Boosting the Structural and Electrochemical Stability of Chloride-Ion-Conducting Perovskite Solid Electrolytes by Alkali Ion Doping.

The use of chloride-based solid electrolytes derived from Lewis acid‒base reactions enables the construction of various new rechargeable batteries, such as chloride ion batteries (CIBs). However, a critical problem with these electrolytes is their poor stability under low-temperature, moist, or electrochemical conditions, which can lead to deterioration of the phase structure and a loss of ion conduction. Herein, the robust cubic structure of tin-based perovskite chloride-a chloride ion conductor-is achieved by alkali ion doping at the tin site via direct mechanical milling. The as-prepared cubic CsSn0.925Na0.075Cl2.925 (CSNC) electrolyte exhibits outstanding structural stability over a broad temperature range of 213-473 K or under a high relative humidity of up to 90%, at which the typical chloride electrolytes previously reported deteriorate because of moisture. Importantly, mild annealing can modify the microstructure of the CSNC, resulting in a two fold increase in ionic conductivity and an increase in electrochemical stability, which is superior to those of other chloride electrolytes reported in previous studies. The effective chloride-ion transfer and wide electrochemical window of the CSNC are further demonstrated in different solid-state CIBs.

Fluorine-Free Cycloaliphatic Epoxy-Based Siloxane Nanohybrid Binder with High Polar Hydroxyl Group Content Enabling LiFePO4-Type Battery with High Electrochemical Performance and Stability.

LiFePO4-type (LFP) batteries have attracted significant attention in most battery manufacturing industries due to their long lifespan, high-temperature safety, and low cost of raw materials. However, as an active material, LFP still suffers from several intrinsic drawbacks, including poor conductivity, a low Li+ diffusion coefficient, low capacity, and a lack of electrochemical stability, primarily due to conventional fluorine-based binders. Here, we report a simple yet effective approach to developing a fluorine-free binder based on a robust cycloaliphatic epoxy-based siloxane nanohybrid material (CES) to achieve high electrochemical stability in LFP batteries. The high content of silanol moieties in CES induces a strong affinity for the active material and conductive agent, significantly improving rheological (thixotropy) and mechanical (adhesion and cohesion) properties, which enable the formation of a uniformly coated electrode. As a result, we achieved superior electrochemical performance and stability in CES-applied electrodes compared to those with conventional fluorine-based binders. We investigate the reasons behind the contribution of CES to the electrochemical stability of LFP batteries through various analyses. The high thermal and oxidation stability of CES effectively prevents degradation of LFP-based active materials. Our binder development strategy offers a significant breakthrough in replacing conventional fluorine-based binders, advancing the development of high-performance and stable secondary batteries.

Diethylenetriaminepentaacetic Acid-based Conducting Solid Polymer Electrolytes Impede Lithium Dendrites and Impart Antioxidant Capacity in Lithium-Ion Batteries.

In the development of lithium-ion batteries (LIBs), cheaper and safer solid polymer electrolytes are expected to replace combustible organic liquid electrolytes to meet the larger market demand. However, low ionic conductivity and inadequate cycling stability impede their commercial viability. Herein, a novel flexible conducting solid polymer electrolytes (CSPEs) based on polyvinyl alcohol (PVA) and ion-polarized diethylenetriaminepentaacetic acid (P-DETP) is developed for the first time and applied in LIBs. PVA and P-DETP form a compact polymer network through hydrogen bonding, enhancing the thermomechanical stability of CSPE while restricting the migration of larger anions. Furthermore, density functional theory calculations confirm that P-DETP can facilitate the dissociation of Li+-TFSI- via electrostatic attraction, resulting in increased mobility of lithium ions. Additionally, P-DETP contributes to the formation of a stable electrode-electrolyte interface layer, effectively suppressing the growth of lithium dendrites and improving antioxidant capacity. These synergistic effects enable CSPE to exhibit remarkable properties including high ionic conductivity (2.8 × 10-4 S cm-1), elevated electrochemical potential (5.1 V), and excellent lithium transference number (0.869). Notably, the P-DETP/LiTFSI CSPE demonstrates stable performance not only in LiFePO4 batteries but also adapts to high-nickel ternary LiNi0.88Co0.06Mn0.06O2 cathode, highlighting its immense potential for application in high energy density LIBs.

Organic Cationic-Coordinated Perfluoropolymer Electrolytes with Strong Li+-Solvent Interaction for Solid State Li-Metal Batteries.

