Hierarchically heterogeneous interface structuring strategy for microenvironment-regulating and self-decontaminating biodegradable meta-membranes

Hierarchically heterogeneous interface structuring strategy for microenvironment-regulating and self-decontaminating biodegradable meta-membranes | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Hierarchically heterogeneous interface structuring strategy for microenvironment-regulating and self-decontaminating biodegradable meta-membranes Huan Xu, Shao-Zhen Wang, Xinjian He, Xing-Hua Wei, Guiying Zhu, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7509740/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Precise functionalization of heterogeneous interfaces in nanofibers is essential for advanced personal protective membranes. Here, we demonstrate a hierarchically heterogeneous interface structuring (HHIS) strategy to fabricate microenvironment-regulating and self-decontaminating meta-membranes (MRSD-PLA) by embedding zeolitic imidazolate framework-8 (ZIF-8) nanocrystals within poly(lactic acid) (PLA) fibers and anchoring F-TiO2 nanoblocks on their surfaces, creating an electronegativity contrast that directs electron migration and charge redistribution. ZIF-8 of porosity and electroactivity could enable charge capture/storage and trans-membrane transport (water vapor transmission rate: 4018 g·m⁻2·d⁻1; air permeability > 60 mm·s⁻1 at 100 Pa). Combined with the hydrophobicity and self-cleaning capability from F-TiO2, a sustained charge migration establishes a closed-loop capture-storage-regeneration cycle. This results in self-powered sensitive monitoring and a high PM0.3 filtration efficiency of 99.3% yet a low pressure drop of 51.9 Pa (quality factor: 0.11 Pa⁻1) Moreover, MRSD-PLA inhibit bacterial growth and balance robust mechanical strength with biodegradability, showcasing great potential for high-performance personal protection. Physical sciences/Materials science/Soft materials/Polymers Physical sciences/Engineering/Chemical engineering Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Multifunctional personal protective equipment plays is critical in fields including healthcare, aerospace, and specialized operations 1,2 . However, conventional protective materials often fail to simultaneously deliver high protective performance, physiological comfort, and environmental sustainability. For instance, most high-efficiency protective materials depend on high-basis-weight nonwovens or dense coatings to provide barrier properties, but this severely restricts air permeability and moisture transport 3,4 . Similarly, electret materials exhibit charge decay under high-humidity conditions, resulting in a substantial loss of protection performance 5 . Furthermore, the large-scale disposal of single-use protective gear raises growing ecological concerns. Therefore, developing advanced intelligent protective materials that integrate multiple functionalities has become a critical research focus in materials science and engineering. The stability of human microenvironmental parameters, such as moisture-thermal balance and cleanliness at the skin-textile surface, is critically linked to the wearing comfort, health safety, and functional efficacy of protective membranes 6,7 . Although dense structures can confer certain barrier properties against pollutants, they often severely restrict air permeability and moisture transport, thereby hindering the maintenance of a stable microenvironment 2,8 . Conversely, porous breathable materials often exhibit inherent surface hydrophilicity or low roughness, making them susceptible to liquid penetration and pollutant adhesion, and thus incapable of self-cleaning 9 . In this context, nanofiber membranes have emerged as a promising platform for simultaneous microenvironment regulation and hydrophobic self-cleaning, owing to their high specific surface area, tunable porous architecture, and facile surface modifiability. The interconnected porous networks of these membranes facilitate efficient moisture vapor and gas transport 10 . By precisely tailoring their porosity and pore size distribution, they can effectively accommodate human metabolic heat and moisture dissipation, thereby maintaining moisture-thermal balance at the skin surface. However, the inherent limitations of single-component nanofiber membranes still hinder their ability to meet the comprehensive requirements of complex application scenarios 11 . In recent years, nanofiber-based heterogeneous interface engineering has become a pivotal strategy for enhancing the performance of multifunctional nanocomposites. Using nanofibers as structural scaffolds, hierarchical heterogeneous interfaces with distinct component gradients, controllable microtopography, and tunable electronic structures can be constructed 12,13 . This is achieved by precisely regulating the interfacial interactions, geometric configurations, and chemical environments of heterogeneous components located within the fiber core, on the fiber surface, or between adjacent fibers, Such engineering offers insights into the structural design and functional optimization of advanced protective membranes 14,15 . For example, heterogeneous interfaces formed between metal-organic frameworks (MOFs) and polymers can utilize the high porosity of MOFs to facilitate molecular transport 16 , while also enabling charge storage through coordination interactions 17,18 . Similarly, interfaces between modified metal oxides and fibers enable functional integration through surface modification 19,20 . However, current research predominantly focuses on single-component or single-interface functional designs, lacking systematic strategies for constructing hierarchical heterogeneous structure. The absence of multiscale and hierarchically organized interface engineering leads to inefficient allocation of functionalities, such as microenvironment regulation, self-decontamination, and high-performance protection, across distinct interfacial levels 21,22 . Consequently, this results in inadequate functional synergy and limits their applicability in complex advanced protection scenarios. In this work, we disclose a hierarchically heterogeneous interface structuring (HHIS) strategy to develop meta-membranes (MRSD-PLA) with microenvironment-regulating and self-decontamination capabilities, thereby overcoming the trade-off between structural integrity and functional performance in personal protective membranes. It refers to a hierarchical structure with emergent functionality, achieved through the spatial organization and interfacial coupling between the two phases. Using biodegradable poly(lactic acid) (PLA) as the structural scaffold, this strategy involves embedding highly porous and electroactive zeolitic imidazolate framework-8 (ZIF-8) nanocrystals, which are composed of zinc ions coordinated with 2-methylimidazole ligands forming a robust microporous framework within the individual fibers. The ordered pore channels of ZIF-8 facilitate the directional transport of small molecules (e.g., water vapor and air), thereby effectively regulating temperature and humidity across the membrane. Simultaneously, low-surface-energy and photocatalytically active fluorinated titanium dioxide (F-TiO 2 ) nanoblocks are anchored on the fiber surfaces. The fluorinated modification introduces hydrophobicity and strong electronegativity, which enable self-decontamination and create deep charge traps. By modulating the electronic structure at the heterogeneous interfaces between ZIF-8 and F-TiO 2 , this process induces directed electron migration and spatial charge redistribution, establishing a continuous “capture-storage-regeneration” charge cycling mechanism. This structure not only enhances the filtration efficiency of charged pollutants such as particulate matter (PM) and pathogens but also mitigates performance degradation under harsh conditions like high-humidity, thereby ensuring long-term stability in protection. This work provides a theoretical foundation and a technical paradigm for developing multifunctional integrated materials for multifunctional personal protection. Results Synthesis of the MRSD-PLA Multifunctional personal protective membranes used in medical surgical gowns and space suits need to rigorously balance high barrier performance, breathable comfort, and mechanical stability, while also integrating multifunctional properties to meet the complex demands of specialized environments 23 . Accordingly, we employ a hierarchically heterogeneous interface structuring (HHIS) strategy to fabricate microenvironment-regulating and self-decontaminating meta-membranes (MRSD-PLA). These membranes integrate multiple functionalities including isolation protection, moisture-wicking permeability, self-cleaning, and signal conversion, aiming to overcome the performance degradation commonly exhibited by traditional protective materials under complex environmental conditions. The core architecture of MRSD-PLA consisted of biodegradable PLA nanofibers serving as the structural scaffold. ZIF-8 nanocrystals with high porosity and electrochemical activity were embedded into individual PLA fibers via electrospinning. This ptocess formed ordered molecular transport channels that facilitate the directional diffusion of air and water vapor, thereby dynamically regulating the skin microenvironment (Fig. 1a). The abundant coordinatively unsaturated sites in ZIF-8 serve as efficient electron traps for charge capture and storage. Simultaneously, F-TiO 2 nanoblocks with low surface energy and high electronegativity were anchored onto the fiber surface via electrospray, enabling hydrophobic self-cleaning and the formation of deep charge traps. Under external environmental disturbances, interfacial charges may undergo transient dissipation. However, the heterogeneous structure facilitates directional migration of stored charges from ZIF-8 toward the interface, thereby promptly replenishing depleted surface charges 24 . This process establishes a closed-loop “capture-storage-regeneration” cycle, enabling sustained and stable electrostatic forces. The hierarchically heterogeneous interface structurings effectively suppress performance degradation under extreme environments and significantly enhance the environmental adaptability and service reliability of the membranes. The MRSD-PLA leverage their hierarchically interface structure to enable unidirectional transport of sweat vapor and metabolic heat to the external environment, while their hydrophobically functionalized surface effectively blocks the penetration of liquid contaminants (Fig. 1b). The selectively designed mass-thermal transmission channels within the membranes ensure microenvironmental stability at the skin-membrane interface without compromising their protective performance. Owing to the abundant charges stored in ZIF-8 nanocrystals and the deep charge traps created by F-TiO 2 nanoblocks 25 , the membranes facilitate continuous electrostatic interception by remotely capturing pathogen-bearing aerosols and submicron particles via strong electrostatic interactions. Even under high-humidity conditions, the MRSD-PLA maintain high surface potential along wtih stable dynamic charge retention and regeneration capabilities, thereby substantially mitigating the impact of environmental humidity fluctuations on protective efficacy. The inherent piezoelectric-triboelectric properties of the heterogeneous structured fibers enable real-time responses to mechanical motions, converting these stimuli into quantifiable voltage, current, and charge signals for continuous monitoring of physiological status of the wearer 26 . Furthermore, through the structural integration of nanocrystal-mediated charge storage, a mechanically stable PLA scaffold, and photocatalytically active hydrophobic nanoblocks, MRSD-PLA achieve self-cleaning and antibacterial functionality while balancing mechanical strength during use with biodegradability after disposal. Based on the internal structural regulation and surface functional modification of nanofibers, we fabricated MRSD-PLA with hierarchically heterogeneous interface structures. These meta-membranes not only overcome the inherent trade-off between protective efficacy and wearing comfort but also provide a crucial theoretical framework and a technical paradigm for developing next-generation multifunctional integrated intelligent protective materials, advancing personal protective membranes toward intelligence, sustainability and adaptability to various scenarios. The macroscopic properties of nanofiber membranes featuring heterogeneous interface structures are collectively determined by their microstructural morphology, chemical composition and crystalline configuration. Fiber diameter distribution and pore architecture collectively regulate the air permeability, moisture vapor transmission and purification performance of the membrane 27 . Composition dictates the physicochemical characteristics, whereas the crystal structure and heterogeneous interfaces dominate the mechanical stability and spatial charge redistribution. Elucidating these structure-property relationships offers critical insights into enhancing the regulation of human microenvironments and improving protection performance 28 . Figure 2 illustrates the microscopic morphology, chemical composition and interfacial characteristics of MRSD-PLA. ZIF-8 nanocrystals were synthesized via a thermodynamically driven coordination self-assembly process between zinc ions (Zn 2 ⁺) and 2-methylimidazole ligands (Fig. 2a). Imidazole molecules bridge Zn 2 ⁺ as structural nodes, forming a highly porous crystalline framework with well-defined channel networks. The short-chain organic linkers and precise metal–ligand coordination geometry endow ZIF-8 with a high specific surface area suitable for gas adsorption, while facilitating efficient molecular transport pathways that enhance mass transfer kinetics. The abundant coordinatively unsaturated Zn 2 ⁺ sites serve as effective electron traps, enabling efficient charge capture and storage while establishing continuous charge conduction networks throughout the framework. Moreover, covalent grafting of fluorinated functional groups onto the TiO 2 surface significantly reduced surface energy, thereby enhancing hydrophobicity (Fig. 2b and Supplementary Fig. 1), and formed