Exceptional Stability Research Articles

In Situ Formation of Stable Dual-Layer Solid Electrolyte Interphase for Enhanced Stability and Cycle Life in All-Solid-State Lithium Metal Batteries.

All-solid-state lithium metal batteries have emerged as a promising solution to overcoming the energy density and safety challenges associated with conventional lithium-ion batteries. Solid polymer electrolytes, particularly those based on poly(vinylidene fluoride) (PVDF) and dimethylformamide (DMF), demonstrate significant potential. However, interfacial side reactions between residual DMF solvents and lithium metal present substantial challenges. In this study, we investigate the in situ formation of solid electrolyte interphase protective layers to mitigate these side reactions. By incorporating F-rich additives, such as fluoroethylene carbonate and lithium difluorophosphate, we successfully establish a dual-layer inorganic SEI structure characterized by an outer LiF layer and an inner Li2O layer. Consequently, our approach extends the cycle life of lithium symmetric batteries to 3000 h. Additionally, the Li||LiFePO4 solid-state battery demonstrates exceptional stability, enduring 400 cycles at a 1C rate with an impressive capacity retention of 84%. This strategic methodology effectively leverages the benefits of residual solvents, ensuring both enhanced battery efficiency and long-term operational stability for PVDF-based all-solid-state lithium metal batteries.

Sulfonated poly(aryl ether) proton exchange membrane with excellent dimensional stability for hydrogen production by water electrolysis

The use of proton exchange membrane water electrolysis (PEMWE) for hydrogen production is considered a promising technology due to its high theoretical current density, gas purity, and energy efficiency. In this study, a fluorinated sulfonated hydrocarbon polymer was used to prepare hydrocarbon−based membranes for PEMWE that displayed exceptional stability. Notably, the SFPAE-60 membrane has a proton conductivity of up to 293.1 mS cm−2 at 80 °C and 100%RH, but its volumetric swelling ratio is only 47 %. Its dimensional stability is significantly better than that of previously reported sulfonated poly (aryl ether)−based proton exchange membranes (>100 %). The PEMWE based on the SFPAE-60 membrane achieves a current density of over 4800 mA cm−2 at 2.0V, confirming the membrane's applicability in actual water electrolysis. The results indicate that the electrolyte membrane of fluorinated sulfonated hydrocarbon polymer performs well in the PEM electrolyzer.

Multiscale Defective Interfaces for Realizing Na-CO2 Batteries With Ultralong Lifespan.

Despite their favorable high energy density and potential for CO2 recycling, Na-CO2 batteries have been held back by limitations in cycling capability, stemming from the sluggish CO2 reduction/evolution reaction (CO2RR/CO2ER) kinetics at CO2 cathode and unmanageable deposition/stripping of metallic Na at the anode upon cycling. Herein, a "two-in-one" electrode with multiscale defective FeCu interfaces (CP@FeCu) is presented, which is capable of improving the CO2RR/CO2ER kinetics of CO2-breathing cathode, while modulating sodium deposition behavior. Experimental and theoretical investigations reveal multiscale defective FeCu interfaces are responsible for the enhancement of sodiophilicity and catalytic properties. The defect and valence oscillation effects originate in multiscale defective FeCu interfaces, effectively facilitating the adsorption of reactants and decomposition of Na2CO3 during CO2RR/CO2ER processes, along with exceptional cycling stability of 2400 cycles (4800h) at 5µAcm-2. Meanwhile, the CP@FeCu with sodium affinity creates a uniform electric field and robust adsorption for Na, making initial nucleation sites more conducive to Na deposition and achieving dendrite-resistant and durable anodes. This work offers a scientific insight into the functionalization design of "two-in-one" electrodes, which is essential for a unified solution to the challenges in sodium anodes and CO2 cathodes.