The practical application of solid-state polymer lithium-metal batteries (LMBs) is plagued by the inferior ionic conductivity of the applied polymer electrolytes (PEs), which is caused by the coupling of ion transport with the motion of polymer segments. Here, solvated molecules based on ionic liquid and lithium salt with strong Li+-solvent interaction are inserted into an elaborately engineered perfluoropolymer electrolyte via ionic dipole interaction, extensively facilitating Li+ transport and improving mechanical properties. The intensified formation of solvation structures of contact ion pairs and ionic aggregates, as well as the strong electron-withdrawal properties of the F atoms in perfluoropolymers, give the PE high electrochemical stability and excellent interfacial stability. As a result, Li||Li symmetric cells demonstrate a lifetime of 2500 h and an exceptionally high critical current density above 2.3 mA cm-2, Li||LiFePO4 batteries exhibit consistent cycling for 550 cycles at 10 C, and Li||uncoated LiNi0.8Co0.1Mn0.1O2 cells achieve 1000 cycles at 0.5 C with an average Coulombic efficiency of 98.45 %, one of the best results reported to date based on PEs. Our discovery sheds fresh light on the targeted synergistic regulation of the electro-chemo-mechanical properties of PEs to extend the cycle life of LMBs.

Enhanced mechanical and surface chemical stability in cobalt-free, high-nickel cathode materials for lithium-ion batteries.

Cobalt-free, high-nickel cathode materials are essential for the sustainable evolution of energy storage technologies, reducing the dependence on resources with significant environmental and social implications and simultaneously improving the efficiency and cost effectiveness of batteries. This paper introduces a cobalt-free, high-nickel cathode material called 0.01B-LiNi0.98Mg0.01Zr0.01O2 (NMZB) developed using a novel blend of elements to enhance mechanical and surface chemical stability. Detailed evaluations confirmed the successful integration of Mg, Zr, and B into the particles, with Mg and Zr primarily located within the particle interior and B predominantly on the surface. This unique elemental configuration significantly improves the stability of the bulk phase and surface structure of the material. In addition, the refinement of primary particles within NMZB further enhances its mechanical stability. As a result, NMZB exhibits exceptional electrochemical stability, achieving 90.5 % capacity retention after 200 cycles at a 1C rate. This compositional strategy incorporates a high nickel content into layered materials while eliminating cobalt, which is crucial for advancing the development of cost effective and high-performance lithium-ion battery technology.

High ionic conductivity materials Li3YBr6and Li3LaBr6for solid-state batteries: first-principles calculations.

High ionic conductivity solid-state electrolytes are essential for powerful solid-state lithium-ion batteries. With density functional theory andab initiomolecular dynamics simulations, we investigated the crystal structures of Li3YBr6and Li3LaBr6. The lowest energy configurations with uniform distribution of lithium ions were identified. Both materials have wide electrochemical stability windows (ESW): 2.64 V and 2.57 V, respectively. The experimental ESW for Li3YBr6is 2.50 V. Through extrapolating various temperature diffusion results, the conductivity of Li3YBr6was obtained at room temperature, approximately 3.9 mS cm-1, which is comparable to the experimental value 3.3 mS cm-1. Li3LaBr6has a higher conductivity, a 100% increase compared with Li3YBr6. The activation energies of Li3YBr6and Li3LaBr6through the Arrhenius plot are 0.26 eV and 0.24 eV, respectively, which is also close to the experimental value of 0.30 eV for Li3YBr6. This research explored high ionic conductivity halide materials and will contribute to developing solid-state lithium-ion batteries.

Electrochemical Stability of MXenes in Water Based on Constant Potential AIMD Simulations.

MXene has been recently explored as promising electrocatalytic materials to accelerate the electrocatalytic process for hydrogen evolution, but their dynamic stability under electrochemical conditions remains elusive. Here we performed first-principle ab initio molecular dynamics calculations to reveal the electrochemical stability of Ti2CTx MXene in different aqueous environments. The results revealed the high vulnerability of the pure and vacancy-defected Ti2CO2 MXene towards water attack, leading to surface oxidation of MXene under neutral electrochemical condition that formed adsorbed oxygen species to Ti and dissociated proton in solution. The surface oxidation of Ti2CO2 could be prevented in the acid condition or in the neutral condition under the negative potential. Differently, the fully F- or OH-functionalized Ti2CF2 and Ti2C(OH)2 as well as the mixed functionalized Ti2C(O0.5OH0.5)2 and Ti2CO1.12F0.88 are highly stable under various electrochemical conditions, which can effectively prevent close contact between water and surface Ti atoms via electronic repulsion or steric hindrance. These findings provide atomic level understanding of the aqueous stability of MXene and provide useful strategies to prevent degradation and achieve highly stable MXenes.