deep-level charge traps via its high electronegativity. This fluorination treatment selectively modifies the surface chemistry without compromising the bulk crystallinity of TiO 2 , allowing improvements of both wetting behavior and surface electronic properties. Scanning electron microscopy (SEM) images revealed that ZIF-8 nanocrystals possess a well-defined rhombic dodecahedral morphology. They were closely packed through intercrystalline interactions, facilitating the formation of continuous gas transport channels and maximizing pore accessibility. F-TiO 2 nanoblocks consisted of aggregated nanoparticles measuring 30−50 nm, and their disordered stacking created micro/nano-scale pores. Using the electrospinning-electrospray technique, we fabricated membranes with anchored F-TiO 2 at mass fractions of 0%, 2%, 4% and 6%, designated as P-PLA, MRSD-PLA2, MRSD-PLA4 and MRSD-PLA6, respectively, with ZIF-8 mass fractions of 25%, 22.2%, and 20% (Fig. 2c-f). The incorporation of ZIF-8 increased the conductivity of the spinning solution, which promoted sufficient stretching of the polymer chains under the electric field and resulted in fiber refinement (Supplementary Figs. 2, 3). Control experiments conducted on the PLA@ZIF-8 membrane (without F-TiO 2 ) revealed that the embedded ZIF-8 nanocrystals primarily contributed to the enhanced charge storage and water vapor transmission rate (WVTR), while the synergistic combination with surface-anchored F-TiO 2 nanoblocks was crucial for achieving superior hydrophobicity, the highest surface potential, and optimal filtration efficiency through the formation of hierarchical heterogeneous interfaces. These slit-like pore structures enhance gas flux and mass transfer efficiency, thereby improving the air purification performance. Notably, ZIF-8 nanocrystals formed bead-on-string configurations within the fibers, whereas the anchored F-TiO 2 nanoblocks created nanoscale protrusions, pores and surface textures via stacking and aggregation. These components cooperatively constructed hierarchical heterogeneous interfaces both on and within individual fibers. Elemental mapping confirmed the uniform spatial distribution of characteristic elements including carbon (C), nitrogen (N), zinc (Zn) and fluorine (F) (Supplementary Fig. 4a). The mass fractions of F-TiO 2 in the composite membranes were verified by thermogravimetric analysis (TGA), which confirmed that the measured values were in good agreement with the nominal loadings, thereby affirming the reliability of the electrospray process (Supplementary Fig. 4b). The Fourier-transform infrared (FTIR) spectra in Figure 2g-j reveal the characteristic functional groups of MRSD-PLA. P-PLA exhibited a C=O stretching vibration peak at 1750 cm⁻ 1 , along with characteristic C−O absorption peaks at 1180 cm⁻ 1 and 1080 cm⁻ 1 . Following the incorporation of ZIF-8 and F-TiO 2 , MRSD-PLA spectra exhibited asymmetric stretching vibrations of aromatic and aliphatic C−H bonds from the imidazole ring at 3135 cm⁻ 1 and 2928 cm⁻ 1 , respectively. The absorption peak at 1480 cm⁻ 1 corresponded to C=N stretching in the imidazole ring, while the peak at 1383 cm⁻ 1 was attributed to the stretching vibrations of interfacial −CH 3 and O−O groups. The introduction. of nanoparticles renders the electron cloud distribution in PLA chains more uniform, reduces the force constant of chemical bonds, and consequently causes a red shift in absorption peaks. The X-ray diffraction (XRD) analysis was employed not only to verify the successful incorporation of ZIF-8 nanocrystals within the PLA matrix but also to elucidate their role as nucleating agents that modulate the crystallization behaviour of PLA, which is crucial for understanding the enhanced mechanical and charge-storage properties of the composite membranes (Fig. 2k). Specifically, P-PLA displayed a broad, weak diffraction peak, indicating low crystallinity that is typical of processed PLA. In contrast, MRSD-PLA exhibited sharp, strong diffraction peaks at 7.3°, 10.5° and 12.8°, corresponding to the (011), (002) and (112) crystal planes of ZIF-8 nanocrystals 29 . Moreover, the increased intensity and sharpness of these peaks with higher ZIF-8 loading indicate that ZIF-8 acts as a nucleating agent, promoting the crystallization of PLA. This insight is critical for understanding the enhanced mechanical and charge-storage properties of the composite membranes 30 . The nitrogen adsorption-desorption isotherms indicated that the specific surface areas of MRSD-PLA2, MRSD-PLA4, and MRSD-PLA6 were 168, 185, and 209 m 2 ·g⁻ 1 (Fig. 2l), which was significantly higher than that of the P-PLA membrane (18 m 2 ·g⁻ 1 ). This substantial increase originates from the synergistic contribution of the embedded ZIF-8 nanocrystals, which introduce intrinsic micropores, and the nanoscale surface roughness created by the anchored F-TiO 2 nanoblocks. We speculate that the micropores originate from ZIF-8 nanocrystals, the mesopores from inter-nanoblock spaces and fiber surface textures, and the macropores from the inter-fiber voids. This multiscale porous network is directly responsible for the enhanced gas adsorption capacity and provides abundant pathways for efficient vapor and gas transport. The mechanical performance of MRSD-PLA under tensile loading is shown in Figure 2m and 2n. Compared with P-PLA, MRSD-PLA demonstrated higher tensile strength and elastic modulus. ZIF-8 nanocrystals act as reinforcing fillers that suppress crack propagation, F-TiO 2 nanoblocks enhance interfacial adhesion through the formation of heterogeneous structures, and PLA nanofibers provide a continuous matrix for structural support. The combined effect of these components enables MRSD-PLA to withstand greater external stresses before deformation or fracture, thereby significantly improving its mechanical properties 31 . Heterogeneous composite fiber membranes with multilevel roughness were constructed by embedding ZIF-8 nanocrystals within individual nanofibers while anchoring low-surface-energy F-TiO 2 nanoblocks on the surface to create protrusions and fine textures. The hydrophobically modified heterogeneous fiber surface traps air within grooves and pores. This causes water droplets to primarily contact the entrapped air and rough protrusions, thereby significantly reducing the actual solid-liquid contact area 32 . By leveraging HHIS strategy, the water contact angle (WCA) of MRSD-PLA6 increased to 137.4° (Fig. 3a), which is significantly higher than that of P-PLA. MRSD-PLA form interconnected microscale and nanoscale pores through random fiber stacking, enabling gas permeation via mass transfer driven by molecular thermal motion and concentration gradients (Fig. 3b). The micro-nano protrusions formed by low-surface-energy F-TiO 2 yield a high WCA and suppress water spreading and penetration. This prevents water from clogging the fiber interstices or ZIF-8 micropores, thereby ensuring efficient transport of gases and water vapor. Meanwhile, these heterogeneous interfaces significantly increase the specific surface area, providing more active sites for adsorption and diffusion processes while promoting the evaporation and diffusion of water molecules at the fiber surfaces 33 . This structure helps to avoid moisture accumulation and heat retention at the interface, thereby enhancing the overall moisture permeability. Water vapor permeability tests showed that the hierarchical pore structure of MRSD-PLA6 enables water vapor to undergo Fickian diffusion driven by concentration gradients, achieving coupled transport of water vapor and heat 34 . Owing to the concerted regulation of chemical composition and microstructure, condensed water droplets can remain suspended on the surface for extended periods without penetration, demonstrating excellent water resistance and air permeability (Fig. 3c). Microenvironment regulation The MRSD-PLA6 maintained a high WCA over extended periods, demonstrating superior wetting resistance and stability against time-dependent wetting degradation (Fig. 3d). Furthermore, the differential hydrophobicity design reduces liquid water retention on the membrane surface, facilitating easy removal with minimal residue. The low surface energy of F-TiO 2 , combined with the inherent hydrophobicity of the nanofibers, generates a high interfacial energy barrier that significantly enhances liquid repellency. This performance surpasses that of conventional hydrophobic materials, which are often prone to aging. These anti-wetting characteristics enable MRSD-PLA to consistently repel various liquids (including water and bodily fluids), thereby providing a reliable barrier for personal protective equipment (Fig. 3e and Supplementary Fig. 5). The self-cleaning mechanism arises because the adhesion force between particles and the hydrophobic surface of MRSD-PLA6 is weaker than the cohesive force within water droplets (Fig. 3f). Consequently, rolling water droplets can carry and remove surface contaminants. This process is governed by the interplay between surface wettability regulation and heterogeneous interface structuring, which promotes rapid contaminant detachment from the fiber surfaces 2 . The macroscopic properties of nanofiber membranes including air permeability, moisture vapor transmission and mechanical performance, directly influence the comfort, durability, and application scope of textile-integrated products. The MRSD-PLA6 exhibited a WVTR value of 4018 g·m⁻ 2 ·d⁻ 1 , significantly surpassing that of most commercial protective materials (Fig. 3g). It should be noted that the reported WVTR value of 4018 g·m⁻ 2 ·d⁻ 1 was obtained under controlled conditions (25°C, 90% RH) using the standard cup method. This value exceeds the commonly referenced threshold of 2000 g·m⁻ 2 ·d⁻ 1 , which is derived from protective clothing standards under similar testing environments, ensuring adequate moisture dissipation during perspiration. The incorporation of ZIF-8 and F-TiO 2 not only avoids increasing resistance to water vapor transmission but also facilitates the development of heterogeneous structured fibers with optimized pore morphology and surface characteristics, thereby enhancing water vapor diffusion efficiency (Fig. 3h). Air permeability, a key indicator for evaluating energy exchange and cellular metabolic environments, is critical for reducing the risks of skin inflammation and thermal stress 35 . MRSD-PLA demonstrated efficient gas transport owing to their high specific surface area, high porosity and interconnected networks, achieving air permeability values above 60 mm·s⁻ 1 . In contrast, P-PLA exhibited an air permeability of only 46.8 mm·s⁻ 1 due to its dense structure and limited porosity (Fig. 3i). The highly porous structure of ZIF-8 and the resulting heterogeneous interfaces provide abundant nanoscale transport pathways for gases and vapor, including diffusion along fiber surfaces and heterogeneous boundaries, through intrinsic ZIF-8 channels, and through interparticle spaces among F-TiO 2 nanoblocks (Fig. 3j and Supplementary Fig. 6). Electroactive sensing The electroactivity of the heterogeneous structured nanofiber membranes, fabricated via HHIS strategy, originates from a persistent electrostatic field induced at the surface through dielectric polarization. The surface potential of MRSD-PLA6 reached 5.8 kV, representing a 75.7% increase compared to P-PLA (Fig. 4a). Crucially, the low surface energy and hierarchically rough structure of MRSD-PLA6 effectively suppresse carrier migration and markedly mitigate charge dissipation caused by environmental factors 36 , enabling the membrane to maintain high potential stability for over 90 days. In contrast, P-PLA exhibited significant charge decay due to water infiltration-induced ion conduction and dipole relaxation. The surface-enriched highly electronegative fluorine-containing functional groups in MRSD-PLA attract and localize interfacial carriers, restricting their free migration and further enhancing interfacial dielectric properties through the formation of a stable polarized interface. Consequently, MRSD-PLA achieve a high relative dielectric constant and energy storage density while maintaining low dielectric loss. At a frequency of 10 3 Hz, the relative dielectric constant of MRSD-PLA6 reached 1.72, which is 1.24 times that of P-PLA (Fig. 4b). The observed deviations of some data points from the fitting curve are attributed to the inherent heterogeneity in the distribution of charge traps and interfacial polarization across the hierarchically structured composite fibers (Fig. 4c). Electrostatic adsorption experiments further demonstrated that the enhanced electrostatic interactions overcame the kinetic barriers of particles in airflow, endowing MRSD-PLA6 with efficient capture of fine particles (inset of Fig. 4c). During high-voltage electrospinning, external electric fields drive the rearrangement of PLA molecular chains, inducing the aligned orientation of dipoles. This alignment enhances the overall dipole moment of the material (Fig. 4d). The electroactive ZIF-8 nanocrystals embedded within the PLA fibers adsorb and stabilize free charges through coordination bond polarization and π-electron delocalization. This mechanism effectively suppresses charge dissipation in the nonpolar PLA. Simultaneously, the high electronegativity of F-TiO 2 nanoblocks enhances their ability to confine surface charges through interfacial dipole-dipole interactions, thereby reducing environmental charge dissipation. Owing to differences in their energy band structures, two types of heterogeneous interfaces which are formed between ZIF-8 and PLA, and between F-TiO 2 and the PLA surface, generate charge traps at these interfaces 37 . These traps capture free charges generated during triboelectric or polarization processes, significantly extending the charge lifetime and thereby increasing the surface electrostatic accumulation (Fig. 4e). The stabilization of internal charges, combined with external charge confinement and cooperative dipole alignment, collectively enhances the surface activity of MRSD-PLA. This combination establishes a solid foundation for its exceptional electrostatic performance in applications such as air purification. The heterogeneous structured fibers in MRSD-PLA form localized charge-transfer channels that significantly enhance the conversion efficiency