Complex Redox Research Articles

A complex and dynamic redox network regulates oxygen reduction at photosystem I in Arabidopsis.

Thiol-dependent redox regulation of enzyme activities plays a central role in regulating photosynthesis. Beside the regulation of metabolic pathways, alternative electron transport is subjected to thiol-dependent regulation. We investigated the regulation of O2 reduction at photosystem I. The level of O2 reduction in leaves and isolated thylakoid membranes depends on the photoperiod in which plants are grown. We used a set of Arabidopsis (Arabidopsis thaliana) mutant plants affected in the stromal, membrane and lumenal thiol network to study the redox protein partners involved in regulating O2 reduction. Light-dependent O2 reduction was determined in leaves and in thylakoids of plants grown in short day and long day conditions using a spin-trapping electron paramagnetic resonance (EPR) assay. In wild type samples from short day conditions, reactive oxygen species (ROS) generation was double that of samples from long day conditions, while this difference was abolished in several redoxin mutants. An in vitro reconstitution assay showed that thioredoxin m, NADPH-dependent reductase C and NADPH are required for high O2 reduction levels in thylakoids from plants grown in long day conditions. Using isolated photosystem I, we also showed that reduction of a photosystem I protein is responsible for the increase in O2 reduction. Furthermore, differences in the membrane localization of m-type thioredoxins and 2-Cys peroxiredoxin were detected between thylakoids of short day and long day plants. Overall, we propose a model of redox regulation of O2 reduction according to the reduction power of the stroma and the ability of different thiol-containing proteins to form a network of redox interactions.

Investigating perimidine precursors for the synthesis of new multiredox polymers

We present a new simple approach for electrochemical synthesis of semi-condensed ambipolar perinone polymers with phthaloperine (p1) or phenanthroline (p2) skeleton from available and cheap perimidine precursors. Polymerization of perimidine derivatives varies in efficiency depending on the monomer, but overall is highly efficient, especially when electropolymerization is used. Electrooxidation is well controllable and provides a certain characteristic share of new bonds in the structure of perimidine polymers: semi-ladder bis-perimidine unit, ladder bis-perimidine unit, and protonated bis-perimidine unit. Polymer p2 obtained with higher efficiency was put through broader analysis (UV–Vis, IR, ESR and quantum-chemical calculations). As indicated, donor–acceptor structure and specific intermolecular interactions of p2 assure its electrical conductivity and complex redox activity. Although protonated bonds break π-conjugation in the structure of the macromolecule, there is also a diradical state that favors intermolecular interactions and intermolecular π-conjugation channels within bis-perimidine segments. It has been proven that there is a diradical state which appears as an intermediate state between the oxidized and reduced states of the protonated polymer unit. This work positions perimidine polymers as a versatile ambipolar multiredox p- and n-type conductor, indicating a potential for expanding perinone-based perylene-diperimidine polymers for innovative electronics and (bio)sensors.

A complex and dynamic redox network regulating oxygen reduction at photosystem I

A complex and dynamic redox network regulating oxygen reduction at photosystem I

Mechanistic insights into molybdenum immobilization within geopolymer waste form

Molybdenum (Mo) tends to form highly mobile, non-sorbing complex redox species, which complicates its immobilization and encapsulation in cement and glass matrices. This study explores the potential of incorporating Mo into an alternative green cementitious material known as geopolymer (GP). By employing X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), morphological analysis, and nitrogen adsorption-desorption techniques, we obtained comprehensive insights into the chemical behavior of Mo and its impact on the morphology and structure of the GP matrix. XRD and TGA analysis demonstrated that increasing Mo content significantly enhances the crystallinity and thermal stability of the GP matrix, attributed to Mo field effects. High-resolution SEM, TEM, and EDS mapping revealed the structural encapsulation of Mo-rich cavities within the GP waste form. A decrease in leaching rates with higher Mo content, alongside reduced pore volume and pore size, underscores the material's chemical durability. Post-leaching characterizations confirmed that the GP retains excellent structural strength with minimal changes in mesoporosity and surface area. This resilience highlights the effectiveness of GPs in immobilizing non-sorbing species like MoO32−, making them ideal for long-term waste management.

Energetics and Redox Kinetics of Pure Ferrocene-Terminated N-Heterocyclic Carbene Self-Assembled Monolayers on Gold.