Electrochemical Investigation of PEDOT:PSS/Graphene Aging in Artificial Sweat.

Herein, we investigate the potential application of a composite consisting of PEDOT:PSS/Graphene, deposited via spray coating on a flexible substrate, as an autonomous conducting film for applications in wearable biosensor devices. The stability of PEDOT:PSS/Graphene is assessed through electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and linear polarization (LP) during exposure to an artificial sweat electrolyte, while scanning electron microscopy (SEM) was employed to investigate the morphological changes in the layer following these. The results indicate that the layers exhibit predominant capacitive behavior in the potential range of -0.3 to 0.7 V vs. Ag/AgCl, with a cut-off frequency of approximately 1 kHz and retain 90% capacity after 500 cycles. Aging under exposure to air for 6 months leads only to a minor increase in impedance, demonstrating potential for storage under non-demanding conditions. However, prolonged exposure (>48 h) to the artificial sweat causes significant degradation, resulting in an impedance increase of over 1 order of magnitude. The observed degradation raises important considerations for the long-term viability of these layers in wearable biosensor applications, prompting the need for additional protective measures during prolonged use. These findings contribute to ongoing efforts to enhance the stability and reliability of conducting materials for biosensors in health care and biotechnology applications.

Fluorine-Like BH4-Doped Li6PS5Cl with Improved Ionic Conductivity and Electrochemical Stability.

Sulfide-based solid electrolytes with high ionic conductivity have attracted a lot of attention. However, the incompatibility and interfacial instability of sulfides with the lithium metal anode have emerged as pivotal constraints on their development. To address this challenge, we proposed and successfully synthesized the BH4- doped argyrodite-type electrolyte Li6PS5Cl0.9(BH4)0.1 by mechanical ball milling and annealing. This electrolyte not only exhibits an exceptionally high ionic conductivity of 2.83 × 10-3 S cm-1 at 25 °C but also demonstrates outstanding electrochemical stability. The Li/Li6PS5Cl0.9(BH4)0.1/Li symmetric cell can stably run for more than 400 h at a current density of 0.2 mA cm-2. In sharp contrast, although the F- doped sample, Li6PS5Cl0.3F0.7, can highly improve Li6PS5Cl's electrochemical stability, the ionic conductivity will reduce dramatically to 6.63 × 10-4 S cm-1. The stepwise current method reveals a critical current density of 3.5 mA cm-2 for Li6PS5Cl0.9(BH4)0.1, which makes it a competitive sulfide-based solid electrolyte. This research offers valuable insights for designing new borohydride-containing solid electrolytes.

Chlorine-Rich Na6-xPS5-xCl1+x: A Promising Sodium Solid Electrolyte for All-Solid-State Sodium Batteries.

Developing argyrodite-type, chlorine-rich, sodium-ion, solid-state electrolytes with high conductivity is a long-term challenge that is crucial for the advancement of all-solid-state batteries (ASSBs). In this study, chlorine-rich, argyrodite-type Na6-xPS5-xCl1+x solid solutions were successfully developed with a solid solution formation range of 0 ≤ x ≤ 0.5. Na5.5PS4.5Cl1.5 (x = 0.5), displaying a highest ionic conductivity of 1.2 × 10-3 S/cm at 25 °C, which is more than a hundred times higher than that of Na6PS5Cl. Cyclic voltammetry and electrochemical impedance spectroscopy results demonstrated that the rich chlorine significantly enhanced the ionic conductivity and electrochemical stability, in addition to causing a reduction in activation energy. The Na5.5PS4.5Cl1.5 composite also showed the characteristics of a pure ionic conductor without electronic conductivity. Finally, the viability of Na5.5PS4.5Cl1.5 as a sodium electrolyte for all-solid-state sodium batteries was checked in a lab-scale ASSB, showing stable battery performance. This study not only demonstrates new composites of sodium-ionic, solid-state electrolytes with relatively high conductivity but also provides an anion-modulation strategy to enhance the ionic conductivity of argyrodite-type sodium solid-state ionic conductors.