Cauliflower-like Ni/NiCoP@Boron-doped diamond composite electrodes for high-performance symmetric supercapacitors

Due to the lack of electrocatalytic active sites, the supercapacitors (SCs) even based on the most stable sp3 carbon material (Boron-doped diamond) suffer from poor capacitance and low energy density. Herein, a cauliflower-like biphasic Ni/NiCoP layer has been successfully deposited on the BDD film and further applied as binder-/current collector-free SC electrodes. In a redox-active aqueous electrolyte (0.05 M Fe(CN)63−/4− + 1.0 M KOH), the Ni/NiCoP@BDD electrode with exceptional cyclic stability (∼89.0 % after 10,000 cycles) delivers a specific capacitance of 256.1 mF cm−2 at a current density of 30 mA cm−2, about 2 times higher than that in inert electrolyte. Furthermore, such a symmetric PC device provides a desired energy density of 70.0 Wh kg−1 at a high power density of 3601 W kg−1.

First-principles calculations to investigate thermodynamic, mechanical and electronic properties of Penta-C72 carbon under pressure effect

The current work explores the mechanical characteristics, band structure modifications, elastic constant changes, and anisotropy of the carbon allotrope Penta-C72 at high pressure. First-principles simulations were used to analyse the structural features, stability, electronic, mechanical, and thermodynamic properties of Penta-C72, a metastable sp3 -bonded structure made up of carbon pentagons joined by bridge-like connections. The structural and dynamical stability of Penta-C72 under high pressure is confirmed using formation energy, phonon band maps, and thermodynamic properties. Besides, Born's mechanical stability criterion is fulfilled based on the elastic constants of Penta-C72, indicating its mechanical stability. Also, the anisotropic mechanical behaviour is shown by the material. Using the Reuss, Voigt, and Hill approximations, the elastic moduli under high pressure were computed, including bulk modulus (K), shear modulus (G), and Young's modulus (E). Besides, Penta-C72 exhibits a rise in anisotropy and moduli with increasing pressure. This investigation explores the changes in the band gap upon variation in the pressure. It is observed that there is a transition from semiconducting to metallic property above 10 GPa. Beyond 10 GPa, the material exhibits metallic behaviour. The study emphasizes that Penta-C72’s exceptional mechanical stability, directional anisotropy, and customisable electronic characteristics make it a strong contender for various engineering applications.

Confined Gelation Synthesis of Flexible Barium Aluminate Nanofibers as a High-Performance Refractory Material.

Barium aluminate (BAO) ceramics are highly sought after as a kind of high-temperature refractory material due to their exceptional thermal stability in both vacuum and oxygen atmospheres, but their inherent brittleness results in rapid hardening, imposing a negative impact on the overall construction performance. Here, we report a strategy to synthesize flexible BAO nanofibers with a needle-like structure through confined-gelation electrospinning followed by in situ mineralization. The confined gelation among the colloidal particles promotes the formation of precursor nanofibers with high continuity and a large aspect ratio. The resulting flexible BAO nanofiber membranes are bendable, stretchable, and can even be woven, exhibiting a softness (12 mN) that is lower than that of tissue paper (27 mN). Additionally, they are capable of withstanding hundreds to thousands of continuous buckling and bending at 50% deformation without tearing. More importantly, the low emissivity of the flexible BAO nanofiber membranes ensures excellent thermal insulation at 1300 °C while preserving structural integrity and performance stability. In this sense, our strategy can be easily scaled up to produce flexible yet tough oxide ceramic membranes for a wider range of applications.

Bi-Functional Interfacial Modification enables Highly-Exposed Zn(002) Crystal Facet towards Durable Zn Metal Batteries.