N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on gold have received considerable attention, but little is known about the lateral interactions between neighboring NHC molecules, their stability when subjected to aggressive oxidizing/reducing conditions, and their interactions with solution ions, all of which are essential for their use in a wide range of applications. To address these deficiencies, we present a comprehensive investigation of two different ferrocene (Fc)-terminated NHC SAMs with different chain lengths and linking groups. Pure monolayers of Fc-terminated NHCs display only a single, symmetrical pair of redox peaks, implying the formation of a homogeneous SAM structure with uniformly distributed Fc/Fc+ redox centers. By comparison, pure Fc-alkylthiol SAMs exhibit complex and impractical redox chemistry and require surface dilution in order to achieve reproducible properties. The NHC SAMs examined in this study exhibit very fast Fc redox kinetics and comparable or even superior stability against the application of multiple potential cycles or long-time holding at constant potential compared to alkylthiol SAMs. Furthermore, ion pairing of Fc+ and hydrophobic perchlorate and other hydrophilic anions is observed with Fc-NHC SAMs, highlighting conditions favorable for future applications of these monolayers. This study should therefore shed light on the very promising characteristics of redox-active NHC SAMs as an alternative to traditional Fc-alkylthiol SAMs for multiple practical applications, including in sensors and electrocatalysis.

Redox-active vitamin C suppresses human osteosarcoma growth by triggering intracellular ROS-iron–calcium signaling crosstalk and mitochondrial dysfunction

Pharmacological vitamin C (VC) has gained attention for its pro-oxidant characteristics and selective ability to induce cancer cell death. However, defining its role in cancer has been challenging due to its complex redox properties. In this study, using a human osteosarcoma (OS) model, we show that the redox-active property of VC is critical for inducing non-apoptotic cancer cell death via intracellular reactive oxygen species (ROS)-iron-calcium crosstalk and mitochondrial dysfunction. In both 2D and 3D OS cell culture models, only the oxidizable form of VC demonstrated potent dose-dependent cytotoxicity, while non-oxidizable and oxidized VC derivatives had minimal effects. Live-cell imaging showed that only oxidizable VC caused a surge in cytotoxic ROS, dependent on iron rather than copper. Inhibitors of ferroptosis, a form of iron-dependent cell death, along with classical apoptosis inhibitors, were unable to completely counteract the cytotoxic effects induced by VC. Further pharmacological and genetic inhibition analyses showed that VC triggers calcium release through inositol 1,4,5-trisphosphate receptors (IP3Rs), leading to mitochondrial ROS production and eventual cell death. RNA sequencing revealed down-regulation of genes involved in the mitochondrial electron transport chain and oxidative phosphorylation upon pharmacological VC treatment. Consistently, high-dose VC reduced mitochondrial membrane potential, oxidative phosphorylation, and ATP levels, with ATP reconstitution rescuing VC-induced cytotoxicity. In vivo OS xenograft studies demonstrated reduced tumor growth with high-dose VC administration, concomitant with the altered expression of mitochondrial ATP synthase (MT-ATP). These findings emphasize VC's potential clinical utility in osteosarcoma treatment by inducing mitochondrial metabolic dysfunction through a vicious intracellular ROS-iron-calcium cycle.

Ru3@Mo2CO2 MXene single-cluster catalyst for highly efficient N2-to-NH3 conversion.

Single-cluster catalysts (SCCs) representing structurally well-defined metal clusters anchored on support tend to exhibit tunable catalytic performance for complex redox reactions in heterogeneous catalysis. Here we report a theoretical study on an SCC of Ru3@Mo2CO2 MXene for N2-to-NH3 thermal conversion. Our results show that Ru3@Mo2CO2 can effectively activate N2 and promotes its conversion to NH3 through an association mechanism, in which the rate-determining step of NH2* + H* → NH3* has a low energy barrier of 1.29eV. Notably, with the assistance of Mo2CO2 support, the positively charged Ru3 cluster active site can effectively adsorb and activate N2, leading to 0.74 |e| charge transfer from Ru3@Mo2CO2 to the adsorbed N2. The supported Ru3 also acts as an electron reservoir to regulate the charge transfer for various intermediate steps of ammonia synthesis. Microkinetic analysis shows that the turnover frequency of the N2-to-NH3 conversion on Ru3@Mo2CO2 is as high as 1.45×10-2 s-1 site-1 at a selected thermodynamic condition of 48bar and 700K, the performance of which even surpasses that of the Ru B5 site and Fe3/θ-Al2O3(010) reported before. Our work provides a theoretical understanding of the high stability and catalytic mechanism of Ru3@Mo2CO2 and guidance for further designing and fabricating MXene-based metal SCCs for ammonia synthesis under mild conditions.