Self-Healing Ionogel-Enabled Self-Healing and Wide-Temperature Flexible Zinc-Air Batteries with Ultra-Long Cycling Lives.

Hydrogel-based zinc-air batteries (ZABs) are promising flexible rechargeable batteries. However, the practical application of hydrogel-based ZABs is limited by their short service life, narrow operating temperature range, and repair difficulty. Herein, a self-healing ionogel is synthesized by the photopolymerization of acrylamide and poly(ethylene glycol) monomethyl ether acrylate in 1-ethyl-3-methylimidazolium dicyanamide with zinc acetate dihydrate and first used as an electrolyte to fabricate self-healing ZABs. The obtained self-healing ionogel has a wide operating temperature range, good environmental and electrochemical stability, high ionic conductivity, satisfactory mechanical strength, repeatable and efficient self-healing properties enabled by the reversibility of hydrogen bonding, and the ability to inhibit the production of dendrites and by-products. Notably, the self-healing ionogel has the highest ionic conductivity and toughness compared to other reported self-healing ionogels. The prepared self-healing ionogel is used to assemble self-healing flexible ZABs with a wide operating temperature range. These ZABs have ultra-long cycling lives and excellent stability under harsh conditions. After being damaged, the ZABs can repeatedly self-heal to recover their battery performance, providing a long-lasting and reliable power supply for wearable devices. This work opens new opportunities for the development of electrolytes for ZABs.

A 2.4 V Aqueous Zinc-Ion Battery Enabled by the Photoelectrochemical Effect of a Modified BiOI Photocathode: Shattering the Shackle of the Electrochemical Window of an Aqueous Electrolyte.

Aqueous zinc-ion batteries emerge as a promising energy storage system with merits of high security, abundance, and being environmentally benign. But the low operating voltages of aqueous electrolytes restrict their energy densities. Previous reports have mostly focused on modifying the electrolytes to enlarge the operating voltages of aqueous zinc-ion batteries. However, either extra-expensive salts or potential safety hazards of organic additives are considered to be adverse for practical large-scale applications. Here, a proof-of-concept to enlarge the operating voltage of an aqueous zinc-ion battery by incorporating a well-designed semiconductor photocathode is proposed, which produces a photovoltage (Vph) across the semiconductor/liquid junction (SCLJ) interface to elevate the output voltage of zinc-ion battery under irradiation. The operating voltage of an aqueous zinc-ion battery can be markedly raised from 1.78 (thermodynamic limit) to 2.4 V when a BiOI nanoflake array photocathode with good surface modification is introduced, achieving a round-trip efficiency of 114.3% and a 34.8% increase of energy density compared to the theoretical value. The successive ionic layer adsorption and reaction modified surface effectively passivates surface trap defects of the BiOI photocathode and thus enlarges its Vph from 60 to 240 mV under irradiation. This study provides a design to enlarge the output voltages of aqueous zinc-ion batteries and other energy storage systems, providing insight into widening the voltage window, which is that the operating voltages are determined by photocathode under irradiation and not restricted by the electrochemical stability window of dilute aqueous electrolytes.

Low-Temperature controlled synthesis of nanocast mixed metal oxide spinels for enhanced OER activity.

The controlled cation substitution is an effective strategy for optimizing the density of states and enhancing the electrocatalytic activity of transition metal oxide catalysts for water splitting. However, achieving tailored mesoporosity while maintaining elemental homogeneity and phase purity remains a significant challenge, especially when aiming for complex multi-metal oxides. In this study, we utilized a one-step impregnation nanocasting method for synthesizing mesoporous Mn-, Fe-, and Ni-substituted cobalt spinel oxide (Mn0.1Fe0.1Ni0.3Co2.5O4, MFNCO) and demonstrate the benefits of low-temperature calcination within a semi-sealed container at 150-200 °C. The comprehensive discussion of calcination temperature effects on porosity, particle size, surface chemistry and catalytic performance for the alkaline oxygen evolution reaction (OER) highlights the importance of humidity, which was modulated by a pre-drying step. The catalyst calcined at 170 °C exhibited the lowest overpotential (335 mV at 10 mA cm-2), highest current density (433 mA cm-2 at 1.7 V vs. RHE, reversible hydrogen electrode) and further displayed excellent stability over 22 h (at 10 mA cm-2). Furthermore, we successfully adapted this method to utilize cheap, commercially available silica gel as a hard template, yielding comparable OER performance. Our results represent a significant progress in the cost-efficient large-scale preparation of complex multi-metal oxides for catalytic applications.