Zn-ion batteries (ZIBs) have garnered growing interest in large-scale energy storage devices for the high safety, high theoretical capacity and low electrochemical potential. Nevertheless, their widespread applications are significantly impeded by dendrite formation, hydrogen evolution and corrosion reactions of Zn anodes. Herein, a bi-functional polyacrylic acid (PAA) modified-Zn anode (Zn-PAA) is designed to concurrently inhibit Zn dendrite formation and alleviate side reactions. The bi-functional PAA coating not only selectively acid-etches the active Zn crystal facets to guide the planar deposition along the highly-exposed Zn(002) crystal facet, but also facilitate uniform Zn deposition through coordination between the polymer functional groups and Zn2+. Meanwhile, the electrically-insulated PAA protective layer effectively separates Zn anodes from the electrolyte and modulates the solvation structure of Zn2+.6H2O, significantly suppressing side reactions. Consequently, the assembled Zn-PAA//Zn-PAA symmetrical cell delivers an outstanding cycling stability of 1600 h at 1 mA cm-2 and 1 mAh cm-2. The assembled KVO//Zn-PAA full cell shows exceptional cycling stability over 1500 cycles at 2.0 A g-1 with a high Coulombic efficiency approaching 100%. The facile bi-functional surface modification strategy, which enables to finely tune the crystal facet texture and ion distribution manner, opens up a groundbreaking path towards safe and durable ZIBs.

Convenient synthesis of phthalonitrile‐containing mono‐benzoxazines with exceptional thermal stability and improved curing activity

AbstractSimple synthesis and high performance are eternal pursuit for polymers. To lower the curing temperature, lower the melt viscosity and improve the processability of high performance phthalonitrile resins, a solvent‐free method was applied to synthesize three from different phenols. Their chemical structure was confirmed by FTIR and NMR spectra, the curing behavior was investigated by DSC and rheology. It was found that the polymerization of phthalonitrile groups could be effectively promoted by benzoxazine moieties and the curing temperature of phthalonitrile groups dropped to around 240°C. Consequently, owing to the high curing reactivity, polymers obtained at relatively low curing temperature possessed high crosslinking density and extremely high thermal stability. P‐apn‐200, which was cured at 200°C, showed 5 wt% weightloss temperature (Td5) of 472°C and char yield (Yc) of 75.77% at 800°C. Moreover, the polymers obtained after curing at 280°C showed superior dimensional stability, CN‐apn‐280 showed extremely low linear expansion coefficient (CTE) of 10.7 ppm/°C. And mP‐apn‐280 showed HR capacity of 3.99 J/g‧K, peak HRR of 4.0 W/K and total HR of 0.8 kJ/g.

Ultra-Stable Aqueous Zinc Anodes: Enabling High-Performance Zinc-Ion Batteries via a ZnSiF6-Derived Protective Interphase.

Zinc-ion batteries (ZIBs) hold immense promise as next-generation energy storage solutions, however, the practical application of zinc anodes is hindered by dendrite formation and parasitic side reactions. Engineering a stable solid- eletrolyte interphase (SEI) is crucial for addressing these issues. This study proposes a novel strategy to enhance Zn anode performance by incorporating a ZnSiF6 additive into a standard ZnSO4 (ZSO) electrolyte. The ZnSiF6 additive facilitates the formation of a stable, fluorine-rich SEI on the Zn anode surface. Characterization reveals a hierarchical SEI structure, primarily composed of porous alkali zinc sulfate (ZHS) with embedded ZnF2. This unique architecture promotes rapid zinc ion desolvation and efficient transport, enhances corrosion resistance, and mitigates hydrogen evolution. Consequently, ZnSiF6-modified cells exhibit exceptional cycling stability, exceeding 3000 hours at 0.5 mA cm-2 and 560 hours at 10 mA cm-2, significantly outperforming ZSO-based cells. The modified cells also achieve high areal capacities (10 mAh cm-2), indicating superior zinc utilization. This work provides key insights for designing stable electrode/electrolyte interfaces, contributing to the development of high-performance aqueous ZIBs.

Multiplex Collagen Fingerprinting for the Staging of Hepatic Fibrosis Using High-Precision Fluorescence-Guided SERS Imaging.