of mechanical energy to electrical energy by facilitating interfacial charge separation and migration. COMSOL simulations reveal the fundamental triboelectrification mechanism: during contact-separation cycles, enhanced surface polarization and charge storage capacity drive the accumulation of opposite charges at the interfaces 19,38 . Subsequent charge release during separation generates a significant electrical potential (Fig. 4f). The surface roughness created by F-TiO 2 on the fiber surfaces increases the contact area for friction, while the substantial electronegativity difference further enhances charge separation efficiency. Simultaneously, the electroactivity of ZIF-8 facilitates charge transfer through polarization effects, increasing the charge generated per triboelectric event. Furthermore, favorable energy band alignment at the heterogeneous interfaces reduces the energy barrier for interfacial charge transfer, thereby accelerating the directional transmission of triboelectric signals (Fig. 4g). The triboelectric output was measured in a contact-separation mode between the meta-membranes and an external counter electrode (Supplementary Fig. 7). The electrical output performance of MRSD-PLA with different F-TiO 2 loadings is shown in Figure 4h-j. Specifically, MRSD-PLA6 exhibited an open-circuit voltage of 22.3 V, a short-circuit current of 67.5 nA and a transferred charge of 8.2 nC, representing improvements of 248%, 224%, and 925%, respectively, compared to P-PLA. Charges accumulate predominantly at the interface between the nanomaterials and PLA fibers, where these heterogeneous interfaces serve as efficient sites for charge separation 39 . The well-matched energy levels between ZIF-8 and F-TiO 2 generate electric fields at the interfaces, which facilitate the separation of tribologically induced charges and suppress electron recombination. Thus, the complementary roles of F-TiO 2 in charge separation and ZIF-8 in charge storage and transfer synergistically enhanced the triboelectric output performance 40 . Even under high-humidity conditions, the micro-nano rough structures on the heterogeneous structured fiber surface trap air, forming a barrier that prevents direct contact between water molecules and charge storage sites. This mechanism maintains stable charge transfer during contact electrification and electrostatic induction. MRSD-PLA6 exhibited only 10.3% voltage attenuation under gradient humidity conditions (Fig. 4k), effectively avoiding the charge neutralization and performance degradation commonly observed in P-PLA. The spatial charge redistribution induced by heterogeneous interfaces drives directional electron migration, enabling continuous conversion of mechanical energy to electrical energy over repeated cycles 41 . MRSD-PLA6 maintained a stable voltage output over 500 seconds of continuous operation (Fig. 4l), demonstrating enormous potential for long-term energy storage, signal transmission and real-time physiological monitoring. Air purification Efficient filtration of aerosols, droplet nuclei and pathogen-laden particles ranging from 0.3 to 5 μm in size is critical for constructing high-performance bidirectional protective systems 42 . Medical surgical gowns provide effective barriers against tissue debris, bodily fluid aerosols and environmental pathogenic microorganisms generated during surgical procedures. Furthermore, PM can infiltrate the precision components of spacesuits, directly disrupting critical life support systems including oxygen supply and temperature regulation. Capitalizing on the excellent surface electroactivity, water resistance and air permeability of MRSD-PLA, we systematically evaluated their air purification performance under various operating conditions. MRSD-PLA with heterogeneous interface structures exhibited high filtration efficiency for the most penetrating PM 0.3 across varying flow rates (Fig. 5a, b). At a flow rate of 10 L·min⁻ 1 , MRSD-PLA maintained a PM 0.3 filtration efficiency exceeding 99.1% with a pressure drop of only 51.9 Pa, demonstrating high purification efficiency and low energy consumption even at elevated flow rates. When the flow rate increased to 85 L·min⁻ 1 , P-PLA showed a significant decrease in filtration efficiency to 71.3%, accompanied by a pressure drop exceeding 400 Pa. In contrast, MRSD-PLA exhibited only a slight decrease in efficiency and a limited increase in flow resistance (Supplementary Figs. 8, 9). As the flow rate increases, the two membranes exhibit markedly distinct performance trends, fundamentally attributable to the combined contribution of enhanced structural stability, charge retention and mass transfer efficiency in MRSD-PLA, achieved through the embedding of ZIF-8 nanocrystals and surface anchoring of F-TiO 2 nanoblocks. For P-PLA, elevated flow rates generate an aerodynamic drag force on PM that exceeds its limited electrostatic adsorption capacity, leading to the penetration of submicron particles through the membrane 43 . Concurrently, its relatively weak fiber network undergoes compaction under high-velocity airflow, reducing the effective porosity and contracting the pore size, thereby significantly increasing air resistance. In contrast, ZIF-8 nanocrystals embedded within the fibers introduce abundant nanopores and a high specific surface area. These features enhance physical interception mechanisms including size exclusion and surface adsorption, while also providing stable charge storage sites, thereby maintaining superior electrostatic capture performance (Supplementary Fig. 10). The surface-anchored F-TiO 2 nanoblocks leverage their high electronegativity and crystalline-amorphous heterogeneous interfaces to form deep charge traps on the fiber surfaces. These traps sustain a robust electrostatic field through continuous charge collection and storage, enabling effective capture of PM. Furthermore, the multiscale structural modulation of both the fiber interior and surface significantly enhances the mechanical strength of the nanofiber membranes. This enhancement enables the membranes to resist deformation under high flow rates, maintain an interconnected porous structure, and effectively suppress pressure drop increase. The hierarchically heterogeneous structure endows MRSD-PLA with dual advantages: high-efficiency particulate matter capture and low pressure loss at high flow rates, achieved through electrostatic enhancement and physical capture mechanisms. This structural superiority was further confirmed by higher quality factor ( QF ) values (Fig. 5c). Notably, the MRSD-PLA6 membrane demonstrates a more favourable combination of high filtration efficiency and lower pressure drop compared to conventional high-efficiency filtration media such as N95 melt-blown layers and fiberglass filters (Supplementary Table 1). We fabricated nanofiber membranes with heterogeneous interface structures via HHIS strategy and modulated their surface wettability to systematically evaluate the effect of water washing on PM filtration efficiency. Before washing, MRSD-PLA6 maintained 95% filtration efficiency for PM 2.5 at 85 L·min⁻ 1 through combined physical interception (e.g., inertial impaction and Brownian diffusion) and electrostatic adsorption (deep charge traps and heterogeneous interfaces), whereas P-PLA, lacking such structural design, exhibited only 88.2% efficiency (Fig. 5d). After 30 minutes of immersion in water and subsequent drying, the PM 2.5 filtration efficiency of P-PLA decreased to 65.4%, whereas that of MRSD-PLA6 decreased from 98.6% to 89.1% (Fig. 5e). Furthermore, the F-TiO 2 nanoblocks remain stable owing to strong interfacial adhesion, demonstrating excellent structural robustness, environmental tolerance and reusability without observable detachment, as confirmed by SEM imaging after regeneration and washing cycles (Supplementary Fig. 11). More importantly, owing to its stable charge storage and structural recovery mechanisms, MRSD-PLA6 maintained highly efficient and stable PM 2.5 filtration over extended periods (Fig. 5f). The performance stability can be explained by three mechanisms: (1) Strong hydrophobic groups reconfigure the hydration ion coordination structure at the solid-liquid interface, inhibiting charge dissipation induced by water ionization and thereby enhancing charge retention from an interfacial chemistry perspective; (2) Although interfacial charge undergoes transient dissipation under external disturbances, the heterojunction electric field drives migration of stored charges from ZIF-8 to the interface, promptly compensating for surface charge loss and establishing a “capture-storage-regeneration” cycle that enables self-sustaining electric fields 7,44 ; (3) The sustained charge migration from ZIF-8 to the interfaces establishes a closed-loop capture-storage-regeneration cycle, which is supported by the exceptional stability of surface potential, filtration efficiency under high humidity, and triboelectric output (Supplementary Figs. 12, 13). Under high-humidity conditions, filtration efficiency is a critical indicator for evaluating the charge stability, structural integrity and operational reliability of protective membranes. After 10 minutes of testing at 90% RH, the PM 2.5 filtration efficiency of P-PLA decreased from 89.5% to 76.4%, whereas that of MRSD-PLA6 declined from 98.4% to 89.5% (Fig. 5g). Concurrently, the pressure drop of P-PLA increased to 632 Pa, while that of MRSD-PLA6 increased to only 222 Pa (Fig. 5h). Notably, the fluorinated interface constructed by surface-anchored F-TiO 2 nanoblocks suppresses water molecule-mediated charge shielding through three synergistic effects: forming a hydrophobic physical barrier to reduce direct water-membrane contact, modulating the interfacial hydration structure to inhibit ion conduction-induced charge dissipation, and synergizing with heterogeneous interfacial charge traps to enhance charge confinement, which collectively ensure the stable surface potential and filtration performance of MRSD-PLA6 under high-humidity conditions. The exceptional water vapor permeability of MRSD-PLA can be further elucidated by considering the Knudsen and surface diffusion mechanisms within its hierarchical pore network. The pore size distribution indicated a substantial fraction of mesopores (2-50 nm) (Fig. 5i). Given that the mean free path of water vapor (~110 nm) is comparable to or larger than these pore diameters, Knudsen diffusion, where molecule-wall collisions dominate, becomes a significant contributor to the overall mass transfer. Concurrently, the high specific surface area, predominantly provided by the microporous ZIF-8, facilitates the adsorption and subsequent surface diffusion of water molecules (Fig. 5j). This mechanism involves the hopping of adsorbed molecules along the pore walls under a concentration gradient. Thus, the concerted action of Knudsen diffusion through the pore volume and surface diffusion along the extensive internal surface area creates highly efficient pathways for water vapor transport, which is of paramount importance for effective microenvironment regulation. Under challenging conditions, ZIF-8 nanocrystals within the heterogeneous structured fibers stabilize free charges through their electroactivity, while F-TiO 2 nanoblocks confine surface charges via interfacial dipole effects due to their strong electronegativity. The heterogeneous interfaces create charge traps through band alignment differences, collectively establishing a persistent electrostatic field that actively captures submicron and nanoparticles. Meanwhile, the microporous structure of ZIF-8 forms nanoscale capture channels within the fibers, and F-TiO 2 nanoblocks create micro-nano rough structures on the fiber surfaces. Together, they form a multilevel physical capture network that integrates interception, inertial impaction and diffusion mechanisms, enabling efficient filtration of particles across different size ranges. As discrete embeddings within PLA fibers, ZIF-8 nanocrystals avoid clogging internal micropores and inter-fiber macropores while facilitating continuous airflow pathways, thereby reducing bypass losses. The low surface energy of F-TiO 2 nanoblocks inhibits pore adhesion caused by water molecule adsorption, while their surface micro-nano structure induces an air slip effect that reduces viscous resistance at the airflow-fiber interface 45 . This synergy produces filtration performance and stability that surpass what can be achieved by systems based on either mechanism individually (Fig. 5k, l). Self-decontamination and biodegradability The warm and humid microenvironment that forms on the skin surface during prolonged outdoor activity promotes bacterial proliferation 46 . Microorganisms can metabolize nutrients in sweat to proliferate rapidly, disrupting the physiological barrier of the skin and potentially inducing inflammation or even local infection. This highlights the urgent need for materials capable of microenvironment regulation and active self-decontamination. The antibacterial properties of MRSD-PLA against Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ) were evaluated using the plate counting method (Fig. 6a). It is worth noting that the P-PLA membrane exhibited a minor reduction in bacterial viability, which may be attributed to the inherent low surface energy of PLA. MRSD-PLA exhibited high inactivation efficiency against both bacterial strains, and their antibacterial performance improved notably with increasing F-TiO 2 nanoblocks content. Specifically, MRSD-PLA6 demonstrated a bacterial inhibition rate of 90.3%, which was significantly higher than that of P-PLA (Fig. 6b). Through micro-nano structural characterization and molecular-level analysis, the multi-mechanism antibacterial activity of MRSD-PLA with heterogeneous interface structures was further elucidated (Fig. 6c). The Zn 2 ⁺ coordination sites in ZIF-8 and surface hydroxyl groups on F-TiO 2 act synergistically to enhance reactions between photogenerated charge carriers and adsorbed O 2 /H 2 O molecules on the material surface 47 . This leads to the generation of highly oxidative free radicals, primarily reactive oxygen species (ROS). The generated ROS penetrate bacterial cell membranes, degrade nucleic acids and proteins, disrupt cellular integrity, and ultimately cause metabolic dysfunction leading to bacterial