Theoretical Investigation of the Adsorbate and Potential-Induced Stability of Cu Facets During Electrochemical CO2 and CO Reduction.

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO2RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first-principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate-dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO2RR conditions. We identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO2RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO2RR conditions is likely attributed to differences in CO* coverage between these facets.

Polymerizable Deep Eutectic Solvent-Based Polymer Electrolyte for Advanced Dendrite-Free, High-Rate, and Long-Life Li Metal Batteries.

The recently developed advanced electrolytes possess many crucial qualities, including robust stability, Li dendrite-free, and comparable interface compatibility, for the manufacturing of Li metal batteries with a high energy density. In this study, lithium bis(trifluoromethane)sulfonimide, acrylamide, and succinonitrile were first used to design a polymerizable monomer. Then, it went through in situ thermal polymerization to attain a new solid polymer electrolyte [named poly(PDES)]. The synthesized poly(PDES) electrolyte achieved higher ionic conductivity (∼1.89 × 10-3 S cm-1), oxidation potential (∼5.10 V versus Li+/Li), and a larger lithium-ion transfer number (∼0.63). Moreover, poly(PDES) was nonflammable and could effectively inhibit the formation of Li dendrites. As a result, the assembled batteries using the poly(PDES) electrolyte for both Li||LiFePO4 and Li||LiNi0.8Co0.1Mn0.1O2 exhibited excellent interface compatibility and electrochemical performances. This poly(PDES) electrolyte has promising potential for broad application in lithium-metal batteries with elevated energy density and safety performance in the near future.

Building Stable Solid-State Potassium Metal Batteries.

Solid-state potassium metal batteries (SPMBs) are promising candidates for the next generation of energy storage systems for their low cost, safety, and high energy density. However, full SPMBs are not yet reported due to the K dendrites, interfacial incompatibility, and limited availability of suitable solid-state electrolytes. Here, stable SPMBs using a new iodinated solid polymer electrolyte (ISPE) are presented. The functional ions reconstruct ion transport channels, providing efficient potassium ion transport. ISPE shows a combination of high ionic conductivity, superior interfacial compatibility, and electrochemical stability. In situ alloying and iodinated interlayer increase K metal compatibility for prolonged cycling with low polarization. Moreover, the ISPE enables SPMBs with Prussian blue cathode stable operation at a high voltage of 4.5 V, a superior rate capability, and long-term cycling over 3000 cycles (4.2 V vs K+/K) with an ultra-high coulombic efficiency of 99.94%. More importantly, a classic solid-state potassium metal pouch cell achieves 4.2 V stable cycling over 800 cycles with a high retention of 93.6%, presenting a new development strategy for secure and high-performance rechargeable solid-state potassium metal batteries.

Inorganic All-Solid-State Sodium Batteries: Electrolyte Designing and Interface Engineering.

Inorganic all-solid-state sodium batteries (IASSSBs) are emerged as promising candidates to replace commercial lithium-ion batteries in large-scale energy storage systems due to their potential advantages, such as abundant raw materials, robust safety, low price, high-energy density, favorable reliability and stability. Inorganic sodium solid electrolytes (ISSEs) are an indispensable component of IASSSBs, gaining significant attention. Herein, this review begins by discussing the fundamentals of ISSEs, including their ionic conductivity, mechanical property, chemical and electrochemical stabilities. It then presents the crystal structures of advanced ISSEs (e.g., ß/ß''-alumina, NASICON, sulfides, complex hydride and halide electrolytes) and the related issues, along with corresponding modification strategies. The review also outlines effective approaches for forming intimate interfaces between ISSEs and working electrodes. Finally, current challenges and critical perspectives for the potential developments and possible directions to improve interfacial contacts for future practical applications of ISSEs are highlighted. This comprehensive review aims to advance the understanding and development of next-generation rechargeable IASSSBs.

Polyoxometalate Li3 PW12 O40 and Li3 PMo12 O40 Electrolytes for High-energy All-solid-state Lithium Batteries.