Hepatic fibrosis is a common chronic liver disease, and its severe progression can culminate in cirrhosis and hepatocellular carcinoma (HCC). Precise diagnosis and staging of hepatic fibrosis are essential to prevent liver cirrhosis and HCC. Simultaneous detection of multiplex collagen biomarkers within liver tissue is crucial for staging hepatic fibrosis. We herein for the first time constructed multiplex collagen fingerprinting for the staging of hepatic fibrosis using high-precision fluorescence-guided surface-enhanced Raman scattering (SERS) imaging. SERS/fluorescent probes, collectively referred to as SF, comprising silver nanoparticles (Ag NPs), Raman reporters, and FAM-labeled collagen targeting peptides. These probes exhibit exceptional aqueous dispersion and stability, attributed to the increased number of Asp residues in CTP. Meanwhile, SF probes, namely SF-I, SF-IV, and SF-D have demonstrated specific targeting of type I, type IV, and denatured collagen, respectively, within hepatic fibrotic tissues. The results from fluorescence-guided SERS imaging underscore the method's capacity for typing, localization, and quantification of collagen, thus providing novel insights into collagen's role in the development of hepatic fibrosis. The collagen fingerprinting strategy offers a potent toolkit for the multifaceted profiling of collagen superfamilies, holding significant implications for the precise staging of hepatic fibrosis.

Robust Light Detection from Ultraviolet to Near‐Infrared with ZnGa2O4/p‐Si Heterojunction Photodiode and Its Application for Optoelectronic Physically Unclonable Functions

AbstractThe Si‐based self‐powered broadband photodiode (SSBP) is prized for its ability to swiftly detect light across a wide spectrum without requiring an external voltage. However, boosting its efficiency remains challenging due to its high refractive index and limited UV light penetration. A combination of Si with ZnGa2O4, an ultra‐wide‐bandgap spinel material, can bring new opportunities to address these shortcomings of SSBP. In this study, a ZnGa2O4/p‐Si heterojunction photodiode is presented, which is capable of detecting UV to near‐infrared light autonomously. Operating without bias, this device exhibits excellent rectification and detects wavelengths from 265 to 1000 nm, achieving impressive performance metrics such as a photo‐to‐dark current ratio of 5.8 × 104, response speed of less than 3 ms, responsivity of 117 mA W−1, and specific detectivity of 5.5 × 1012 Jones while the photodiode demonstrates exceptional stability and durability under harsh conditions. The versatility of this device is demonstrated by applying it to the optical imaging sensors and physically unclonable security devices. This study provides new inspirations for the development of the energy‐efficient and emerging optical sensing technologies.

Exceptional stability of the sugammadex-solasodine complex: Insights from experimental and theoretical studies

Sugammadex (SGM) is the first cyclodextrin (CD)-based selective relaxant binding agent. We investigated its ability to capture natural aminosteroid phytotoxins, and assessed its potential as an antidote for intoxication. Solasodine (SS), a toxic alkaloid from the Solanaceae family, was chosen as the model compound. Complexation was studied using nuclear magnetic resonance (NMR) spectroscopy, molecular modelling, and isothermal titration calorimetry (ITC). NMR in various D2O/DMSO‑d6 media revealed a particularly stable inclusion-type complex, identifying a slow exchange process between the CD and the aminosteroid along with a less significant fast exchange between DMSO and SGM. Using various NMR techniques, the structure and kinetic/thermodynamic parameters of the inclusion complex were explored. Theoretical calculations showed the secondary amino head of SS near the carboxylate ends of the SGM sidechains, facilitating intermolecular ionic interactions. ITC experiments in an aqueous environment provided Ka stability constants of 7.03 × 106 M−1 and 4.17 × 106 M−1 at 25 °C and 37 °C, respectively, similar to previously reported SGM complexes with aminosteroid neuromuscular blockers. Finally, SGM significantly increased cell survival and reduced SS toxicity in mHippoE-14 mouse hippocampal embryonic cells, supporting the hypothesis that SGM could act as an antidote to SS's toxic effects.