Machine Learning Approach to Vertical Energy Gap in Redox Processes.

A straightforward approach to calculating the free energy change (ΔG) and reorganization energy of a redox process is linear response approximation (LRA). However, accurate prediction of redox properties is still challenging due to difficulties in conformational sampling and vertical energy-gap sampling. Expensive hybrid quantum mechanical/molecular mechanical (QM/MM) calculations are typically employed in sampling energy gaps using conformations from simulations. To alleviate the computational cost associated with the expensive QM method in the QM/MM calculation, we propose machine learning (ML) methods to predict the vertical energy gaps (VEGs). We tested several ML models to predict the VEGs and observed that simple models like linear regression show excellent performance (mean absolute error ∼0.1 eV) in predicting VEGs in all test systems, even when using features extracted from cheaper semiempirical methods. Our best ML model (extra trees regressor) shows a mean absolute error of around 0.1 eV while using features from the cheapest QM method. We anticipate our approach can be generalized to larger macromolecular systems with more complex redox centers.

Unveiling the microstructure and promising electrochemical performance of heavily phosphorus-doped diamond electrodes

The challenge of doping synthetic diamond with phosphorus stems from the atomic size mismatch between phosphorus and carbon atoms, which previously hindered achieving high phosphorus doping levels. This limitation delayed the exploration of phosphorus-doped diamond (PDD) in electrochemical applications, where it holds potential as a novel and appealing electrode material because PDD uniquely combines diamond's exceptional properties with phosphorus atoms inducing n-type conductivity. In this study, heavily doped PDD electrodes were successfully developed using chemical vapour deposition, followed by comprehensive microstructural and electrochemical characterisations. The influence of phosphorus doping, manipulated via high phosphine gas concentration or time-dependant precursor gas flow control, on the PDD properties was thoroughly examined. PDD layers grown at higher phosphine concentrations demonstrated enhanced phosphorus incorporation, leading to a higher prevalence of fine nano-crystalline diamond grains and non-diamond carbon components, while also slowing the growth rate. Notably, a distinct PDD sample produced under dynamic gas flow with lower phosphine concentration revealed larger grain sizes, increased effective deposition rate, and improved phosphorus levels compared to its counterpart synthesized under static conditions. Cyclic voltammetry in a 1 mol L−1 KCl solution revealed a low double-layer capacitance (<11 µF cm−2) in all as-grown PDD electrodes. However, significant differences between the samples emerged during the experiments conducted with redox probes [Ru(NH3)6]3+/2+ and [Fe(CN)6]3−/4−. Particularly, higher phosphorus content promoted well-developed voltammograms, significantly reduced peak-to-peak separation values, faster electron transfer rates, and increased peak currents. Furthermore, the possibility of using heavily P-doped diamond electrodes for the detection of two organic analytes, dopamine and ascorbic acid, was successfully manifested. All in all, the as-grown, highly P-doped diamond electrodes proved their ability, first time ever, to record well-defined signals of both inorganic redox probes and complex organic compounds, unravelling their potential in electroanalysis and sensor development and broadening the scope of PDD utilisation.

Modeling groundwater redox conditions at national scale through integration of sediment color and water chemistry in a machine learning framework

Redox conditions play a crucial role in determining the fate of many contaminants in groundwater, impacting ecosystem services vital for both the aquatic environment and human water supply. Geospatial machine learning has previously successfully modelled large-scale redox conditions. This study is the first to consolidate the complementary information provided by sediment color and water chemistry to enhance our understanding of redox conditions in Denmark. In the first step, the depth to the first redox interface is modelled using sediment color from 27,042 boreholes. In the second step, the depth of the first redox interface is compared against water chemistry data at 22,198 wells to classify redox complexity. The absence of nitrate containing water below the first redox interface is referred to as continuous redox conditions. In contrast, discontinuous redox conditions are identified by the presence of nitrate below the first redox interface. Both models are built using 20 covariate maps, encompassing diverse hydrologically relevant information. The first redox interface is modelled with a mean error of 0.0 m and a root-mean-squared error of 8.0 m. The redox complexity model attains an accuracy of 69.8 %. Results indicate a mean depth to the first redox interface of 8.6 m and a standard deviation of 6.5 m. 60 % of Denmark is classified as discontinuous, indicating complex redox conditions, predominantly collocated in clay rich glacial landscapes. Both maps, i.e., first redox interface and redox complexity are largely driven by the water table and hydrogeology. The developed maps contribute to our understanding of subsurface redox processes, supporting national-scale land-use and water management.

