化学最新文献

Lithium phosphate (Li₃PO₄) is a promising buffer layer for stabilizing electrolyte-electrode interface in thin-film all-solid-state supercapacitors (ASSSCs). However, the chemical stability of Li₃PO₄ is limited by the dissociation of weak P-O-P bonds under operational conditions, leading to interfacial degradation. Here, we systematically investigate the role of oxygen partial pressure (P_O) during sputtering deposition in tailoring the chemical bonding configuration of Li₃PO₄ films. By precisely controlling P_O, we effectively convert unstable P-O-P bonds into robust PO and Li-O-P configurations, significantly enhancing both the stability and ionic conductivity of the Li₃PO₄ layer. Consequently, the optimized Li₃PO₄-coated ASSSC displays much better electrochemical performance than the no-coated one in terms of its higher specific capacitance (∼22.5 vs. 9.0 mF cm^-2 at 0.5 μA cm^-2), superior rate capability (∼11.2 vs. 0.9 mF cm^-2 at 30.0 μA cm^-2) and better cycling stability (∼92.9% vs. 77.8% of the retained capacity after 20,000 cycles). Furthermore, the device exhibits superior electrochromic functionality, showcasing its dual potential for energy storage and smart window applications.

Sodium (Na) metal with high theoretical specific capacity (1166 mAh g^-1) and low redox potential (-2.714 V vs. SHE) is considered as one of the most promising anode materials for Na-ion batteries. However, its practical application is hindered by dendrite growth and volume expansion. To address these challenges, Ag nanoparticles (Ag NPs) are sputtered onto the surface of a carbon cloth (CC) surface to construct a sodiophilic composite framework (CC/Ag NPs) for Na deposition. With this design, density functional theory calculations reveal that, thermodynamically, Ag NPs enhance Na- ions adsorption and reduce the Na nucleation energy barrier. Kinetically, the sodiophilic Ag NPs lower the Na deposition overpotential, while the porous structure of the CC and the NaF-rich solid electrolyte interphase facilitate Na-ions diffusion, synergistically promoting uniform Na grain growth. Additionally, the Ag NPs can adsorb fluorine, inducing the formation of a NaF-rich interface that improves interfacial stability. COMSOL Multiphysics simulations and morphological observations further confirm that the sodiophilic framework effectively suppresses dendrite formation. Consequently, CC/Ag NPs-Na||Na₃V₂(PO₄)₃ full cells retain a capacity of 90 mAh g^-1 after 400 cycles at 1C. This work provides a reference for designing advanced 3D frameworks for Na deposition.

Due to the solvated structure of Zn²⁺, a large amount of bound water is released during (de)intercalation to impact the lattice of the electrode material and aggravate the dissolution of vanadium actives, which seriously restricts the practical application of vanadium-based cathodes. Herein, a cathode-electrolyte interface pre-desolvation structure is constructed using polyvinyl alcohol (PVA) in this study. The solvation structure of Zn²⁺ is regulated through the confinement effect of polymer chains, significantly lowering the desolvation energy barrier, thereby mitigating lattice damage to the electrode material and dissolution of active substances. Moreover, three-dimensional porous conductive network constructed by combining carbon nanotubes (CNT) and flame-reduced graphene oxide (FRGO) effectively enhances the electrode conductivity and ion migration rate. The flexible electrode (PNVO@CG) constructed by effectively integrating NH₄V₄O₁₀ (NVO) with the substrate exhibits excellent rate performance and cycle stability, which remains a capacity of 428.1 mAh/g after 140 cycles at 0.5 A/g and 208.8 mAh/g after 4000 cycles at 15 A/g. In particular, the flexible PNVO@CG thin film battery has a maximum specific capacity of 396.7 mAh/g and maintains an excellent capacity stability during bending for 180°. Further integration of flexible pack cells with solar panels offers the possibility of renewable energy storage. This study provides a new opportunity of cathodes for the long-lifespan and flexible wearable ZIBs.

Polymerization-deposition (PD) pathway offers a promising route for low-carbon wastewater treatment, yet their efficiency under ultra-low oxidant dosage remains challenging. Herein, interfacial asymmetric oxygen vacancies (As-Ov) were constructed in hollow Co₃O₄/CeO₂ composites (H-Co30Ce-Ov) using glucose-derived hydrothermal carbon microspheres as sacrificial templates. The interfacial As-Ov drives an electron-transfer pathway (ETP) for phenol (PN) removal via peroxymonosulfate (PMS) activation to generate phenoxy radicals. These radicals subsequently underwent coupling reactions to form oligomeric products, resulting in effective COD removal via a PD-dominated process under ultra-low PMS dosage. Mechanistic investigations, including in situ Raman and electrochemical analyses, confirms the critical role of the coordination environment of As-Ov in controlling PMS activation behavior and reaction kinetic. Moreover, the H-Co30Ce-Ov exhibited excellent catalytic activity toward electron-rich pollutants, high PMS utilization efficiency and good stability across different water matrices. This study provides a rational strategy to enhance PD-based catalytic oxidation and offers new insights into resource-oriented pollutant removal in wastewater treatment.

