorous Prochilodus lineatus (the main commercial fish) was the only species found in all sites. The species correlated positively with oxygen in the tributaries and with turbidity, redox potential, and nutrients in Tietê (DistLM) (rainy season). Recovery measures are urgently required.

Leaching of NMC industrial black mass in the presence of LFP

This study focuses on the effect of an emerging source of waste, lithium iron phosphate (LFP) cathode materials, on the hydrometallurgical recycling of the currently dominant industrial battery waste that is rich in transition metals (Ni, Co, Mn, and Li). The effects of the dosage of LFP, initial acidity, and timing of LFP reductant addition were investigated in sulfuric acid (H2SO4) leaching (t = 3 h, T = 60 °C, ω = 300 rpm). The results showed that addition of LFP increased both transition metal extraction and acid consumption. Further, the redox potential was lowered due to the increased presence of Fe2+. An initial acidity of 2.0 mol/L H2SO4 with acid consumption of 1.3 kg H2SO4/kg black mass provided optimal conditions for achieving a high leaching yield (Co = 100%, Ni = 87.6%, Mn = 91.1%, Li = 100%) and creating process solutions (Co 8.8 g/L, Ni 13.8 g/L, Li 6.7 g/L, Mn 7.6 g/L, P 12.1 g/L) favorable for subsequent hydrometallurgical processing. Additionally, the overall efficiency of H2O2 decreased due to its decomposition by high concentrations of Fe2+ and Mn2+ when H2O2 was added after t = 2 h, leading to only a minor increase in final battery metals extraction levels.

Variations in flavin redox states during extracellular electron transfer and electron conduction in Shewanella oneidensis

Flavin is one of the most prevalent redox molecules utilized by electroactive bacteria. Electroactive bacteria form a three-dimensional architecture with multiple cell assemblages on electrodes in bioelectrochemical systems. This provokes the importance of unveiling the redox chemistry of flavins during electron transfer not only at the bacteria/electrode interface but also inside cell assemblages. However, it has been difficult to directly compare the redox species contributing to each electron transfer reaction. In this study, to simultaneously detect the flavin redox species at the electrode surface and those in cell assemblages, we conducted bipotentiometric cyclic voltammetry on a colony of Shewanella oneidensis MR-1. The bipotentiometric data showed that flavin mononucleotide proceeds the redox cycle at − 0.43 V (vs. standard hydrogen electrode) in the MR-1 colony assignable to the semiquinone/hydroquinone redox cycle, which was supported by experiments with semiquinone scavenger and gene deletion mutants. Notably, the peak at − 0.43 V was not detected at the electrode surface, indicating that the flavin redox cycles and redox potentials involved in the electron transfer inside MR-1 assemblages differ from those at the MR-1/electrode interface. The measurement system presented herein offers a platform to clarify the redox reactions in cell assemblages as well as at the bacteria/electrode interface.

Tuning the Thermochemistry and Reactivity of a Series of Cu-Based 4H+/4e- Electron-Coupled-Proton Buffers.

Electron-coupled-proton buffers (ECPBs) store and deliver protons and electrons in a reversible fashion. We have recently reported an ECPB based on Cu and a redox-active ligand that promoted 4H+/4e- reversible transformations (J. Am. Chem. Soc. 2022, 144, 16905). Herein, we report a series of Cu-based ECPBs in which the ability of these to accept and/or donate H• equivalents can be tuned via ligand modification. The thermochemistry of the 4H+/4e- ECPB equilibrium was determined using open-circuit potential measurements. The reactivity of the ECPBs against proton-coupled electron transfer (PCET) reagents was also analyzed, and the results obtained were rationalized based on the thermochemical parameters. Experimental and computational analysis of the thermochemistry of the H+/e- transfers involved in the 4H+/4e- ECPB transformations found substantial differences between the stepwise (namely, BDFE1, BDFE2, BDFE3, and BDFE4) and average bond dissociation free energy values (BDFEavg.). Our analysis suggests that this "redox unleveling" is critical to promoting the disproportionation and ligand-exchange reactions involved in the 4H+/4e- ECPB equilibria. The difference in BDFEavg. within the series of Cu-based ECPBs was found to arise from a substantial change in the redox potential (E1/2) upon modification of the ligand scaffold, which is not fully compensated for by a change in the acidity/basicity (pKa), suggesting "thermochemical decompensation".