Enhanced structural stability and durability in lithium-rich manganese-based oxide via surface double-coupling engineering

Lithium-rich manganese-based oxides (LRMOs) exhibit high theoretical energy densities, making them a prominent class of cathode materials for lithium-ion batteries. However, the performance of these layered cathodes often declines because of capacity fading during cycling. This decline is primarily attributed to anisotropic lattice strain and oxygen release from cathode surfaces. Given notable structural transformations, complex redox reactions, and detrimental interface side reactions in LRMOs, the development of a single modification approach that addresses bulk and surface issues is challenging. Therefore, this study introduces a surface double-coupling engineering strategy that mitigates bulk strain and reduces surface side reactions. The internal spinel-like phase coating layer, featuring three-dimensional (3D) lithium-ion diffusion channels, effectively blocks oxygen release from the cathode surface and mitigates lattice strain. In addition, the external Li3PO4 coating layer, noted for its superior corrosion resistance, enhances the interfacial lithium transport and inhibits the dissolution of surface transition metals. Notably, the spinel phase, as excellent interlayer, securely anchors Li3PO4 to the bulk lattice and suppresses oxygen release from lattices. Consequently, these modifications considerably boost structural stability and durability, achieving an impressive capacity retention of 83.4% and a minimal voltage decay of 1.49 mV per cycle after 150 cycles at 1 C. These findings provide crucial mechanistic insights into the role of surface modifications and guide the development of high-capacity cathodes with enhanced cyclability.

Enhanced Electron Transfer Rates Between Surface-Attached Dye Molecules with Large Pendant Moieties and Co3+/2+ Complex Redox Mediators

Enhanced Electron Transfer Rates Between Surface-Attached Dye Molecules with Large Pendant Moieties and Co^3+/2+ Complex Redox Mediators

Advances on Single‐Atom‐Based Dual‐Site Photocatalysts: Fundamentals, Mechanisms, and Applications

Single‐atom catalysts (SACs) have emerged as leading‐edge research in the field of photocatalysis due to outstanding photocatalytic performance, maximum atomic utilization efficiency, and well‐defined catalytic active sites. However, the singular functionality of active sites in SACs restricts their applications in complex redox reactions involving multiple intermediates and reaction pathways. To circumvent this limitation, a second site comprising single atoms (SA), alloys, clusters, or nanoparticles is proposed to establish SA‐based dual‐site photocatalysts (SA DSPs). While maintaining 100% atomic utilization, the second site and site–site collaboration endow SA DSPs with superior photocatalytic activities to surpass those of SACs. In this review, the latest investigations on SA DSPs featuring diverse compositions, electronic and geometric configurations, site–site collaboration, and metal–support interactions are summarized. Thereafter, the mechanisms underlying enhanced photocatalytic activities are elucidated regarding the roles of the dual sites in charge‐carrier dynamics and surface reactivity. Furthermore, the state‐of‐the‐art applications in photocatalytic hydrogen evolution, CO2 reduction, and methane oxidation, etc., over SA DSPs are discussed. It is anticipated that this review will offer insights into precise control and design of dual sites in photocatalysts, thereby advancing photocatalysis toward commercial viability.

Regulating anionic redox reversibility in Li-rich layered cathodes via diffusion-induced entropy-assisted surface engineering