Dendrite‐Free Zn Anode Modified with Prussian Blue Analog for Ultra Long‐Life Zn‐Ion Capacitors

AbstractThe main challenge for aqueous zinc‐ion capacitors is the low stability of zinc anode. In this study, a Prussian blue analog (PBA) has been coated on the surface of zinc foil to create an inorganic protective layer. This layer features a three‐dimensional open microporous structure, which not only endows it with excellent pseudocapacitive properties but also serves as an effective barrier against dendrite growth. The presence of PBA coating can increase the nucleation point of zinc ions and provide a low‐energy barrier for the rapid migration of zinc ions. Hence, the PBA@Zn ||PBA@Zn symmetric cell exhibits exceptional cycling stability, enduring over 1400 h of operation at a current density of 1 mA cm−2 and a capacity of 1 mAh cm−2. The PBA@Zn||AC capacitor demonstrated a discharge capacity of 46.23 mAh g−1 after 10 000 cycles at a current density of 1 A g−1, with a capacity retention of 92.41%, whereas the discharge capacity of Zn||AC capacitor is only 16.02 mAh g−1, with a capacity retention of 23.13%. The PBA@Zn||AC capacitor exhibited remarkable endurance and stability, retaining a substantial discharge capacity of 32.7 mAh g−1 after 10 000 cycles at 10 A g−1. Density Functional Theory (DFT) calculations also show that PBA has a strong interaction with Zn and exhibits superior zincophilic ability. This study reports industrially applicable low‐cost Prussian blue analogs as artificial interfacial protective layers for improving the cycling stability of zinc anode with a low‐energy barrier for rapid migration of zinc ions especially at high current density.

Sol-gel-based synthesis of high-capacity-NaCoO2 cathode for advanced sodium-ion batteries

This study presents a successful synthesis of phase-pure P2-NaCoO2 by improving the sol-gel-based calcination temperature, yielding a highly crystalline, well-ordered material having P63/mmc hexagonal symmetry, ideal for reversible sodium-ion batteries (SIBs). Advanced physicochemical techniques confirm its pure hexagonal crystal structure along with the desired stoichiometry. NaCoO2 in Na/1M-NaClO4/NaCoO2 cell demonstrates multiple redox peaks for Co3+/Co4+ redox couple, signifying stable multiphase transitions during charge/discharge cycles and exhibiting exceptional structural and electrochemical stability. The cell demonstrates a high discharge specific-capacity of 155.85 mAh/g at 0.1C with outstanding discharge capacity retention of 136.98, 100.6, 84.78, 78.31, and 72.46 mAh/g at the C-rates of 0.15, 0.2, 0.3, 0.5, and 1.0C, respectively, outperforming previously reported values. It shows a remarkable discharge-energy density of 466.04 Wh/kg at 0.1C. Additionally, the small solution and charge transfer resistance with extremely low double-layer capacitance signifies its excellent electrolyte conductivity and potential for high energy density and slow discharge application. These results imply that NaCoO2 is a high-performance and high-capacity cathode material for lightweight and compact SIBs.

Fabrication and characterization of low-cost ceramic membranes from coal fly ash and natural sand

Coal fly ash, an industrial solid waste product, and natural sand, a commonly available and inexpensive natural material, were used to fabricate ceramic membranes that are both affordable and sustainable. These ceramic membranes were fabricated by the uniaxial compaction technique using a manual hydraulic pressing machine. The effects of various fabrication parameters such as the sintering temperature and the amount of natural sand utilized, on the properties of the resulting ceramic membranes were extensively evaluated. X-ray fluorescence (XRF) analysis of the starting materials confirmed the presence of SiO2 and Al2O3, two key inorganic materials required for the fabrication of ceramic membranes. Heavy metals present in the raw coal fly ash were leached out prior to the fabrication process. The coal fly ash and natural sand were mixed in different proportions and the fabricated ceramic membranes were characterized using Fourier transform infrared spectroscopy (FTIR), Scanning electron microscope (SEM), X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDS), and Thermogravimetric analysis (TGA). The properties of the optimized membranes were further studied to ascertain their mechanical strength, chemical stability, porosity, water absorption, water permeability, and shrinkage behaviour. The membrane fabricated with 20 wt% sand content and at 1000 °C sintering temperature had pore size of 0.64 µm and 34.7 % porosity, exhibited good mechanical strength (7.71 MPa), and exceptional chemical stability. The membrane also showed a remarkable water permeability of 32.23 L/m2/h. This study showed that natural sand and coal fly ash can be efficiently employed to develop a multifunctional filtration membrane with adjustable properties that can be utilized in water purification.