death. Furthermore, the strong electrostatic attraction generated at the heterogeneous interface of the material firmly adsorbs bacteria onto the fiber surfaces, prolonging their exposure to ROS and thereby enhancing bactericidal efficacy 48 . Simultaneously, electrostatic interactions can disrupt the electrochemical potential balance across bacteria membranes, inhibit nutrient active transport and key metabolic enzyme activities, thereby effectively hindering bacterial proliferation (Fig. 6d). The constructed heterogeneous interface not only expands the light absorption range but also enhances electrostatic field stability 49 . Electrostatic adsorption acts to prolong bacterial residence time on the fiber surface, thereby synergistically enhancing the efficacy of the photocatalytic ROS generation. The widespread use of personal protective equipment, such as surgical gowns and isolation suits, has intensified waste management challenges and environmental burdens. Biodegradable materials can be progressively broken down by microorganisms in natural environments such as soil and compost, ultimately mineralizing into carbon dioxide and water (Supplementary Fig. 14). To assess the degradation behavior of membranes with heterogeneous interface structures, P-PLA and MRSD-PLA6 were subjected to burial experiments in moist soil at 40 °C. This environment simulated naturally warm, humid conditions to accelerate polymer chains scission through enhanced microbial metabolism and enzymatic catalysis 14,50 . After 84 days of burial, both P-PLA and MRSD-PLA6 underwent significant degradation and lost their structural integrity (Fig. 6e). The menbranes exhibited considerable degradation processes, providing direct experimental evidence for assessing the environmental lifecycle of such biodegradable protective materials and for regulating their degradation behavior via HHIS strategy. SEM images revealed abundant colonization by microorganisms capable of secreting PLA-degrading enzymes on the surfaces of both P-PLA and MRSD-PLA6 (Supplementary Fig. 15). Enzymatic hydrolysis cleaves the PLA molecular chains into small, environmentally benign molecules 51 . In vitro biodegradation kinetics showed that the membranes exhibited significant fiber fracture and embrittlement within 14 days, followed by extensive structural disintegration by day 28, and further fragmentation into millimeter-scale debris between days 42 and 56 (Supplementary Fig. 16). The quantitative degradation analysis confirmed the biodegradability of MRSD-PLA, showing a mass loss exceeding 75% over 84 days. Although the interfacial modifications in MRSD-PLA6 partially suppressed initial microbial attachment, the inherent biodegradability of the PLA ultimately dominated the degradation process under prolonged environmental stress. The HHIS strategy enables dual regulation of material performance and degradability: During service life, the heterogeneous interfaces formed by ZIF-8 and F-TiO 2 synergistically maintains mechanical properties and functional stability of the material. After disposal, the material undergoes orderly degradation through microbial enzymatic hydrolysis, achieving functional integration from efficient protection to minimal environmental impact 52 ,53 . This strategy provides a sustainable solution for the structural design and functional customization of disposable medical protective equipment. Discussion In summary, we fabricate meta-membranes (MRSD-PLA) that integrate adaptive microenvironment-regulating and self-decontaminating capabilities via a hierarchical heterogeneous interface structuring strategy. The embedding of highly electroactive, porous ZIF-8 nanocrystals within the fibers creates efficient molecular transport pathways. Consequently, the MRSD-PLA exhibit high moisture permeability (4018 g·m⁻ 2 ·d⁻ 1 ) and air breathability (>60 mm·s⁻ 1 ), facilitating rapid sweat and heat dissipation for real-time microenvironment regulation. Meanwhile, surface-anchored F-TiO 2 nanoblocks, characterized by low surface energy and high electronegativity, enable self-decontamination through combined hydrophobicity and photocatalytic activity. The synergistic effect between the internally embedded and surface modification constructs heterogeneous fiber interface. This architecture generates micro-nano roughness and deep charge traps, which promote directional electron transfer and spatial charge redistribution. Consequently, performance degradation under fluctuating environmental conditions is effectively mitigated. Even under high-humidity conditions, MRSD-PLA maintain a stable surface potential, reliable electrical signal transmission and high PM filtration efficiency. The hierarchical heterogeneous structures synergistically inhibit bacterial proliferation through multiple mechanisms, while also balancing mechanical strength during use with biodegradability post-disposal. This work establishes a paradigm for the rational design of next-generation, high-performance personal protective membranes. Methods Materials Poly(lactic acid) (PLA) with a molecular weight of 1.63 × 10 5 g·mol⁻ 1 was procured from Total Corbion PLA Co., Ltd., Thailand. Non-woven cellulose fabrics (60 g·m⁻ 2 ) was bought by Sateri Fiber Co. Ltd., China. N, N-dimethylformamide (DMF, purity > 98.0%) and dichloromethane (DCM, purity > 98.0%) were supplied by Sinopharm Chemical Reagent Co., Ltd. (China). Zinc acetate dihydrate (C 4 H 10 O 6 Zn), 2-methylimidazole, titanium(IV) isopropoxide (TTIP), isopropyl alcohol (IPA), ethanol (EtOH), and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) were obtained from Macklin Biochemical Co., Ltd. Synthesis of ZIF-8 nanocrystals Zinc acetate dihydrate (0.55 g) and 2-methylimidazole (4.1 g) were separately dissolved in deionized water (60 mL). The resulting mixture was transferred to a microwave reactor and heated at 140 °C for 10 minutes. The product was collected by centrifugation and vacuum-dried at 80 °C for 12 h to remove solvent, yielding ZIF-8 nanocrystals with high electroactivity and porosity. Synthesis of F-TiO 2 nanoblocks A mixture of 10 mL TTIP and 40 mL IPA was vigorously stirred and then added dropwise to a 1:1 (v/v) solution of deionized water and IPA to initiate hydrolysis.. The resulting mixture was transferred to a microwave reactor and heated at 180 °C for 1 h. The product was collected by centrifugation, vacuum-dried and then calcined in a tube furnace at 500 °C for 1 h to obtain anatase-phase titanium dioxide (TiO 2 ). Subsequently, the TiO 2 (2.0 g) was dispersed into a mixture containing (5.0 g) and ethanol (45.0 g) for surface fluorination. This treatment yielded fluorinated TiO 2 (F-TiO 2 ) nanoblocks with low surface energy and high electronegativity. Preparation of P-PLA nanofiber membranes PLA granules (1.0 g) were dissolved in a mixed solvent of DMF and DCM (3:7, v/v) under continuous stirring for 12 h to form a homogeneous electrospinning solution. Electrospinning was conducted at an applied voltage of 30 kV and a feed rate of 1.0 mL·min⁻ 1 . The process was carried out for 1.5 h under ambient conditions (25 °C, 35 ± 5% RH). The resulting nanofiber membranes were vacuum-dried at 40 °C for 12 h to obtain the pristine PLA membrane, denoted as P-PLA. Preparation of MRSD-PLA meta-membranes PLA (1.0 g) and ZIF-8 (0.4 g) nanocrystals were dissolved in a mixed solvent of DMF and DCM (3:7, v/v) under vigorous stirring to form a homogeneous spinning solution. Hydrophobic F-TiO 2 nanoblocks (0.2, 0.4 and 0.6 g) were individually dispersed in ethanol (10 mL) by ultrasonication to obtain stable F-TiO 2 suspensions. The spinning solution was electrospun using the previously described parameters. Simultaneously, the F-TiO 2 suspensions were deposited onto the forming fibers via electrospray. This co-axial process fabricated the microenvironment-regulating and self-decontaminating meta-membranes (MRSD-PLA). The electrospray process was conducted under the following conditions: an applied voltage of 30 kV, a feed rate of 1.0 mL·min⁻ 1 and a duration of 15 min. All processes were performed under ambient conditions (25 °C, 35 ± 5% RH). The resulting membranes were designated as MRSD-PLA2, MRSD-PLA4, and MRSD-PLA6, corresponding to the different mass fractions of F-TiO 2 . Characterization and test analysis The molecular structure of MRSD-PLA was characterized by Fourier transform infrared spectroscopy (FTIR, PerkinElmer Spectrum 3) and X-ray diffraction (XRD, Bruker D8 Advance). The specific surface area was determined by applying the Brunauer-Emmett-Teller (BET) model, and the pore size distribution (PSD) was calculated using non-local density functional theory (NLDFT). The electroactivity and triboelectric properties were evaluated in contact-separation mode using an MCE-3G servo-electric cylinder system. The output current, voltage and charge were recorded using a Keithley 6514 electrometer and a Keithley 2400 source meter. Additional characterization parameters are detailed in the Supplementary Information. Moisture permeability and air breathability tests The gas permeation properties were evaluated using a differential pressure method. A membrane sample with an effective area of 20 cm 2 was sealed between two chambers. The upstream chamber was filled with high-purity test gases at a constant pressure of 100 kPa, and the downstream chamber was evacuated and maintained under a dynamic vacuum. The steady-state gas flux was quantified with a soap-film flowmeter and the permeability was calculated based on Fick’s law of diffusion. The water vapor transmission rate (WVTR) was determined using the standard cup method (gravimetric method) under controlled conditions (25 °C, 90 ± 2% RH). The cited threshold of >2000 g·m⁻ 2 ·d⁻ 1 is based on industry standards for protective textiles (ISO 15496 and ASTM F1868), which also specify comparable testing environments to ensure consistent performance evaluation across materials. The membrane was securely sealed over a cup containing a desiccant (e.g., anhydrous calcium chloride) to create a constant humidity gradient. The mass change of the cup was periodically measured using a high-precision electronic balance. The WVTR was calculated from the steady-state mass change per unit time and normalized to the effective membrane area. Commercial counterparts include: Mask: activated carbon mask, Bao Weikang Co., China; PP: PurCotton® Everyday Non-medical Mask, Winner Medical Co., China; Cotton: PurCotton® Cotton Facial Mask, Winner Medical Co., China. Air purification performance evaluation The filtration performance against indoor PM was evaluated using a homemade air filtration testing system. The airflow rates were set to specific gradients of 10, 32, 65, and 85 L·min⁻ 1 using a high-precision flow pump, corresponding to the face velocities of 2.2, 6.9, 14.1, and 18.0 cm·s⁻ 1 (Supplementary Table 2). Sodium chloride (NaCl) aerosol particles, generated by a nebulizer, were employed as the test challenge. The filtration efficiency was measured simultaneously upstream and downstream of the membrane using two laser particle counters. The pressure drop across the membrane was monitored in real-time with high-precision differential pressure sensors. To evaluate washing durability, the membranes were immersed in deionized water to remove surface-accumulated PM and then recovered through a standard drying process Their filtration performance was re-tested post-recovery. The environmental humidity was controlled by the saturated salt solution method and continuously monitored with a digital humidity sensor. This setup enabled the evaluation of filtration performance under high-humidity conditions. For each membrane sample, measurements were replicated at three separate locations to ensure data representativeness and reliability. The values are reported as the mean ± standard deviation. Antibacterial performance test The MRSD-PLA were sectioned into 7 × 7 cm 2 samples for antibacterial testing. Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538 were selected as model Gram-negative and Gram-positive bacterial strains, respectively. After culture and serial dilution in nutrient broth, 500 μL aliquots of the bacterial suspension were spread evenly onto agar plates. The inoculated plates were then incubated at 37 °C for 24 h under constant illumination. The antibacterial activity was quantitatively assessed using the standard plate count method, and the bacterial reduction rate was calculated. The antibacterial tests under simulated sunlight were designed to evaluate the photocatalytic component of the antibacterial mechanism. The performance under dark or low-light conditions, relevant to real-use scenarios, is supported by the synergistic effects of electrostatic adsorption and ion release. Degradation behavior analysis The biodegradation of the membrane specimens was evaluated using a natural soil burial test. A natural soil burial method was employed to assess specimen degradation. Membrane samples (5 × 5 cm 2 ) were buried at a depth of 5 cm in vessels filled with a standard test soil. The vessels were then placed in an outdoor environment, thereby exposing the samples to natural weathering factors, including solar radiation and precipitation. To sustain microbial activity, fresh soil was supplemented at 7-day intervals. The surface morphology of the samples was regularly examined by optical microscopy to assess the degradation progression based on visual criteria such as cracking, discoloration, or fragmentation. Declarations Data Availability The data supporting the findings of this study are included within the Article and its Supplementary Information. Source data are provided with this paper. Acknowledgements The research work was supported by the National Key R&D Program of China (Nos. 2024YFC3015003 and 2023YFC3011704), the National Natural Science Foundation of China (Nos. 52573054, 52174222 and 52003292), the China Postdoctoral Science Foundation (2024M763565), the Opening Project of State Key Laboratory of Polymer Materials Engineering (Sichuan University) (No. sklpme2023-3-6). Author contributions H.X. and X.J.H. conceived the idea and designed the experiments. S.-Z.W. and G.Y.Z. performed the experiments. X.H.W., J.-L.G., Z.H., and Y.Z. contributed to materials characterizations. X.-P.L. and G.J.F. joined the discussion of the data and gave helpful suggestions. S.