Journal of Colloid and Interface Science最新文献

Na₄Fe₃(PO₄)₂P₂O₇ (NFPP) emerges as a cost-effective structurally stable and environmentally benign cathode material, exhibiting significant potential in the energy storage of sodium-ion batteries. However, inherent low ionic mobility and electronic conductivity of NFPP have affected its power performance. In this study, high-valence transition metal cations (Mo⁶⁺, Ta⁵⁺, Nb⁵⁺, and W⁶⁺) are doped within the NFPP lattice, which induces internal electronic rearrangement and average valence state decrease of Fe cations through distortion of locally corner-sharing FeO polyhedra. The increased FeO bond lengths within Mo-doped NFPP crystals and altered electronic cloud distribution further validates this ionic charge compensation mechanism. High-valence metal-doping can also decrease the bandgap, enhance average electronic conductivity, as well as lower Na⁺ migration barrier, thus increasing Na⁺ diffusion coefficient by three orders of magnitude. Therefore, the optimized Na₄Fe_2.91Mo_0.09(PO₄)₂P₂O₇ cathode material demonstrates excellent rate performance and outstanding cycling stability (retaining 85.86% capacity after 1300 cycles at 1C). In addition, the universal effectiveness of the high-valence transition metal doping strategy is verified by investigation of Ta⁵⁺, Nb⁵⁺, and W⁶⁺ doping based on experimental characterizations and theoretical calculations. These findings provide a new perspective to modulate electronic structure and ionic transport pathway of NFPP, and shedding light on great application prospects of iron-based mixed polyanion cathode materials.

Lithium metal batteries demand electrolytes that combine high ionic conductivity with mechanical robustness and interfacial stability. This study presents a novel composite gel polymer electrolyte (GPE) engineered by integrating a cyano-functionalized polysiloxane (PCMS) frameworks, diethylene glycol dimethyl ether (DEGDME) plasticizers, and electrospun polyacrylonitrile (PAN) nanofiber scaffolds. The optimized GPE system achieves an exceptional combination of properties: high ionic conductivity (3.3 × 10^-3 S cm^-1 at 30 °C), outstanding Li⁺ transference number (0.79), and remarkable mechanical strength (3.9 MPa). Theoretical calculations and experimental analyses collectively confirm that the -CN groups competitively coordinate with Li⁺, restructuring the solvation environment to favor TFSI^- anion participation, thereby facilitating the formation of a robust solid electrolyte interphase (SEI) enriched with LiF and Li₃N. As a result, the GPE demonstrates a wide electrochemical stability window (5.3 V vs. Li⁺/Li) and stable lithium plating/stripping for 1000 h at 0.1 mA cm^-2. Additionally, LiFePO₄/GPE/Li full cells achieve 94.9% capacity retention after 500 cycles at 0.5C, while NCM811/GPE/Li cells deliver a high discharge capacity of 153.8 mAh g^-1 with 86.5% retention after 150 cycles. This work establishes a scalable and promising strategy for the development of high-performance lithium metal batteries.

Hydrogen-bonded organic frameworks (HOFs) are considered as potential choice for future energy storage systems due to their adjustable chemistry, environmental benignity, and cost-effectiveness. However, the electrochemical reaction mechanisms of the HOFs remain elusive. Herein, we demonstrate the site-selective electrochemical storage of alkaline metal ions (Li⁺, Na⁺, and K⁺) in porphyrin-based hydrogen-bonded organic framework (PFC-72-Co). Through systematic experimental and theoretical investigations, three active sites are identified, namely, carbonyl site (site 1), porphyrin site (site 2), and interstitial site (site 3). The carbonyl functional group can accommodate all alkaline metal ions (Li⁺, Na⁺, K⁺), whereas the porphyrin and interstitial sites are selective only for Li⁺ ions. As a result, the monomer Co-TCPP, with its abundant active sites, is a promising anode material for potassium-ion batteries, hosting 7 K⁺ ions and delivering a reversible capacity of 247.6 mAh g^-1. In contrast, the PFC-72-Co framework, owing to its low solubility in the electrolyte, serves as a stable anode for lithium-ion batteries, exhibiting ultrahigh cycling stability of over 10,000 cycles. This work provides new understanding of the electrochemical reaction mechanisms of organic materials for alkaline metal-ion batteries.

Low-temperature CO₂ methanation efficiently enables efficient conversion of CO₂ into methane under mild conditions, presenting substantial potential for enhanced energy efficiency and economic feasibility. However, achieving highly efficient low-temperature CO₂ activation remains a critical challenge due to inherent kinetic constraints. In this study, the inverse-supported Ce/Ni catalyst (11 mol% Ce/Ni) was synthesized, which achieved 82% CO₂ conversion and nearly 100% CH₄ selectivity under photothermal synergy at 220 °C (300 W xenon lamp, 300-2500 nm, 1.5 W·cm^-2), outperforming most conventional nickel-based catalysts. Moreover, the catalyst exhibited outstanding long-term stability, with only an 8% activity loss after 100 h of continuous operation. This superior performance was attributed to its CeO₂-Ni interfacial configurations and abundant oxygen vacancies. In situ diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that the CO₂ methanation over this catalyst proceeds via a dual-intermediate pathway involving CO* and HCOO*, with photothermal synergy significantly accelerating the intermediate conversion without altering the intrinsic reaction pathway. This study establishes an innovative strategy for designing low-temperature and high-performance CO₂ methanation catalysts via the integration of an inverse Ce/Ni configuration with photothermal synergy.