Improvement of Self-Driven Nanowire-Based Ultraviolet Photodetectors by Metal-Organic Frameworks for Controlling Humanoid Robots.

Self-driven photodetectors (PDs) hold significant potential for the development of new information devices, which boast the advantages of ultralow power consumption and straightforward fabrication. In this study, we have proposed and demonstrated a self-driven ultraviolet PD utilizing gallium nitride/metal-organic framework (GaN/MOF) heterojunction nanowires successfully. By introducing Gd-ETTC MOFs on the surface of GaN nanowires, the photocurrent and responsivity of the device can be improved by approximately 75% under 310 nm illumination. Furthermore, they can also be effectively enhanced under visible light illumination. Owing to the appropriate energy level alignment, Gd-ETTC MOFs can serve as both a light harvester and a hole conductor, facilitating the efficient absorption, separation, and transmission of photogenerated carriers. It has been observed that due to reduced interface resistance, MOFs can enhance the charge transport through the acceleration of charge transfer. Furthermore, the PD equipped with MOFs is capable of continuous operation for 30,000 s, a feat attributable to the exceptional stability of both GaN nanowires and Gd-ETTC MOFs. By implementation of the humanoid robot systems, the control commands from the self-driven PD can drive the humanoid robot to execute different actions. The PD-equipped autonomous feedback system of a humanoid robot enables a seamless integration of light perception with intelligent robotic actions. Therefore, the design and demonstration of GaN/MOF nanowires hold significant reference value for further enhancing the performance of PDs and broadening their applications in ultralow-power artificial intelligence systems, humanoid intelligent robots, etc.

Direct ink writing of engineered MOF-based hybrid composite empowering dendrite free zinc ion battery anode

The relationship between morphology and electrochemical performance of zinc-ion battery (ZIB) anodes is crucial. Optimizing zinc-ion intercalation efficiency, suppressing dendrite formation, and mitigating shape changes are achievable through thoughtful anode architecture design. Herein, we have engineered a hybrid composite by coordinating a metal-organic framework with phenolic formaldehyde resin using a direct ink writing approach to rationally design a gridline-patterned 3DP-UiON-PHC@Zn. This anode in a symmetrical cell shows exceptional stability with a low voltage hysteresis of 15 mV at 0.1 mA cm−2 over 2375 h and 67 mV at 0.5 mA cm−2 over 4470 h. When paired with a 3DP-VOC@Al cathode in a full cell, it achieves a remarkable areal capacity of 85.1 mAh cm2 (94.8 %) and maintains a capacity retention of 122 mAh g−1 (88.6 %) over 900 cycles at 0.1 A g−1. It also offers a power density of 69.1 W kg−1 and an energy density of 34.6 Wh kg−1. Kinetic analysis reveals that the charge storage mechanism is primarily capacitive (94.7 %). This study concludes that DIW significantly improves anode performance by minimizing dendrite growth and improving electrochemical stability, while the 3D-printed hybrid composite ensures robust mechanical stability and a porous structure.