-Z.W. and H.X. wrote the manuscript. All authors participated in drafting the paper, and gave approval to the final version of the manuscript. Competing interests The authors declare no competing interests. Additional information Supplementary information The online version contains supplementary material available at Correspondence and requests for materials should be addressed to Xinjian He or Huan Xu. Peer review information Nature Communications thanks the anonymous reviewers for their contribution to the peer review of this work. A peer review file is available. Reprints and permissions information is available at Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. 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Supplementary Files SourceDataFigure3.xlsx Dataset 2 SourceDataFigure5.xlsx Dataset 4 SourceDataFigure2.xlsx Dataset 1 SourceDataFigure4.xlsx Dataset 3 SourceDataSupplementaryInformation.xlsx Dataset 7 SupplementaryInformationRe.pdf Supplementary Information SourceDataFigure6.xlsx Dataset 5 SourceData.pptx Dataset 6 RSFLTM.pdf Reporting summary Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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08:12:03","extension":"pdf","order_by":3,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":1667313,"visible":true,"origin":"","legend":"","description":"","filename":"ReportingSummary.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/672d1c4328218f8c813b61fb.pdf"},{"id":99588300,"identity":"c9c6ea92-6774-41ce-9c35-7cb2da9ac455","added_by":"auto","created_at":"2026-01-06 08:12:03","extension":"pdf","order_by":4,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":7645023,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryInformationRe.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/60b634182fd9fe5495e05da9.pdf"},{"id":99792932,"identity":"06a14be5-c5d9-437a-9f16-4538b7037327","added_by":"auto","created_at":"2026-01-08 13:28:53","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":1338925,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSynthetic routes and application scenarios of MRSD-PLA. a \u003c/strong\u003eConstructing heterogeneous interfaces within nanofibers via electrospinning-electrospray. \u003cstrong\u003eb\u003c/strong\u003e Microenvironment regulation and environmentally adaptive multifunctional integration for personal protection.\u003c/p\u003e","description":"","filename":"image1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/f76f4a06dbafac41e44f17b5.jpeg"},{"id":99792988,"identity":"9fc1ab68-d2ca-4430-b6a0-8a3b97b4902a","added_by":"auto","created_at":"2026-01-08 13:30:47","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1743030,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eStructural features of MRSD-PLA.\u003c/strong\u003e Synthetic routes and microstructure of (\u003cstrong\u003ea\u003c/strong\u003e) ZIF-8 nanocrystals and (\u003cstrong\u003eb\u003c/strong\u003e) F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks. SEM images of (\u003cstrong\u003ec\u003c/strong\u003e) P-PLA, (\u003cstrong\u003ed\u003c/strong\u003e) MRSD-PLA2, (\u003cstrong\u003ee\u003c/strong\u003e) MRSD-PLA4 and (\u003cstrong\u003ef\u003c/strong\u003e) MRSD-PLA6. FTIR spectra of MRSD-PLA in the ranges of (\u003cstrong\u003eg\u003c/strong\u003e) 4000−650 cm\u003csup\u003e−1\u003c/sup\u003e, (\u003cstrong\u003eh\u003c/strong\u003e) 1500−1300 cm\u003csup\u003e−1\u003c/sup\u003e, (\u003cstrong\u003ei\u003c/strong\u003e) 1250−1150 cm\u003csup\u003e−1\u003c/sup\u003e and (\u003cstrong\u003ej\u003c/strong\u003e) 1160−1020 cm\u003csup\u003e−1\u003c/sup\u003e. \u003cstrong\u003ek\u003c/strong\u003e XRD patterns of MRSD-PLA. \u003cstrong\u003el\u003c/strong\u003e Nitrogen adsorption-desorption isotherms of ZIF-8 and MRSD-PLA. \u003cstrong\u003em\u003c/strong\u003e, \u003cstrong\u003en\u003c/strong\u003e Stress−strain curves and tensile strength of MRSD-PLA.\u003c/p\u003e","description":"","filename":"image2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/23a3ba2b2b8bc43145d4cc41.jpeg"},{"id":99792267,"identity":"e92844f1-9ee6-4b8b-978f-ebd70777aa4e","added_by":"auto","created_at":"2026-01-08 13:17:18","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1787767,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eWater vapor permeability and air breathability of MRSD-PLA.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e Water contact angle of MRSD-PLA. \u003cstrong\u003eb\u003c/strong\u003eMultiscale structural and functional evolution of MRSD-PLA. \u003cstrong\u003ec\u003c/strong\u003e Water vapor permeability test of MRSD-PLA6. \u003cstrong\u003ed\u003c/strong\u003e Time-resolved wetting dynamics and droplet detachment behavior of MRSD-PLA6. \u003cstrong\u003ee\u003c/strong\u003e Liquid repellency performance of MRSD-PLA6. \u003cstrong\u003ef\u003c/strong\u003eSelf-cleaning process of MRSD-PLA6 under sand-water mixture contamination. \u003cstrong\u003eg\u003c/strong\u003e Comparison of WVTR between MRSD-PLA6 and commercial counterparts. \u003cstrong\u003eh\u003c/strong\u003e Schematic illustration of the waterproof and breathable mechanisms.\u003cstrong\u003ei\u003c/strong\u003e Air permeability of MRSD-PLA. \u003cstrong\u003ej\u003c/strong\u003eSchematic illustration of gasand vapor transport pathways in MRSD-PLA.\u003c/p\u003e","description":"","filename":"image3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/102c989f5e6cec2aca6e864f.jpeg"},{"id":99588287,"identity":"d812bad5-5b63-486a-a6e2-904c2d86b12d","added_by":"auto","created_at":"2026-01-06 08:12:03","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":2428455,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMechanisms of directed electron migration and charge redistribution in MRSD-PLA.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e Surface potential decay of MRSD-PLA over 90 days. \u003cstrong\u003eb\u003c/strong\u003e Relative dielectric constants of MRSD-PLA. \u003cstrong\u003ec\u003c/strong\u003e Correlation between surface potential and relative dielectric constants of MRSD-PLA. The inset shows the electrostatic adsorption assessment of MRSD-PLA6. \u003cstrong\u003ed\u003c/strong\u003e Surface electrostatic potential distribution of PLA molecular chains before and after polarization. \u003cstrong\u003ee\u003c/strong\u003e Schematic illustration of spatial charge modulation in nanofibers via HHIS Strategy. \u003cstrong\u003ef\u003c/strong\u003e Simulated potential distribution during the contact-separation cycle. \u003cstrong\u003eg\u003c/strong\u003e Schematic of electron trajectories across heterogeneous interfaces. Electrical output performance of MRSD-PLA, including (\u003cstrong\u003eh\u003c/strong\u003e) open-circuit voltage, (\u003cstrong\u003ei\u003c/strong\u003e) short-circuit current and (\u003cstrong\u003ej\u003c/strong\u003e) transferred charge. \u003cstrong\u003ek\u003c/strong\u003e Open-circuit voltage of MRSD-PLA6 under different humidity gradients. \u003cstrong\u003el\u003c/strong\u003e Output stability of open-circuit voltage in MRSD-PLA6 over 500 s cycling. (\u003cstrong\u003el\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e1\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e-l\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e) Open-circuit voltage fluctuations at different time intervals during cycling.\u003c/p\u003e","description":"","filename":"image4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/497a57a9665673fff74bde64.jpeg"},{"id":99792938,"identity":"5bf3b60c-e0bc-414b-9bbd-144f269d1ca1","added_by":"auto","created_at":"2026-01-08 13:28:54","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":1666795,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAir filtration performance and mechanisms of MRSD-PLA.\u003c/strong\u003e Plots of (\u003cstrong\u003ea\u003c/strong\u003e) PM\u003csub\u003e0.3\u003c/sub\u003e filtration efficiency, (\u003cstrong\u003eb\u003c/strong\u003e) pressure drop and (\u003cstrong\u003ec\u003c/strong\u003e) quality factor of MRSD-PLA at varying airflow rates. PM\u003csub\u003e2.5\u003c/sub\u003e filtration efficiency of MRSD-PLA6 (\u003cstrong\u003ed\u003c/strong\u003e) before and (\u003cstrong\u003ee\u003c/strong\u003e) after water washing. \u003cstrong\u003ef\u003c/strong\u003e Long-term stability of PM\u003csub\u003e2.5\u003c/sub\u003e filtration efficiency for MRSD-PLA6 after water washing. The inset shows SEM image after filtration. (\u003cstrong\u003eg\u003c/strong\u003e) PM filtration efficiency and (\u003cstrong\u003eh\u003c/strong\u003e) pressure drop of MRSD-PLA6 under high-humidity conditions. (\u003cstrong\u003ei\u003c/strong\u003e) Pore size distribution and (\u003cstrong\u003ej\u003c/strong\u003e) porosity of MRSD-PLA. \u003cstrong\u003ek\u003c/strong\u003e Schematic illustration of electrostatic interactions and the functional mechanism in MRSD-PLA. \u003cstrong\u003el\u003c/strong\u003e Schematic illustration of dynamic charge balance induced by heterogeneous interface structuring.\u003c/p\u003e","description":"","filename":"image5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/f3ae9be0e927f3db5ccc1342.jpeg"},{"id":99792972,"identity":"34a04642-0141-4a29-a58a-cac93adc318f","added_by":"auto","created_at":"2026-01-08 13:30:45","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":2431755,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAntibacterial mechanisms and compost degradation behavior of MRSD-PLA.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e Antibacterial performance of MRSD-PLA. Blank represents the control group. \u003cstrong\u003eb\u003c/strong\u003e Antibacterial efficiency of MRSD-PLA. \u003cstrong\u003ec\u003c/strong\u003eSchematic illustration of the multi-mechanism antibacterial activity of MRSD-PLA. \u003cstrong\u003ed\u003c/strong\u003e Molecular-level antibacterial mechanism of MRSD-PLA. \u003cstrong\u003ee\u003c/strong\u003eCompost degradation behavior of MRSD-PLA6 after soil burial.\u003c/p\u003e","description":"","filename":"image6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/633f43cc36fe3275463c3417.jpeg"},{"id":100356079,"identity":"5fe40627-9b11-4774-99d7-27e580c12295","added_by":"auto","created_at":"2026-01-16 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08:12:04","extension":"pptx","order_by":8,"title":"","display":"","copyAsset":false,"role":"supplement","size":71702543,"visible":true,"origin":"","legend":"Dataset 6","description":"","filename":"SourceData.pptx","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/7b81ebc07d94e4accbb25251.pptx"},{"id":99588299,"identity":"abd7fb3a-ea7c-4fec-bb04-edcd4261a93c","added_by":"auto","created_at":"2026-01-06 08:12:03","extension":"pdf","order_by":9,"title":"","display":"","copyAsset":false,"role":"supplement","size":3262730,"visible":true,"origin":"","legend":"\u003cp\u003eReporting summary\u003c/p\u003e","description":"","filename":"RSFLTM.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7509740/v1/bd5f0a167fa648adea6987c3.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Hierarchically heterogeneous interface structuring strategy for microenvironment-regulating and self-decontaminating biodegradable meta-membranes","fulltext":[{"header":"Introduction","content":"\u003cp\u003eMultifunctional personal protective equipment plays is critical in fields including healthcare, aerospace, and specialized operations\u003csup\u003e1,2\u003c/sup\u003e. However, conventional protective materials often fail to simultaneously deliver high protective performance, physiological comfort, and environmental sustainability. For instance, most high-efficiency protective materials depend on high-basis-weight nonwovens or dense coatings to provide barrier properties, but this severely restricts air permeability and moisture transport\u003csup\u003e3,4\u003c/sup\u003e. Similarly, electret materials exhibit charge decay under high-humidity conditions, resulting in a substantial loss of protection performance\u003csup\u003e5\u003c/sup\u003e. Furthermore, the large-scale disposal of single-use protective gear raises growing ecological concerns. Therefore, developing advanced intelligent protective materials that integrate multiple functionalities has become a critical research focus in materials science and engineering.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe stability of human microenvironmental parameters, such as moisture-thermal balance and cleanliness at the skin-textile surface, is critically linked to the wearing comfort, health safety, and functional efficacy of protective membranes\u003csup\u003e6,7\u003c/sup\u003e. Although dense structures can confer certain barrier properties against pollutants, they often severely restrict air permeability and moisture transport, thereby hindering the maintenance of a stable microenvironment\u003csup\u003e2,8\u003c/sup\u003e. Conversely, porous breathable materials often exhibit inherent surface hydrophilicity or low roughness, making them susceptible to liquid penetration and pollutant adhesion, and thus incapable of self-cleaning\u003csup\u003e9\u003c/sup\u003e. In this context, nanofiber membranes have emerged as a promising platform for simultaneous microenvironment regulation and hydrophobic self-cleaning, owing to their high specific surface area, tunable porous architecture, and facile surface modifiability. The interconnected porous networks of these membranes facilitate efficient moisture vapor and gas transport\u003csup\u003e10\u003c/sup\u003e. By precisely tailoring their porosity and pore size distribution, they can effectively accommodate human metabolic heat and moisture dissipation, thereby maintaining moisture-thermal balance at the skin surface. However, the inherent limitations of single-component nanofiber membranes still hinder their ability to meet the comprehensive requirements of complex application scenarios\u003csup\u003e11\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn recent years, nanofiber-based heterogeneous interface engineering has become a pivotal strategy for enhancing the performance of multifunctional nanocomposites. Using nanofibers as structural scaffolds, hierarchical heterogeneous interfaces with distinct component gradients, controllable microtopography, and tunable electronic structures can be constructed\u003csup\u003e12,13\u003c/sup\u003e. This is achieved by precisely regulating the interfacial interactions, geometric configurations, and chemical environments of heterogeneous components located within the fiber core, on the fiber surface, or between adjacent fibers, Such engineering offers insights into the structural design and functional optimization of advanced protective membranes\u003csup\u003e14,15\u003c/sup\u003e. For example, heterogeneous interfaces formed between metal-organic frameworks (MOFs) and polymers can utilize the high porosity of MOFs to facilitate molecular transport\u003csup\u003e16\u003c/sup\u003e, while also enabling charge storage through coordination interactions\u003csup\u003e17,18\u003c/sup\u003e. Similarly, interfaces between modified metal oxides and fibers enable functional integration through surface modification\u003csup\u003e19,20\u003c/sup\u003e. However, current research predominantly focuses on single-component or single-interface functional designs, lacking systematic strategies for constructing hierarchical heterogeneous structure. The absence of multiscale and hierarchically organized interface engineering leads to inefficient allocation of functionalities, such as microenvironment regulation, self-decontamination, and high-performance protection, across distinct interfacial levels\u003csup\u003e21,22\u003c/sup\u003e. Consequently, this results in inadequate functional synergy and limits their applicability in complex advanced protection scenarios.