Multifaceted effects of ring fusion on the stability of charged dialkoxyarene redoxmers

Due to their almost unlimited scalability, redox flow batteries can make versatile and affordable energy storage systems. Redox active materials (redoxmers) in these batteries largely define their electrochemical performance, including the life span of the battery that depends on the stability of charged redoxmers. In this study, we examine the effects of expanding the π-system in the arene rings on the chemical stability of dialkoxyarene redoxmers that are used to store positive charge in RFBs. When 1,4-dimethoxybenzene is π-extended to 1,4-dimethoxynaphthalene, a lower redox potential, improved kinetic stability, and longer cycling life are observed. However, when an additional ring is fused to make 9,10-dimethoxyanthracene, the radical cation undergoes rapid O-dealkylation possibly due to increased steric strain that drives methoxy out of the arene plane thus breaking the π-conjugation with O 2p orbitals. On the other hand, the planar structure of 1,4-dimethoxynaphthalene may facilitate second-order reactions of radical cations leading to their neutralization in the bulk. Our study suggests that extending the π-system changes reactivity in multiple (sometimes, opposite) ways, so lowering the oxidation potential through π-conjugation to improve redoxmer stability should be pursued with caution.

Theoretical Study of the Ternary Compound Monolayer CuP2Se for Photocatalytic Water Splitting with Efficient Optical Absorption.

Utilizing photocatalytic method to produce hydrogen by splitting water is an efficient strategy to solve the hotspot issues of energy crisis and environmental pollution. Herein, we systematically investigate the corresponding properties of the reported Cu-bearing ternary compound monolayer CuP2Se by using the first-principle calculations. The monolayer CuP2Se has quite small cleavage energy of 0.51 J/m2, indicating it can be easily produced by the mechanical exfoliation method experimentally. In addition, it is an indirect bandgap semiconductor material which has a moderate value of 1.91 eV. The conduction band minimum (CBM) and valence band maximum (VBM) can perfectly straddle the redox potentials of water when a biaxial strain of -4% to 4% is applied, unveiling the high photocatalytic thermodynamic stability of monolayer CuP2Se in response to the effect of solvent tension. Remarkably, the monolayer CuP2Se also demonstrates significant sunlight capturing ability in the visible region. The outstanding electronic and optical properties suggest that the monolayer CuP2Se is undoubtedly a viable material for photocatalytic water splitting.

Electrochemical Restructuring Driven Catalytic Cycle of Bi-Based Heterojunctions for High-Performance Lithium-Sulfur Batteries.

Restructuring is an important phenomenon in catalytic reactions. Conversion-type materials with suitable redox potential may undergo in situ electrochemically driven restructurings and induce highly active catalytic sites in a working lithium-sulfur battery. Herein, driven by the electrochemical conversion reaction of BiVO4, a reversible catalytic cycle of Bi/amorphous Li3VO4 (a-Li3VO4) and Bi2S3/a-Li3VO4 heterojunctions is constructed, which targets the oxidation of Li2S and the conversion of polysulfide, respectively. The heterostructures and electrochemically driven size confinement provide abundant sites for shuttle restraining and sulfur conversion. Especially, the p-block Bi and Bi2S3 could dramatically reduce the conversion energy barriers of Li2S and polysulfide by virtue of the p-p orbital hybridization, promoting bidirectional reactions of the sulfur cathode. As a result, the corresponding sulfur cathode possesses a high reversible capacity of 7.5 mAh cm-2 after 120 cycles under a high sulfur loading of 10.3 mg cm-2 with a current density of 0.38 mA cm-2. This study furnishes a feasible scheme to obtain highly effective catalysts for bidirectional sulfur redox by utilizing the electrochemically induced restructuring.

Effect of Garlic Extract on the Erythrocyte as a Simple Model Cell

Garlic is known to have diverse effects on mammalian cells, being cytotoxic, especially to cancer cells, but also protect against oxidative stress. Mammalian erythrocyte is a simple cell devoid of intracellular organelles, protein synthesis ability, and most signaling pathways. Therefore, examination of the effects of garlic on erythrocytes allows for revealing primary events in the cellular action of garlic extract. In this study, human erythrocytes or erythrocyte membranes were exposed to garlic extract at various dilutions. Hemoglobin oxidation to methemoglobin, increased binding of hemoglobin to the membrane, and formation of Heinz bodies were observed. Garlic extract depleted acid-soluble thiols, especially glutathione, and induced a prooxidative shift in the cellular glutathione redox potential. The extract increased the osmotic fragility of erythrocytes, induced hemolysis, and inhibited hemolysis in isotonic ammonium chloride, indicative of decreased membrane permeability for Cl− and increased the membrane fluidity. Fluorescent probes indicated an increased level of reactive oxygen species and induction of lipid peroxidation, but these results should be interpreted with care since the extract alone induced oxidation of the probes (dichlorodihydrofluorescein diacetate and BODIPY C11). These results demonstrate that garlic extract induces oxidative changes in the erythrocyte, first of all, thiol and hemoglobin oxidation.