The impact of support selection and Co loading amount on the catalytic performance for methane combustion

Methane (CH4) is a key component of natural gas and is essential for energy production and utilization. However, due to its strong greenhouse effect, efficient catalytic combustion methods are needed to convert it into CO2 and H2O. This study systematically evaluates the catalytic performance of Co, CoO, and Co3O4 in methane catalytic combustion, particularly highlighting the superior activity of Co3O4. To improve catalytic efficiency, this paper examines the effects of SiO2, Al2O3, and CeO2 as support materials using co-precipitation and impregnation methods. The results show a significant improvement in the catalytic activity of Co3O4 supported on CeO2, attributed to CeO2's unique redox properties and high oxygen storage capacity. Additionally, the study explores the impact of different loading amounts (5%, 10%, 15%, 20%) of Co3O4(x)-CeO2 catalysts on their performance. The optimal 10%wt Co3O4–CeO2 catalyst achieves methane conversion rates of 10%, 50%, and 90% at temperatures of 376 °C, 473 °C, and 578 °C, respectively, demonstrating exceptional stability during a 20-h stability test and the ability to adapt to fluctuations in CH4 concentrations in low-oxygen environments, while also exhibiting significant catalytic activity across a range of methane concentrations from 0.5% to 2.5%. These findings provide important theoretical and experimental guidance for the application of cobalt-based catalysts in CH4 combustion, paving the way for future catalyst design and optimization.

Enhancing the conductivity and dispersion properties of polyaniline using ethyl orange

In our research, we developed a novel one-step synthesis method for polyaniline (PANI) using the organic dye Ethyl Orange (EO). This method facilitated the formation of PANI nanorods and significantly enhanced their electrical conductivity, achieving up to 13.5 S cm−1. The structural interaction between EO and PANI was confirmed through Fourier-transform infrared (FTIR) and UV–visible (UV-Vis) spectroscopy. Notably, the inclusion of EO improved PANI's dispersion properties, resulting in a zeta potential of 34 mV in water and excellent dispersibility in various organic solvents. These attributes significantly enhance the application potential of PANI nanorods, especially in protective coatings. Electrochemical impedance spectroscopy (EIS) analysis revealed that EO-PANI/WPU coatings (0.5 wt% EO-PANI) exhibited exceptional electrochemical stability and corrosion resistance in a 3.5 wt% NaCl solution. Specifically, the initial impedance magnitude (Zf=0.01 Hz, 1010 ohms) of EO-PANI/WPU coatings was approximately two orders of magnitude higher than that of traditional WPU coatings (108 ohms). Over time, the EO-PANI coatings demonstrated higher phase angles and impedance, indicating superior electrochemical stability and protective performance.

Development of Group IV Metal Complexes Bearing Thioether-Amido Ligands with Enhanced High-Temperature Catalytic Performance toward Olefin Copolymerization.

The development of homogeneous metal catalysts with both high activity and exceptional thermal stability is crucial for the efficient synthesis of polyolefin elastomers (POEs) through solution-phase olefin polymerization. In this study, a series of Hf (Hf1-Hf5), Zr (Zr1), and Ti (Ti1) complexes featuring thioether-amido ligands were synthesized and carefully characterized using advanced techniques such as 1H and 13C NMR spectroscopy as well as single-crystal X-ray diffraction analysis for Hf4 and Hf5. The results revealed that the catalytic activity and 1-octene incorporation efficiency of these metal complexes followed the trend Hf > Zr > Ti, underscoring the significant impact of the metal center on catalytic performance. Furthermore, the choice of ligands was found to play a critical role in dictating the catalytic properties, with ligands bearing less steric hindrance on the sulfur atom proving to be more favorable for copolymerization reactions. Notably, the Hf complex Hf1, featuring a methyl group on the sulfur atom, displayed exceptional catalytic activity as high as 21,060 kg(polymer)·mol-1(Hf)·h-1 toward ethylene/1-octene copolymerization at 120 °C and produced POE with a high molecular weight (Mw = 6.3 × 104 g·mol-1), relatively narrow distribution (Đ = 2.4), and high incorporation of 1-octene (34.1 mol %). This study demonstrates the potential of tailored ligand design in developing efficient metal catalysts for the production of high-value-added POEs.