Hydrovoltaic power generation technology, which converts the chemical energy from ubiquitous moisture into electrical energy, represents a promising emerging green energy harvesting strategy. The incorporation of renewable biomass materials further enhances the appeal of this approach. In this study, an all wood-based hydrovoltaic electricity generator (WHEG) based on water migration is developed through simple chemical treatment of poplar wood. The removal of lignin releases micro- and nano-scale pores, while maleic anhydride (MAH)-mediated chemical modification enhances surface charge density, collectively improving the electrical output performance of the MAH modified delignified wood (MDW). The WHEG device achieves an open-circuit voltage (V_OC) exceeding 0.3 V during water infiltration and evaporation. Remarkably, the HEG device utilizing ZnC electrodes demonstrates a significantly higher V_OC of about 1.3 V and a power density of 6.2 μW/cm². WHEGs in series can power commercial electronics and self-powered systems. Integrated WHEG units enable customizable power outputs for direct energy storage or supply. Beyond electricity generation, the multifunctional MDW exhibits real-time responsiveness to water droplet movement, offering potential applications in leakage detection and rainfall monitoring. This work provides a novel pathway for designing efficient generators using sustainable materials, thereby expanding the application scope of hydrovoltaic technology.

The serious shuttle effect involving lithium polysulfides (LiPSs) stands as a critical obstacle impeding the advancement of lithium‑sulfur batteries (LSBs). In this paper, flexible NbSe₂/carbon nanofibers (CNF) film was fabricated through electrospinning and calcination processes. The NbSe₂/CNF film possesses efficient conductive network and strong chemical-capturing capabilities for LiPSs. Owing to the synergistic combination, the NbSe₂/CNF composite can remarkably alleviate the shuttling behavior of LiPSs. Consequently, the battery integrated NbSe₂/CNFs interlayer achieves a reversible capacity of 762 mAh g^-1 following 300 cycles at 0.5C. Furthermore, it shows superior rate performance, reaching a capacity of 475 mAh g^-1 when subjected to the high rate of 4C. This study offers a reasonable approach for manufacturing flexible interlayers with optimized structures to boost the electrochemical behavior of LSBs.

Due to high reactivity and oxidative capacity, membrane-based advanced oxidation processes (AOPs) have emerged as promising technologies for wastewater remediation. Herein, a FeOCl-functionalized hollow fiber ceramic membrane (FeOCl@HFCM) was fabricated via a dry-wet spinning phase inversion method, and its performance for recalcitrant organic pollutants degradation was evaluated. The asymmetric catalytic membrane with a 45% dense layer fraction achieved a removal efficiency of 99.8% for methylene blue and a 63.4% total organic carbon reduction rate. The hydraulic retention time was extended to 9.45 ms. COMSOL simulations indicated that increasing the proportion of the dense layer significantly enhanced the local concentration and confinement of reactive oxygen species (ROS), thereby improving pollutant degradation. The catalytic confinement effect generated within the dense layer significantly increased the local concentration of ROS, promoting the non-selective oxidation of pollutants. The membrane reactor exhibited robust stability over 30 days. Liquid chromatography-mass spectrometry and ECOSAR verified that degradation occurs via demethylation and ring-opening reactions driven by ^•OH and ^•O₂^-, producing intermediates with relatively low toxicity. By selectively regulating the structure of the catalyst support, the non-selective and highly efficient oxidation of pollutants was achieved. This study provides guidance for the application of membrane-based AOPs in wastewater treatment.

Ice recrystallization inhibition (IRI) materials are important in both fundamental research and practical applications, but achieving efficient regulation through molecular design remains challenging. Herein, we synthesized a series of imidazole-based ionic liquids with triphenyl groups, 3ph-imi[X], and investigated the influence of various anions on their relationship between self-assembled structures and ice crystal regulation properties. In aqueous solution, 3ph-imi[FeCl₄] was found to form well-defined spindle-shaped nanosheets with crystalline order, whereas the other anions (cl, Br, NO₃, Tb(NO₃)₄, ho(NO₃)₄) yielded conventional spherical micelles. Notably, 3ph-imi[FeCl₄] exhibited strong IRI activity (23.8%) at a rather low concentration (0.32 mM). The mechanism of the high IRI activity was investigated using single crystal X-ray diffraction and molecular dynamics simulations, which indicated that the spacing between its hydrophilic groups (7.07 Å) matched the lattice parameter of hexagonal ice along the c-axis, enabling effective adsorption onto the ice crystal surface thereby inducing interfacial curvature to inhibit ice crystal growth. This study provides new insights for designing high performance IRI materials by optimizing anion selection and molecular assembly to enhance interfacial order and ice matching capability, expanding the potential applications of ionic liquids in low-temperature fields.

Inspired by nature's sophisticated use of light energy, we report a bioinspired antibacterial trap switch operating without exogenous competitors. This work engineers a light-gated supramolecular system where host-guest conformational reorganization between cucurbit[8]uril (CB[8]) and dicationic symmetric azobenzene derivative (Azo-E) enables precise control over antimicrobial agent release. Upon ultraviolet (UV) irradiation triggers E-Z isomerization, enhancing its binding affinity to CB[8] and resulting in steric displacement of the encapsulated antibacterial agent through conformational reorganization. This system achieves >99.9% bacterial eradication, supports reversible switching across four conventional antibacterial agents, and reduces mammalian cell cytotoxicity. Spray-coatable on different biomaterial surfaces, it demonstrates spatial precision for localized disinfection. This molecular engineering establishes a general platform for spatiotemporally precise regulation of bioactive cargoes, enabling adaptive supramolecular systems with infection control.