Implications of Polyoxometalate Properties on the Performance Characteristics of Redox Flow Battery

Abstract Implications of rate coefficients, concentration ratio, and electron-transfer number of the redox species present in the anolyte and catholyte on the performance characteristics of a redox flow battery (RFB) were investigated. Toward this, a polyoxometalate (POM)-V4+/V5+ RFB (with order 104 of magnitude difference in their rate coefficients) was assembled by replacing the anolyte (V2+/V3+) of a well-established vanadium RFB (VRFB); the redox potential of POM is comparable to that of V2+/V3+. The performance of the POM-V4+/V5+ RFB improves by ~100 mV at reasonable operating current densities (~ 200 mA cm-2) as compared to that of a VRFB, in a 5 cm2 cell, even though the solubility of tungstosilicic acid (TSA) is 300 mM as compared to 1.8 M VOSO4. Only four electrons can be reversibly extracted from the POM, although extraction of 14 electrons (theoretical) is possible from TSA, limiting the charging voltage to 1.4 V. Overcharging leads to capacity loss and concentration ratio (Catholyte: Anolyte) impacts the overall performance of RFB. Significant vanadium crossover loss is also observed at the anode side.

Formation of N‐Doped Carbon Nanofibers Decorated with MoP Nanoflakes for Dendrite‐Free Lithium Metal Anode

AbstractMetallic lithium (Li) is recognized as a promising candidate for anode material of Li‐ion batteries owing to high theoretical specific capacity and low redox potential. However, uncontrollable dendrite growth and huge volume expansion during Li plating/stripping processes hinder its practical application. Herein, N‐doped carbon nanofibers@MoP nanoflakes (NCNF@MoP) is developed as a potential host to address the above challenges. During the formation of solid electrolyte interphase, MoP nanoflakes can be changed into metallic Mo with high lithiophilicity and Li3P with high ionic conductivity. The whole composite host is transformed into a mixed ion/electron conducting network to reduce nucleation overpotential and accelerate diffusion kinetics at the electrode/electrolyte interface. As a proof of concept, the symmetric cell using NCNF@MoP host presents a long‐term cycling up to 2500 h with a low nucleation overpotential of 10 mV at 1 mA cm−2. Additionally, the Li‐NCNF@MoP||LiFePO4 full cell demonstrates a good capacity retention of 92.6% over 2200 cycles at a high current density of 5C (1 C = 169 mA g−1).

Operando insights into ammonium-mediated lithium metal stabilization: surface morphology modulation and enhanced SEI development

Lithium-ion batteries (LiBs) with graphite as an anode and lithiated transition metal oxide as a cathode are approaching their specific energy and power theoretical values. To overcome the limitations of LiBs, lithium metal anode with high specific capacity and low negative redox potential is necessary. However, practical application in rechargeable cells is hindered by uncontrolled lithium deposition manifesting, for instance, as Li dendrite growth which can cause formation of dead Li, short circuits and cell failure.The electrochemical behaviour of a protic additive (NH4PF6) in a carbonate-based electrolyte has been investigated by operando confocal Raman spectroscopy, in situ optical microscopy, and X-ray photoelectron spectroscopy, elucidating its functional mechanism. The ammonium cation promotes a chemical modification of the lithium metal anode-electrolyte interphase by producing an N-rich solid electrolyte interphase and chemically modifying the lithium surface morphology by electrochemical pitting. This novel method results in stable lithium deposition and stripping by a decreasing the local current density on the electrode, thus limiting dendritic deposition.

The Functional Role of Disordered Metal Oxides from Active Catalysis to Biological Metabolism

AbstractIt has been observed by many authors that highly active electrocatalysts are frequently “disordered” or “amorphous” in nature. The correlation between this lack of order and functionality is highly debated, with researchers still questioning if this structural property is a simple coincidence of the material preparation method, or if this lack of order has an important functional role for these catalysts. Using metal oxides as an example, how amorphous and disordered metal oxides can react by fundamentally different pathways are explored from more ordered forms with very similar bonding and redox states. The distinction between amorphous, disordered, and crystalline materials is reviewed in different characterization methods and suggests how these material characteristics fundamentally change the reactivity of these materials beyond surface area effects. How disorder can change the underlying thermodynamic stability of a material is explored, which in turn impacts redox potential, proton‐transfer, and electron‐transfer properties. It is these fundamental properties that govern the electrocatalytic activity and microbial metabolism of these materials. It is further argued that understanding the amorphous and disordered state of materials may be key to understanding a range of catalytic reactions; from clean energy reactions to the biological systems that underpin life's existence.