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn this work, we disclose a hierarchically heterogeneous interface structuring (HHIS) strategy to develop meta-membranes (MRSD-PLA) with microenvironment-regulating and self-decontamination capabilities, thereby overcoming the trade-off between structural integrity and functional performance in personal protective membranes.\u0026nbsp;It refers to a hierarchical structure with emergent functionality, achieved through the spatial organization and interfacial coupling between the two phases. Using biodegradable poly(lactic acid) (PLA) as the structural scaffold, this strategy involves embedding highly porous and electroactive zeolitic imidazolate framework-8 (ZIF-8) nanocrystals, which are composed of zinc ions coordinated with 2-methylimidazole ligands forming a robust microporous framework within the individual fibers. The ordered pore channels of ZIF-8 facilitate the directional transport of small molecules (e.g., water vapor and air), thereby effectively regulating temperature and humidity across the membrane. Simultaneously, low-surface-energy and photocatalytically active fluorinated titanium dioxide (F-TiO\u003csub\u003e2\u003c/sub\u003e) nanoblocks are anchored on the fiber surfaces. The fluorinated modification introduces hydrophobicity and strong electronegativity, which enable self-decontamination and create deep charge traps. By modulating the electronic structure at the heterogeneous interfaces between ZIF-8 and F-TiO\u003csub\u003e2\u003c/sub\u003e, this process induces directed electron migration and spatial charge redistribution, establishing a continuous \u0026ldquo;capture-storage-regeneration\u0026rdquo; charge cycling mechanism. This structure not only enhances the filtration efficiency of charged pollutants such as particulate matter (PM) and pathogens but also mitigates performance degradation under harsh conditions like high-humidity, thereby ensuring long-term stability in protection. This work provides a theoretical foundation and a technical paradigm for developing multifunctional integrated materials for multifunctional personal protection.\u0026nbsp;\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e\u003cstrong\u003eSynthesis of the MRSD-PLA\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eMultifunctional personal protective membranes used in medical surgical gowns and space suits need to rigorously balance high barrier performance, breathable comfort, and mechanical stability, while also integrating multifunctional properties to meet the complex demands of specialized environments\u003csup\u003e23\u003c/sup\u003e. Accordingly, we employ a hierarchically heterogeneous interface structuring (HHIS) strategy to fabricate microenvironment-regulating and self-decontaminating meta-membranes (MRSD-PLA). These membranes integrate multiple functionalities including isolation protection, moisture-wicking permeability, self-cleaning, and signal conversion, aiming to overcome the performance degradation commonly exhibited by traditional protective materials under complex environmental conditions. The core architecture of MRSD-PLA consisted of biodegradable PLA nanofibers serving as the structural scaffold. ZIF-8 nanocrystals with high porosity and electrochemical activity were embedded into individual PLA fibers via electrospinning. This ptocess formed ordered molecular transport channels that facilitate the directional diffusion of air and water vapor, thereby dynamically regulating the skin microenvironment (Fig. 1a). The abundant coordinatively unsaturated sites in ZIF-8 serve as efficient electron traps for charge capture and storage. Simultaneously, F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks with low surface energy and high electronegativity were anchored onto the fiber surface via electrospray, enabling hydrophobic self-cleaning and the formation of deep charge traps. Under external environmental disturbances, interfacial charges may undergo transient dissipation. However, the heterogeneous structure facilitates directional migration of stored charges from ZIF-8 toward the interface, thereby promptly replenishing depleted surface charges\u003csup\u003e24\u003c/sup\u003e. This process establishes a closed-loop \u0026ldquo;capture-storage-regeneration\u0026rdquo; cycle, enabling sustained and stable electrostatic forces. The hierarchically heterogeneous interface structurings effectively suppress performance degradation under extreme environments and significantly enhance the environmental adaptability and service reliability of the membranes.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe MRSD-PLA leverage their hierarchically interface structure to enable unidirectional transport of sweat vapor and metabolic heat to the external environment, while their hydrophobically functionalized surface effectively blocks the penetration of liquid contaminants (Fig. 1b). The selectively designed mass-thermal transmission channels within the membranes ensure microenvironmental stability at the skin-membrane interface without compromising their protective performance. Owing to the abundant charges stored in ZIF-8 nanocrystals and the deep charge traps created by F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks\u003csup\u003e25\u003c/sup\u003e, the membranes facilitate continuous electrostatic interception by remotely capturing pathogen-bearing aerosols and submicron particles via strong electrostatic interactions. Even under high-humidity conditions, the MRSD-PLA maintain high surface potential along wtih stable dynamic charge retention and regeneration capabilities, thereby substantially mitigating the impact of environmental humidity fluctuations on protective efficacy.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe inherent piezoelectric-triboelectric properties of the heterogeneous structured fibers enable real-time\u0026nbsp;responses to mechanical motions, converting these stimuli into quantifiable voltage, current, and charge signals\u0026nbsp;for\u0026nbsp;continuous monitoring of physiological status of the wearer\u003csup\u003e26\u003c/sup\u003e. Furthermore, through the structural integration of nanocrystal-mediated charge storage, a mechanically stable PLA scaffold, and photocatalytically active hydrophobic nanoblocks, MRSD-PLA achieve self-cleaning and antibacterial functionality while balancing mechanical strength during use with biodegradability after disposal. Based on the internal structural regulation and surface functional modification of nanofibers, we fabricated MRSD-PLA with hierarchically heterogeneous interface structures. These meta-membranes not only overcome the inherent trade-off between protective efficacy and wearing comfort but also provide a crucial theoretical framework and a technical paradigm for developing next-generation multifunctional integrated intelligent protective materials, advancing personal protective membranes toward intelligence, sustainability and adaptability to various scenarios.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe macroscopic properties of nanofiber membranes featuring heterogeneous interface structures are collectively determined by their microstructural morphology, chemical composition and crystalline configuration. Fiber diameter distribution and pore architecture collectively regulate the air permeability, moisture vapor transmission and purification performance of the membrane\u003csup\u003e27\u003c/sup\u003e. Composition dictates the physicochemical characteristics, whereas the crystal structure and heterogeneous interfaces dominate the mechanical stability and spatial charge redistribution. Elucidating these structure-property relationships offers critical insights into enhancing the regulation of human microenvironments and improving protection performance\u003csup\u003e28\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFigure 2 illustrates the microscopic morphology, chemical composition and interfacial characteristics of MRSD-PLA. ZIF-8 nanocrystals were synthesized via a thermodynamically driven coordination self-assembly process between zinc ions (Zn\u003csup\u003e2\u003c/sup\u003e⁺) and 2-methylimidazole ligands (Fig. 2a). Imidazole molecules bridge Zn\u003csup\u003e2\u003c/sup\u003e⁺ as structural nodes, forming a highly porous crystalline framework with well-defined channel networks. The short-chain organic linkers and precise metal\u0026ndash;ligand coordination geometry endow ZIF-8 with a high specific surface area suitable for gas adsorption, while facilitating efficient molecular transport pathways that enhance mass transfer kinetics. The abundant coordinatively unsaturated Zn\u003csup\u003e2\u003c/sup\u003e⁺ sites serve as effective electron traps, enabling\u0026nbsp;efficient charge capture and storage while establishing continuous charge conduction networks throughout the framework. Moreover, covalent grafting of fluorinated functional groups onto the TiO\u003csub\u003e2\u003c/sub\u003e surface significantly reduced surface energy, thereby enhancing hydrophobicity (Fig. 2b and Supplementary Fig. 1), and formed deep-level charge traps via its high electronegativity. This fluorination treatment selectively modifies the surface chemistry without compromising the bulk crystallinity of TiO\u003csub\u003e2\u003c/sub\u003e, allowing improvements of both wetting behavior and surface electronic properties.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eScanning electron microscopy (SEM) images revealed that ZIF-8 nanocrystals possess a well-defined rhombic dodecahedral morphology. They were closely packed through intercrystalline interactions, facilitating the formation of continuous gas transport channels and maximizing pore accessibility. F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks consisted of aggregated nanoparticles measuring 30\u0026minus;50 nm, and their disordered stacking created micro/nano-scale pores. Using the electrospinning-electrospray technique, we fabricated membranes with anchored F-TiO\u003csub\u003e2\u003c/sub\u003e at mass fractions of 0%, 2%, 4% and 6%, designated as P-PLA, MRSD-PLA2, MRSD-PLA4 and MRSD-PLA6, respectively, with ZIF-8 mass fractions of 25%, 22.2%, and 20% (Fig. 2c-f). The incorporation of ZIF-8 increased the conductivity of the spinning solution, which promoted sufficient stretching of the polymer chains under the electric field and resulted in fiber refinement (Supplementary Figs. 2, 3). Control experiments conducted on the PLA@ZIF-8 membrane (without F-TiO\u003csub\u003e2\u003c/sub\u003e) revealed that the embedded ZIF-8 nanocrystals primarily contributed to the enhanced charge storage and water vapor transmission rate (WVTR), while the synergistic combination with surface-anchored F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks was crucial for achieving superior hydrophobicity, the highest surface potential, and optimal filtration efficiency through the formation of hierarchical heterogeneous interfaces. These slit-like pore structures enhance gas flux and mass transfer efficiency, thereby improving the air purification performance. Notably, ZIF-8 nanocrystals formed bead-on-string configurations within the fibers, whereas the anchored F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks created nanoscale protrusions, pores and surface textures via stacking and aggregation. These components cooperatively constructed hierarchical heterogeneous interfaces both on and within individual fibers. Elemental mapping confirmed the uniform spatial distribution of characteristic elements including carbon (C), nitrogen (N), zinc (Zn) and fluorine (F) (Supplementary Fig. 4a). The mass fractions of F-TiO\u003csub\u003e2\u003c/sub\u003e in the composite membranes were verified by thermogravimetric analysis (TGA), which confirmed that the measured values were in good agreement with the nominal loadings, thereby affirming the reliability of the electrospray process (Supplementary Fig. 4b).