Cobalt-free lithium- and manganese-rich layered oxides (LMROs) are regarded as effective cathode materials for lithium storage due to their high capacity and cost-effectiveness. However, challenges with structural degradation, resulting in poor cyclability and rate performance, have hindered their widespread use. Essentially, rapid structural degradation arises from irreversible and complex redox reactions, triggering oxygen release, transition metal migration, and electrolyte decomposition. To tackle this issue, we propose an epitaxial entropy-assisted construction approach to develop a sturdy surface with adaptable composition, stabilising the surface crystal structure and preventing undesirable interface reactions. This distinct reconstructed surface comprises diverse heterogeneous elements and composite microstructures. The heteroatom-doped layer, with multi-doping sites like Li, O site, and tetrahedral positions, effectively manages the chemical environment and electronic structure of surface lattice oxygen. This epitaxial entropy stabilisation approach, stemming from multi-element synergy, effectively controls redox progress to limit oxygen release and curb transition metal migration, reducing structural decay. Additionally, the composite coated layer, containing oxygen defects and heterogeneous spinel phases, can hinder electrolyte corrosion and promote Li+ transport. Using these epitaxial entropy surface modifications, the LMRO cathode demonstrates regulated anionic redox reversibility and enhanced cycling stability across diverse operational conditions. This epitaxial entropy-assisted surface engineering offers a promising avenue for stabilising high-energy cathode materials.

High Electronic Coupling between Cu Complexes and Oxidized Dyes Confirmed by Measurements of Driving Force Dependent Regeneration Kinetics in Minimal Electrolyte System.

We confirm fast regeneration kinetics between copper complexes and oxidized organic dyes and the major contribution of electronic coupling (HDA). The highest efficiency of dye-sensitized TiO2 solar cells has been shown by employing Cu complex redox couples. Various groups have reported a fast regeneration rate of oxidized dyes by Cu complexes giving a low driving force attributed to low reorganization energy (λ), but the effect of HDA has not been evaluated. The values of HDA and λ can be derived from driving force dependent transient absorption (TA) measurements. However, analyzing TA decay using Cu complexes is not trivial because accelerated recombination by the presence of Cu2+ complexes and biphasic TA decay often complicates the analysis. Here we employ 16 Cu1+ and Co2+ complexes and two dyes. To simplify the system, i.e., making a minimal electrolyte system, Cu2+ and Co3+ complexes and a common additive of 4-tert-butylpyridine are not used. From the driving force dependent TA decays of oxidized dyes by both Cu1+ and Co2+ complexes, λ for the combination of the Cu complexes and dyes is found to be about 0.15 eV lower than that of Co complexes. Approximately 3 to 5 times higher HDA values of Cu complexes than those of Co complexes are obtained, which is the dominant factor for faster rates. The values vary with the structure of the molecules, showing the possibility of increasing the HDA values further. The higher HDA values of a Cu complex than that of a Co complex are also reproduced by quantum chemical calculations.

Label-free electrochemical aptasensor for detection of Acinetobacter baumannii: Unveiling the kinetic behavior of reduced graphene oxide v/s graphene oxide

In this study, we introduce an electrochemical aptasensor for the sensitive detection of Acinetobacter baumannii. This method, based on impedance and current analysis, represents a first-of-its kind platform in the field of A. baumannii detection. We employed a screen-printed carbon electrode modified with both graphene oxide (GO) and reduced graphene oxide (rGO) as the immobilization platform, and the bacteria specific aptamer was employed as the biorecognition element. The aptamer selectively interacts with A. baumannii, causing a decrease in the peak current of the redox complex because the binding biomolecules on the electrode surface hinder the electron transfer of the redox probe. This initial point-of-care-compatible rGO electrochemical aptasensor demonstrated an exceptional sensing performance with an impressive limit of detection of 10 CFU/mL for detecting A. baumannii. This enhanced sensitivity can be attributed to several key factors including structural defects during reduction, increased surface area and improved electron transfer kinetics. The findings of this study highlight the potential of the developed aptasensor as a rapid and reliable detection platform for various pathogenic diseases. By further ensuring seamless integration into clinical practice, these label-free graphene-based aptasensors, with their π-π interactions and other favorable attributes, hold great promise for sensitive and specific pathogen detection, thereby contributing to advancements in healthcare diagnostics.

Chloroplast thiol redox dynamics through the lens of genetically encoded biosensors.

Chloroplasts fix carbon by using light energy and have evolved a complex redox network that supports plastid functions by (i) protecting against reactive oxygen species and (ii) metabolic regulation in response to environmental conditions. In thioredoxin- and glutathione/glutaredoxin-dependent redox cascades, protein cysteinyl redox steady states are set by varying oxidation and reduction rates. The specificity and interplay of these different redox-active proteins are still under investigation, for example to understand how plants cope with adverse environmental conditions by acclimation. Genetically encoded biosensors with distinct specificity can be targeted to subcellular compartments such as the chloroplast stroma, enabling in vivo real-time measurements of physiological parameters at different scales. These data have provided unique insights into dynamic behaviours of physiological parameters and redox-responsive proteins at several levels of the known redox cascades. This review summarizes current applications of different biosensor types as well as the dynamics of distinct protein cysteinyl redox steady states, with an emphasis on light responses.