Solid-state lithium (Li) batteries promise both high energy density and safety while existing solid-state electrolytes (SSEs) fail to satisfy the rigorous requirements of battery operations. Herein, novel polyoxometalate SSEs, Li3 PW12 O40 and Li3 PMo12 O40 , are synthesized, which exhibit excellent interfacial compatibility with electrodes and chemical stability, overcoming the limitations of conventional SSEs. A high ionic conductivity of 0.89 mS cm-1 and a low activation energy of 0.23 eV are obtained due to the optimized three-dimensional Li+ migration network of Li3 PW12 O40 . Li3 PW12 O40 exhibits a wide window of electrochemical stability that can both accommodate the Li anode and high-voltage cathodes. As a result, all-solid-state Li metal batteries fabricated with Li/Li3 PW12 O40 /LiNi0.5 Co0.2 Mn0.3 O2 display a stable cycling up to 100 cycles with a cutoff voltage of 4.35 V and an areal capacity of more than 4 mAh cm-2 , as well as a cost-competitive SSEs price of $5.68 kg-1 . Moreover, Li3 PMo12 O40 homologous to Li3 PW12 O40 was obtained via isomorphous substitution, which formed a low-resistance interface with Li3 PW12 O40 . Applications of Li3 PW12 O40 and Li3 PMo12 O40 in Li-air batteries further demonstrate that long cycle life (650 cycles) can be achieved. This strategy provides a facile, low-cost strategy to construct efficient and scalable solid polyoxometalate electrolytes for high-energy solid-state Li metal batteries.

Functional Sulfate Additive-Derived Interfacial Layer for Enhanced Electrochemical Stability of PEO-Based Polymer Electrolytes.

Solid-state electrolyte batteries have attracted significant interest as promising next-generation batteries due to their achievable high energy densities and nonflammability. In particular, curable polymer network gel electrolytes exhibit superior ion conductivity and interfacial adhesion with electrodes compared to oxide or sulfide solid electrolytes, bringing them closer to commercialization. However, the limited electrochemical stability of matrix polymers, particularly those based on poly (ethylene oxide) (PEO), presents challenges in achieving stable electrochemical performance in high-voltage lithium metal batteries. Here, these studies report a sulfate additive-incorporated thermally crosslinked gel-type polymer electrolyte (SA-TGPE) composed of a PEO-based polymer matrix and a functional sulfate additive, 1,3-propanediolcyclic sulfate (PCS), which forms stable interfacial layers on electrodes. The electrode-electrolyte interface modified by the PCS enhances the electrochemical stability of the polymer electrolyte, effectively alleviating decomposition of the PEO-based polymer matrix on the cathode. Moreover, it also mitigates side reactions of the Ni-rich NCM cathode and dendrites of lithium metal anode. These studies provide a novel perspective by utilizing interfacial modification through electrolyte additives to resolve the electrochemical instability of PEO-based polymer electrolytes in high-voltage lithium metal batteries.

Interfacial and Electronic Modulation of M-Bridged Heterostructures with L-Tryptophan and Transition Metallic Oxides: Enhancing Corrosion Resistance and Photocatalytic Activity.

Despite remarkable advancements in multilayer composite materials, achieving controlled growth on stationary platforms for optimal corrosion protection and photocatalytic capabilities remains a challenge. In this study, we introduce an innovative approach by integrating bifunctional metal-organic frameworks (MOFs) into plasma-electrolyzed layers made on AZ31 Mg alloy. Metallic oxides of Zr, Ti, and W serve as new pivotal centers for MOF formation, while L-tryptophan (Trp) acts as an organic linker. This innovative approach establishes an efficient electron transport system that acts as a functional pathway for creating highly effective and versatile materials. The tunable structure of the MOF/plasma electrolyzed layer enables it to concurrently display electrochemical stability and photocatalytic activity for the photodegradation of organic pollutants. Remarkably, the WOF complex emerges as a standout performer, effectively shielding the substrate from corrosive anion attacks. This sample showcases exceptional photocatalytic efficiency of 99.61% for crystal violet solution, with sustained performance after five cycles and a 72 h corrosion test (96.55% and 98.39% degradation, respectively). Moreover, DFT calculations elucidate the fundamental bonding modes between MOFs and inorganic constituents, delivering comprehensive insights into their structural formation. Our research addresses the critical challenge of achieving controlled growth for enhanced corrosion resistance and photocatalytic activity, demonstrating a novel pathway for creating multifunctional materials with practical applications across various fields.