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe Fourier-transform infrared (FTIR) spectra in Figure 2g-j reveal the characteristic functional groups of MRSD-PLA. P-PLA exhibited a C=O stretching vibration peak at 1750 cm⁻\u003csup\u003e1\u003c/sup\u003e, along with characteristic C\u0026minus;O absorption peaks at 1180 cm⁻\u003csup\u003e1\u003c/sup\u003e and 1080 cm⁻\u003csup\u003e1\u003c/sup\u003e. Following the incorporation of ZIF-8 and F-TiO\u003csub\u003e2\u003c/sub\u003e, MRSD-PLA spectra exhibited asymmetric stretching vibrations of aromatic and aliphatic C\u0026minus;H bonds from the imidazole ring at 3135 cm⁻\u003csup\u003e1\u003c/sup\u003e and 2928 cm⁻\u003csup\u003e1\u003c/sup\u003e, respectively. The absorption peak at 1480 cm⁻\u003csup\u003e1\u003c/sup\u003e corresponded to C=N stretching in the imidazole ring, while the peak at 1383 cm⁻\u003csup\u003e1\u003c/sup\u003e was attributed to the stretching vibrations of interfacial \u0026minus;CH\u003csub\u003e3\u003c/sub\u003e and O\u0026minus;O groups. The introduction. of nanoparticles renders the electron cloud distribution in PLA chains more uniform, reduces the force constant of chemical bonds, and consequently causes a red shift in absorption peaks. The X-ray diffraction (XRD) analysis was employed not only to verify the successful incorporation of ZIF-8 nanocrystals within the PLA matrix but also to elucidate their role as nucleating agents that modulate the crystallization behaviour of PLA, which is crucial for understanding the enhanced mechanical and charge-storage properties of the composite membranes (Fig. 2k). Specifically, P-PLA displayed a broad, weak diffraction peak, indicating low crystallinity that is typical of processed PLA. In contrast, MRSD-PLA exhibited sharp, strong diffraction peaks at 7.3\u0026deg;, 10.5\u0026deg; and 12.8\u0026deg;, corresponding to the (011), (002) and (112) crystal planes of ZIF-8 nanocrystals\u003csup\u003e29\u003c/sup\u003e. Moreover, the increased intensity and sharpness of these peaks with higher ZIF-8 loading indicate that ZIF-8 acts as a nucleating agent, promoting the crystallization of PLA. This insight is critical for understanding the enhanced mechanical and charge-storage properties of the composite membranes\u003csup\u003e30\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe nitrogen adsorption-desorption isotherms indicated that the specific surface areas of MRSD-PLA2, MRSD-PLA4, and MRSD-PLA6 were 168, 185, and 209 m\u003csup\u003e2\u003c/sup\u003e\u0026middot;g⁻\u003csup\u003e1\u003c/sup\u003e (Fig. 2l), which was significantly higher than that of the P-PLA membrane (18 m\u003csup\u003e2\u003c/sup\u003e\u0026middot;g⁻\u003csup\u003e1\u003c/sup\u003e). This substantial increase originates from the synergistic contribution of the embedded ZIF-8 nanocrystals, which introduce intrinsic micropores, and the nanoscale surface roughness created by the anchored F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks. We speculate that the micropores originate from ZIF-8 nanocrystals, the mesopores from inter-nanoblock spaces and fiber surface textures, and the macropores from the inter-fiber voids. This multiscale porous network is directly responsible for the enhanced gas adsorption capacity and provides abundant pathways for efficient vapor and gas transport. The mechanical performance of MRSD-PLA under tensile loading is shown in Figure 2m and 2n. Compared with P-PLA, MRSD-PLA demonstrated higher tensile strength and elastic modulus. ZIF-8 nanocrystals act as reinforcing fillers that suppress crack propagation, F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks enhance interfacial adhesion through the formation of heterogeneous structures, and PLA nanofibers provide a continuous matrix for structural support. The combined effect of these components enables MRSD-PLA to withstand greater external stresses before deformation or fracture, thereby significantly improving its mechanical properties\u003csup\u003e31\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eHeterogeneous composite fiber membranes with multilevel roughness were constructed by embedding ZIF-8 nanocrystals within individual nanofibers while anchoring low-surface-energy F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks on the surface to create protrusions and fine textures. The hydrophobically modified heterogeneous fiber surface traps air within grooves and pores. This causes water droplets to primarily contact the entrapped air and rough protrusions, thereby significantly reducing the actual solid-liquid contact area\u003csup\u003e32\u003c/sup\u003e.\u0026nbsp;By leveraging HHIS strategy, the water contact angle (WCA) of MRSD-PLA6 increased to 137.4\u0026deg; (Fig. 3a), which is significantly higher than that of P-PLA.\u0026nbsp;MRSD-PLA form interconnected microscale and nanoscale pores through random fiber stacking, enabling gas permeation via mass transfer driven by molecular thermal motion and concentration gradients (Fig. 3b).\u0026nbsp;The micro-nano protrusions formed by low-surface-energy F-TiO\u003csub\u003e2\u003c/sub\u003e yield a high WCA and suppress water spreading and penetration. This prevents water from clogging the fiber interstices or ZIF-8 micropores, thereby ensuring efficient transport of gases and water vapor. Meanwhile, these heterogeneous interfaces significantly increase the specific surface area, providing more active sites for adsorption and diffusion processes while promoting the evaporation and diffusion of water molecules at the fiber surfaces\u003csup\u003e33\u003c/sup\u003e. This structure helps to avoid moisture accumulation and heat retention at the interface, thereby enhancing the overall moisture permeability.\u0026nbsp;Water vapor permeability tests showed that the hierarchical pore structure of MRSD-PLA6 enables water vapor to undergo Fickian diffusion driven by concentration gradients, achieving\u0026nbsp;coupled\u0026nbsp;transport of water vapor and heat\u003csup\u003e34\u003c/sup\u003e. Owing to the concerted regulation of chemical composition and microstructure, condensed water droplets can remain suspended on the surface for extended periods without penetration, demonstrating excellent water resistance and air permeability (Fig. 3c).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMicroenvironment regulation\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe MRSD-PLA6 maintained a high WCA over extended periods, demonstrating superior wetting resistance and stability against time-dependent wetting degradation (Fig. 3d). Furthermore, the differential hydrophobicity design reduces liquid water\u0026nbsp;retention on the membrane surface, facilitating easy removal with minimal residue. The low surface energy of F-TiO\u003csub\u003e2\u003c/sub\u003e, combined with the inherent hydrophobicity of the nanofibers, generates a high interfacial energy barrier that significantly enhances liquid repellency. This performance surpasses that of conventional hydrophobic materials, which are often prone to aging.\u0026nbsp;These anti-wetting characteristics enable MRSD-PLA to consistently repel various liquids (including water and bodily fluids), thereby providing a reliable barrier for personal protective equipment (Fig. 3e and Supplementary Fig. 5).\u0026nbsp;The self-cleaning mechanism arises because the adhesion force between particles and the hydrophobic surface of MRSD-PLA6 is weaker than the cohesive force within water droplets (Fig. 3f).\u0026nbsp;Consequently, rolling water droplets can carry and remove surface contaminants. This process is governed by the interplay between surface wettability regulation and heterogeneous interface structuring, which promotes rapid contaminant detachment from the fiber surfaces\u003csup\u003e2\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe macroscopic properties of nanofiber membranes including air permeability, moisture vapor transmission and mechanical performance, directly influence the comfort, durability, and application scope of textile-integrated products.\u0026nbsp;The MRSD-PLA6 exhibited a WVTR value of 4018 g\u0026middot;m⁻\u003csup\u003e2\u003c/sup\u003e\u0026middot;d⁻\u003csup\u003e1\u003c/sup\u003e, significantly surpassing that of most commercial protective materials (Fig. 3g).\u0026nbsp;It should be noted that the reported WVTR value of 4018 g\u0026middot;m⁻\u003csup\u003e2\u003c/sup\u003e\u0026middot;d⁻\u003csup\u003e1\u003c/sup\u003e was obtained under controlled conditions (25\u0026deg;C, 90% RH) using the standard cup method. This value exceeds the commonly referenced threshold of 2000 g\u0026middot;m⁻\u003csup\u003e2\u003c/sup\u003e\u0026middot;d⁻\u003csup\u003e1\u003c/sup\u003e, which is derived from protective clothing standards under similar testing environments, ensuring adequate moisture dissipation during perspiration.\u0026nbsp;The incorporation of ZIF-8 and F-TiO\u003csub\u003e2\u003c/sub\u003e not only avoids increasing resistance to water vapor transmission but also facilitates the development of heterogeneous structured fibers with optimized pore morphology and surface characteristics, thereby enhancing water vapor diffusion efficiency (Fig. 3h). Air permeability, a key indicator for evaluating energy exchange and cellular metabolic environments, is critical for reducing the risks of skin inflammation and thermal stress\u003csup\u003e35\u003c/sup\u003e. MRSD-PLA demonstrated efficient gas transport owing to their high specific surface area, high porosity and interconnected networks, achieving air permeability values above 60 mm\u0026middot;s⁻\u003csup\u003e1\u003c/sup\u003e. In contrast, P-PLA exhibited an air permeability of only 46.8 mm\u0026middot;s⁻\u003csup\u003e1\u003c/sup\u003e due to its dense structure and limited porosity (Fig. 3i). The highly porous structure of ZIF-8 and the resulting heterogeneous interfaces provide abundant nanoscale transport pathways for gases and vapor, including diffusion along fiber surfaces and heterogeneous boundaries, through intrinsic ZIF-8 channels, and through interparticle spaces among F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks (Fig. 3j and Supplementary Fig. 6).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eElectroactive sensing\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe electroactivity of the heterogeneous structured nanofiber membranes, fabricated via HHIS strategy, originates from a persistent electrostatic field induced at the surface through dielectric polarization.\u0026nbsp;The surface potential of MRSD-PLA6 reached 5.8 kV, representing a 75.7% increase compared to P-PLA (Fig. 4a). Crucially, the low surface energy and hierarchically rough structure of MRSD-PLA6 effectively suppresse carrier migration and markedly mitigate charge dissipation caused by environmental factors\u003csup\u003e36\u003c/sup\u003e, enabling the membrane to maintain high potential stability for over 90 days. In contrast, P-PLA exhibited significant charge decay due to water infiltration-induced ion conduction and dipole relaxation.\u0026nbsp;The surface-enriched highly electronegative fluorine-containing functional groups in MRSD-PLA attract and localize interfacial carriers, restricting their free migration and further enhancing interfacial dielectric properties through the formation of a stable polarized interface. Consequently, MRSD-PLA achieve a high relative dielectric constant and energy storage density while maintaining low dielectric loss. At a frequency of 10\u003csup\u003e3\u003c/sup\u003e Hz, the relative dielectric constant of MRSD-PLA6 reached 1.72, which is 1.24 times that of P-PLA (Fig. 4b). The observed deviations of some data points from the fitting curve are attributed to the inherent heterogeneity in the distribution of charge traps and interfacial polarization across the hierarchically structured composite fibers (Fig. 4c). Electrostatic adsorption experiments further demonstrated that the enhanced electrostatic interactions overcame the kinetic barriers of particles in airflow, endowing MRSD-PLA6 with efficient capture of fine particles (inset of Fig. 4c).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eDuring high-voltage electrospinning, external electric fields drive the rearrangement of PLA molecular chains, inducing the aligned orientation of dipoles. This alignment enhances the overall dipole moment of the material (Fig. 4d).\u0026nbsp;The electroactive ZIF-8 nanocrystals embedded within the PLA fibers adsorb and stabilize free charges through coordination bond polarization and \u0026pi;-electron delocalization. This mechanism effectively suppresses charge dissipation in the nonpolar PLA.\u0026nbsp;Simultaneously, the high electronegativity of F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks enhances their ability to confine surface charges through interfacial dipole-dipole interactions, thereby reducing environmental charge dissipation. Owing to differences in their energy band structures, two types of heterogeneous interfaces which are formed between ZIF-8 and PLA, and between F-TiO\u003csub\u003e2\u003c/sub\u003e and the PLA surface, generate charge traps at these interfaces\u003csup\u003e37\u003c/sup\u003e. These traps capture free charges generated during triboelectric or polarization processes, significantly extending the charge lifetime and thereby increasing the surface electrostatic accumulation (Fig. 4e). The stabilization of internal charges, combined with external charge confinement and cooperative dipole alignment, collectively enhances the surface activity of MRSD-PLA. This combination establishes a solid foundation for its exceptional electrostatic performance in applications such as air purification.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe heterogeneous structured fibers in MRSD-PLA form localized charge-transfer channels that significantly enhance the conversion\u0026nbsp;efficiency of mechanical energy to electrical energy by facilitating\u0026nbsp;interfacial charge separation and migration.\u0026nbsp;COMSOL simulations reveal the fundamental triboelectrification mechanism: during contact-separation cycles, enhanced surface polarization and charge storage capacity drive the accumulation of opposite charges at the interfaces\u003csup\u003e19,38\u003c/sup\u003e. Subsequent charge release during separation generates a significant electrical potential (Fig. 4f).\u0026nbsp;The surface roughness created by F-TiO\u003csub\u003e2\u003c/sub\u003e on the fiber surfaces increases the contact area for friction, while the substantial electronegativity difference further enhances charge separation efficiency. Simultaneously, the electroactivity of ZIF-8 facilitates charge transfer through polarization effects, increasing the charge generated per triboelectric event. Furthermore, favorable energy band alignment at the heterogeneous interfaces reduces the energy barrier for interfacial charge transfer, thereby accelerating the directional transmission of triboelectric signals (Fig. 4g).