Redox processes are major regulators of leukotriene synthesis in neutrophils exposed to bacteria Salmonella typhimurium; the way to manipulate neutrophil swarming.

Neutrophils play a primary role in protecting our body from pathogens. When confronted with invading bacteria, neutrophils begin to produce leukotriene B4, a potent chemoattractant that, in cooperation with the primary bacterial chemoattractant fMLP, stimulates the formation of swarms of neutrophils surrounding pathogens. Here we describe a complex redox regulation that either stimulates or inhibits fMLP-induced leukotriene synthesis in an experimental model of neutrophils interacting with Salmonella typhimurium. The scavenging of mitochondrial reactive oxygen species by mitochondria-targeted antioxidants MitoQ and SkQ1, as well as inhibition of their production by mitochondrial inhibitors, inhibit the synthesis of leukotrienes regardless of the cessation of oxidative phosphorylation. On the contrary, antioxidants N-acetylcysteine and sodium hydrosulfide promoting reductive shift in the reversible thiol-disulfide system stimulate the synthesis of leukotrienes. Diamide that oxidizes glutathione at high concentrations inhibits leukotriene synthesis, and the glutathione precursor S-adenosyl-L-methionine prevents this inhibition. Diamide-dependent inhibition is also prevented by diphenyleneiodonium, presumably through inhibition of NADPH oxidase and NADPH accumulation. Thus, during bacterial infection, maintaining the reduced state of glutathione in neutrophils plays a decisive role in the synthesis of leukotriene B4. Suppression of excess leukotriene synthesis is an effective strategy for treating various inflammatory pathologies. Our data suggest that the use of mitochondria-targeted antioxidants may be promising for this purpose, whereas known thiol-based antioxidants, such as N-acetylcysteine, may dangerously stimulate leukotriene synthesis by neutrophils during severe pathogenic infection.

The synthesis and characterization of an iron(VII) nitrido complex

Complexes of iron in high oxidation states are captivating research subjects due to their pivotal role as active intermediates in numerous catalytic processes. Structural and spectroscopic studies of well-defined model complexes often provide evidence of these intermediates. In addition to the fundamental molecular and electronic structure insights gained by these complexes, their reactivity also affects our understanding of catalytic reaction mechanisms for small molecule and bond-activation chemistry. Here, we report the synthesis, structural and spectroscopic characterization of a stable, octahedral Fe(VI) nitrido complex and an authenticated, unique Fe(VII) species, prepared by one-electron oxidation. The super-oxidized Fe(VII) nitride rearranges to an Fe(V) imide through an intramolecular amination mechanism and ligand exchange, which is characterized spectroscopically and computationally. This enables combined reactivity and stability studies on a single molecular system of a rare high-valent complex redox pair. Quantum chemical calculations complement the spectroscopic parameters and provide evidence for a diamagnetic (S = 0) d2 Fe(VI) and a genuine S = 1/2, d1 Fe(VII) configuration of these super-oxidized nitrido complexes.

Opportunities and Challenges of Phosphorus‐based Anodes for Practical Battery Application

AbstractPhosphorus‐based anode materials have attracted considerable attention due to their high theoretical capacity, safe operational potential, and favorable redox chemistry for diverse alkali metal‐ion storage applications. Their excellent performance in lithium storage makes them promising candidates for fast‐charging batteries. However, challenges such as complex redox reactions, substantial volume expansion during lithiation, vulnerability to oxidation, and the lack of a mature mass production process hinder their further development. Current research predominantly focuses on establishing multilevel nanostructures or robust solid electrolyte interphases (SEI) to mitigate volume expansion. Nonetheless, a consensus within the academic community on the maximum degree of volume expansion for practical electrode application in cells is yet to be established. Furthermore, investigations into the kinetics of redox reactions, side reactions in the presence of air or electrolyte, and mass production processes for phosphorus‐based anodes are relatively limited. This comprehensive review meticulously examines these challenges, providing nuanced insights. Additionally, the review offers perspectives on potential advancements in phosphorus‐based anode development, contributing to the ongoing discourse on the future trajectory of research in this domain.