Mo-based materials with 2D layered structure offer advantages such as high specific surface area and adjustable interlayer spacing, as well as multiple valence states of Mo^δ+, are regarded as high potential candidates for the lithium-ion batteries (LIBs) anodes. However, serious volume changes and insufficient conductivity limit their overall electrochemical performance. Herein, nanoflower-like MoS₂/MoN hierarchical heterostructures were successfully constructed on carbon cloth (CC) through a combined hydrothermal followed by nitridation treatment approach, which provides abundant active sites and effectively mitigates stress induced by volume expansion. This unique structure enables the generation of built-in electric field and improves charge transfer efficiency across the interfacial regions significantly, which markedly accelerates interfacial electron transfer and Li⁺ diffusion kinetics. As expected, the MoS₂/MoN@CC electrode can achieve a high reversible capacity of 843.6 mAh g^-1 at 0.1 A g^-1 after 100 cycles, and 612.0 mAh g^-1 at 2.0 A g^-1 after 1000 cycles, demonstrating excellent cycling and rate performances. The assembled MoS₂/MoN@CC// LiFePO₄ full cell shows a remarkable energy density of 410.4 Wh kg^-1 at power density of 310.0 W kg^-1. The heterostructures engineering is of great value for broadening the application of Mo-based materials in LIBs.

Piezoelectric field-driven CO₂ reduction to high-value C₂ products such as ethylene (C₂H₄) offers great potential for addressing global energy and environmental challenges. Nevertheless, piezoelectric CO₂ reduction towards C₂ products remains rarely explored, primarily due to lower free carrier concentration, not suitable reduction potential, and less CC coupling sites. Herein, we report the rational construction of a Z-scheme 1D-BaTiO₃/ 2D-SnS₂ heterojunction with engineered sulfur vacancies. When applied to piezoelectric catalysis, the heterostructure exhibits outstanding performance in both CO₂ reduction to C₂H₄ and H₂O₂ generation. The optimized catalyst achieves CO and C₂H₄ production rates of 301.64 and 62.75 μmol g^-1 h^-1, respectively, with a remarkable C₂H₄ electron selectivity of 54.59%. Simultaneously, a high H₂O₂ generation rate of 585.37 μmol g^-1 h^-1 is obtained in pure water. Composition optimization and defect engineering in SnS₂ expose more edge active sites and increase the free carrier density, while the polarized electric field induced by the piezoelectric effect effectively modulates the band structure of the Z-scheme heterojunction. This synergistic effect facilitate efficient carrier migration, concentrating high energy electron at the SnS₂ surface to promote multi-electron reduction processes. This systudy highlights a promising strategy for designing advanced heterostructured piezoelectric catalysts to efficiently drive multi-electron CO₂ conversion and sustainable chemical production.

High mass transfer efficiency, abundant surface sites, and short carrier migration distance can effectively enhance the photocatalytic performance of the materials. This study innovatively constructs a multiscale periodic macroporous (MPM) structure in the ternary metal oxide NaTaO₃. The MPM architecture overcomes the inherent limitations of single-pore-size materials: large macropores suffer from thick pore walls leading to prolonged charge migration pathways and enhanced recombination, and low specific surface area, while small macropores lack efficient mass transport despite abundant active sites, and exhibit low electron-hole recombination. By synergistically integrating the advantages of both pore sizes, the MPM structure optimizes mass transport kinetics and charge separation efficiency, rendering it well-suited for solid-liquid phase photocatalytic reactions. Consequently, the photocatalytic hydrogen evolution activity of MPM NaTaO₃ is significantly enhanced, thereby establishing a novel strategy for the controlled synthesis of complex ternary metal oxides.

Sodium/potassium-ion batteries (SIBs/PIBs) are promising for large-scale energy storage due to their abundant resources and lithium-ion compatibility. However, their practical application depends on optimizing electrochemical performance, particularly rate capability and cycling stability; therefore, elucidating key mechanisms like electrode evolution, phase transitions, and ion transport is essential for realizing their potential. Traditional ex-situ techniques fail to capture real-time changes in operating batteries, often providing incomplete insights into mechanisms such as capacity degradation and interfacial instability. In-situ characterization overcomes this limitation by enabling direct observation of material dynamics, thereby advancing both fundamental research and practical development of SIBs/PIBs. A comprehensive review of these techniques is crucial to address the increasing demand for sustainable energy storage solutions. This review provides an overview of in-situ techniques, detailing their principles, operational methods, advantages and limitations. It underscores that understanding the principles alone is insufficient; precise interpretation of experimental results is essential for analyzing electrochemical processes. Through examples, we aim to elucidate battery reaction mechanisms and offer strategies for addressing complex electrochemical systems. This article focuses on diffraction- and spectroscopy-based methods (in-situ XRD, XAS, Raman and FTIR), electron microscopy (in-situ TEM, SEM) and in-situ AFM, highlighting their applications in SIBs/PIBs research and offering guidance for future studies.

Dendritic growth and parasitic reactions at the zinc (Zn) anode surface critically limit the performance and durability of aqueous zinc metal batteries (AZMBs). Therefore, a surface etching strategy using leucine was proposed to in-situ regulate the Zn anode interface. During etching, the Zn (101) crystal plane is selectively preserved, and its fast reaction kinetics promote uniform Zn plating. Meanwhile, a stable leucine-zinc interfacial layer is formed on the Zn surface, which increases the contact angle with water and significantly suppresses parasitic reactions, leading to 67.8 % reduction in corrosion. In addition, the leucine-zinc interface provides abundant adsorption-active sites that accelerate the desolvation of Zn(H₂O)₆²⁺, thereby effectively inhibiting dendritic growth, with dendrite height reduced over 50 % compared with Bare Zn. Theoretical calculations reveal that the Zn (101) crystal plane exhibits the strongest affinity and electronic interaction with leucine, which promoted the formation of a stable leucine‑zinc interface layer, effectively protecting the surface from the attack of H⁺ in the etchant. As a result, the modified Zn anode (denoted as Leu@Zn) enables stable cycling for up to 2900 h at 25 mA cm^-2 in symmetric cells and the full cells assembled with MnO₂ cathode delivers a prolonged cycle life of 50,000 cycles at 5 A g^-1.