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe triboelectric output was measured in a contact-separation mode between the meta-membranes and an external counter electrode (Supplementary Fig. 7). The electrical output performance of MRSD-PLA with different F-TiO\u003csub\u003e2\u003c/sub\u003e loadings is shown in Figure 4h-j. Specifically, MRSD-PLA6 exhibited an open-circuit voltage of 22.3 V, a short-circuit current of 67.5 nA and a transferred charge of 8.2 nC, representing improvements of 248%, 224%, and 925%, respectively, compared to P-PLA. Charges accumulate predominantly at the interface between the nanomaterials and PLA fibers, where these heterogeneous interfaces serve as efficient sites for charge separation\u003csup\u003e39\u003c/sup\u003e.\u0026nbsp;The well-matched energy levels between ZIF-8 and F-TiO\u003csub\u003e2\u003c/sub\u003e generate electric fields at the interfaces, which facilitate the separation of tribologically induced charges and suppress electron recombination. Thus, the complementary roles of F-TiO\u003csub\u003e2\u003c/sub\u003e in charge separation and ZIF-8 in charge storage and transfer synergistically enhanced the triboelectric output performance\u003csup\u003e40\u003c/sup\u003e.\u0026nbsp;Even under high-humidity conditions, the micro-nano rough structures on the heterogeneous structured fiber surface trap air, forming a barrier that prevents direct contact between water molecules and charge storage sites. This mechanism maintains stable charge transfer during contact electrification and electrostatic induction.\u0026nbsp;MRSD-PLA6 exhibited only 10.3% voltage attenuation under gradient humidity conditions (Fig. 4k), effectively avoiding the charge neutralization and performance degradation commonly observed in P-PLA.\u0026nbsp;The spatial charge redistribution induced by heterogeneous interfaces drives directional electron migration, enabling continuous conversion of mechanical energy to electrical energy over repeated cycles\u003csup\u003e41\u003c/sup\u003e. MRSD-PLA6 maintained a stable voltage output over 500 seconds of continuous operation (Fig. 4l), demonstrating enormous potential for long-term energy storage, signal transmission and real-time physiological monitoring.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAir purification\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eEfficient filtration of aerosols, droplet nuclei and pathogen-laden particles ranging from 0.3 to 5 \u0026mu;m in size is critical for constructing high-performance bidirectional protective systems\u003csup\u003e42\u003c/sup\u003e.\u0026nbsp;Medical surgical gowns provide effective\u0026nbsp;barriers against tissue debris, bodily fluid aerosols and environmental pathogenic microorganisms generated during surgical procedures.\u0026nbsp;Furthermore, PM can infiltrate the precision components of spacesuits, directly disrupting critical life support systems including oxygen supply and temperature regulation.\u0026nbsp;Capitalizing on the excellent surface electroactivity, water resistance and air permeability of MRSD-PLA, we systematically evaluated their air purification performance under various operating conditions.\u0026nbsp;MRSD-PLA with heterogeneous interface structures exhibited high filtration efficiency for the most penetrating PM\u003csub\u003e0.3\u003c/sub\u003e across varying flow rates (Fig. 5a, b). At a flow rate of 10 L\u0026middot;min⁻\u003csup\u003e1\u003c/sup\u003e, MRSD-PLA maintained a PM\u003csub\u003e0.3\u003c/sub\u003e filtration efficiency exceeding 99.1% with a pressure drop of only 51.9 Pa, demonstrating high purification efficiency and low energy consumption even at elevated flow rates. When the flow rate increased to 85 L\u0026middot;min⁻\u003csup\u003e1\u003c/sup\u003e, P-PLA showed a significant decrease in filtration efficiency to 71.3%, accompanied by a pressure drop exceeding 400 Pa. In contrast, MRSD-PLA exhibited only a slight decrease in efficiency and a limited increase in flow resistance (Supplementary Figs. 8, 9).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAs the flow rate increases, the two membranes exhibit markedly distinct performance trends, fundamentally attributable to the combined contribution of enhanced structural stability, charge retention and mass transfer efficiency in MRSD-PLA, achieved through the embedding of ZIF-8 nanocrystals and surface anchoring of F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks. For P-PLA, elevated flow rates generate an aerodynamic drag force on PM that exceeds its limited electrostatic adsorption capacity, leading to the penetration of submicron particles through the membrane\u003csup\u003e43\u003c/sup\u003e. Concurrently, its relatively weak fiber network undergoes compaction under high-velocity airflow, reducing the effective porosity and contracting the pore size, thereby significantly increasing air resistance. In contrast, ZIF-8 nanocrystals embedded within the fibers introduce abundant nanopores and a high specific surface area. These features enhance physical interception mechanisms including size exclusion and surface adsorption, while also providing stable charge storage sites, thereby maintaining superior electrostatic capture performance (Supplementary Fig. 10).\u0026nbsp;The surface-anchored F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks leverage their high electronegativity and crystalline-amorphous heterogeneous interfaces to form deep charge traps on the fiber surfaces. These traps sustain a robust electrostatic field through continuous charge collection and storage, enabling effective capture of \u0026nbsp;PM. Furthermore, the multiscale structural modulation of both the fiber interior and surface significantly enhances the mechanical strength of the nanofiber membranes. This enhancement enables the membranes to resist deformation under high flow rates, maintain an interconnected porous structure, and effectively suppress pressure drop increase. The hierarchically heterogeneous structure endows MRSD-PLA with dual advantages: high-efficiency particulate matter capture and low pressure loss at high flow rates, achieved through electrostatic enhancement and physical capture mechanisms. This structural superiority was further confirmed by higher quality factor (\u003cem\u003eQF\u003c/em\u003e) values (Fig. 5c).\u0026nbsp;Notably, the MRSD-PLA6 membrane demonstrates a more favourable combination of high filtration efficiency and lower pressure drop compared to conventional high-efficiency filtration media such as N95 melt-blown layers and fiberglass filters (Supplementary Table 1).\u003c/p\u003e\n\u003cp\u003eWe fabricated nanofiber membranes with heterogeneous interface structures via HHIS strategy and modulated their surface wettability to systematically evaluate the effect of water washing on PM filtration efficiency. Before washing, MRSD-PLA6 maintained 95% filtration efficiency for PM\u003csub\u003e2.5\u003c/sub\u003e at 85 L\u0026middot;min⁻\u003csup\u003e1\u003c/sup\u003e through combined physical interception (e.g., inertial impaction and Brownian diffusion) and electrostatic adsorption (deep charge traps and heterogeneous interfaces), whereas P-PLA, lacking such structural design, exhibited only 88.2% efficiency (Fig. 5d). After 30 minutes of immersion in water and subsequent drying, the PM\u003csub\u003e2.5\u003c/sub\u003e filtration efficiency of P-PLA decreased to 65.4%, whereas that of MRSD-PLA6 decreased from 98.6% to 89.1% (Fig. 5e). Furthermore, the F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks remain stable owing to strong interfacial adhesion, demonstrating excellent structural robustness, environmental tolerance and reusability without observable detachment, as confirmed by SEM imaging after regeneration and washing cycles (Supplementary Fig. 11). More importantly, owing to its stable charge storage and structural recovery mechanisms, MRSD-PLA6 maintained highly efficient and stable PM\u003csub\u003e2.5\u003c/sub\u003e filtration over extended periods (Fig. 5f). The performance stability can be explained by three mechanisms: (1) Strong hydrophobic groups reconfigure the hydration ion coordination structure at the solid-liquid interface, inhibiting charge dissipation induced by water ionization and thereby enhancing charge retention from an interfacial chemistry perspective; (2) Although interfacial charge undergoes transient dissipation under external disturbances, the heterojunction electric field drives migration of stored charges from ZIF-8 to the interface, promptly compensating for surface charge loss and establishing a \u0026ldquo;capture-storage-regeneration\u0026rdquo; cycle that enables self-sustaining electric fields\u003csup\u003e7,44\u003c/sup\u003e; (3) The sustained charge migration from ZIF-8 to the interfaces establishes a closed-loop capture-storage-regeneration cycle, which is supported by the exceptional stability of surface potential, filtration efficiency under high humidity, and triboelectric output (Supplementary Figs. 12, 13).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eUnder high-humidity conditions, filtration efficiency is a critical indicator for evaluating the charge stability, structural integrity and operational reliability of protective membranes. After 10 minutes of testing at 90% RH, the PM\u003csub\u003e2.5\u003c/sub\u003e filtration efficiency of P-PLA decreased from 89.5% to 76.4%, whereas that of MRSD-PLA6 declined from 98.4% to 89.5% (Fig. 5g). Concurrently, the pressure drop of P-PLA increased to 632 Pa, while that of MRSD-PLA6 increased to only 222 Pa (Fig. 5h). Notably, the fluorinated interface constructed by surface-anchored F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks suppresses water molecule-mediated charge shielding through three synergistic effects: forming a hydrophobic physical barrier to reduce direct water-membrane contact, modulating the interfacial hydration structure to inhibit ion conduction-induced charge dissipation, and synergizing with heterogeneous interfacial charge traps to enhance charge confinement, which collectively ensure the stable surface potential and filtration performance of MRSD-PLA6 under high-humidity conditions. The exceptional water vapor permeability of MRSD-PLA can be further elucidated by considering the Knudsen and surface diffusion mechanisms within its hierarchical pore network. The pore size distribution indicated a substantial fraction of mesopores (2-50 nm) (Fig. 5i). Given that the mean free path of water vapor (~110 nm) is comparable to or larger than these pore diameters, Knudsen diffusion, where molecule-wall collisions dominate, becomes a significant contributor to the overall mass transfer. Concurrently, the high specific surface area, predominantly provided by the microporous ZIF-8, facilitates the adsorption and subsequent surface diffusion of water molecules (Fig. 5j). This mechanism involves the hopping of adsorbed molecules along the pore walls under a concentration gradient. Thus, the concerted action of Knudsen diffusion through the pore volume and surface diffusion along the extensive internal surface area creates highly efficient pathways for water vapor transport, which is of paramount importance for effective microenvironment regulation.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eUnder challenging conditions, ZIF-8 nanocrystals within the heterogeneous structured fibers stabilize free charges through their electroactivity, while F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks confine surface charges via interfacial dipole effects due to their strong electronegativity. The heterogeneous interfaces create charge traps through band alignment differences, collectively establishing a persistent electrostatic field that actively captures submicron and nanoparticles. Meanwhile, the microporous structure of ZIF-8 forms nanoscale capture channels within the fibers, and F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks create micro-nano rough structures on the fiber surfaces. Together, they form a multilevel physical capture network that integrates interception, inertial impaction and diffusion mechanisms, enabling efficient filtration of particles across different size ranges. As discrete embeddings within PLA fibers, ZIF-8 nanocrystals avoid clogging internal micropores and inter-fiber macropores while facilitating continuous airflow pathways, thereby reducing bypass losses. The low surface energy of F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks inhibits pore adhesion caused by water molecule adsorption, while their surface micro-nano structure induces an air slip effect that reduces viscous resistance at the airflow-fiber interface\u003csup\u003e45\u003c/sup\u003e. This synergy produces filtration performance and stability that surpass what can be achieved by systems based on either mechanism individually (Fig. 5k, l).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSelf-decontamination and biodegradability\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe warm and humid microenvironment that forms on the skin surface during prolonged outdoor activity promotes bacterial proliferation\u003csup\u003e46\u003c/sup\u003e.\u0026nbsp;Microorganisms can metabolize nutrients in sweat to proliferate rapidly, disrupting the physiological barrier of the skin and potentially inducing inflammation or even local infection.\u0026nbsp;This highlights the urgent need for materials capable of microenvironment regulation and active self-decontamination. The antibacterial properties of MRSD-PLA against Escherichia coli (\u003cem\u003eE. coli\u003c/em\u003e) and Staphylococcus aureus (\u003cem\u003eS. aureus\u003c/em\u003e) were evaluated using the plate counting method (Fig. 6a).\u0026nbsp;It is worth noting that the P-PLA membrane exhibited a minor reduction in bacterial viability, which may be attributed to the inherent low surface energy of PLA.\u0026nbsp;MRSD-PLA exhibited high inactivation efficiency against both bacterial strains, and their antibacterial performance improved notably with increasing F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks content. Specifically, MRSD-PLA6 demonstrated a bacterial inhibition rate of 90.3%, which was significantly higher than that of P-PLA (Fig. 6b).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThrough micro-nano structural characterization and molecular-level analysis, the multi-mechanism antibacterial activity of MRSD-PLA with heterogeneous interface structures was further elucidated (Fig. 6c).\u0026nbsp;The Zn\u003csup\u003e2\u003c/sup\u003e⁺ coordination sites in ZIF-8 and surface hydroxyl groups on F-TiO\u003csub\u003e2\u003c/sub\u003e act synergistically to enhance reactions between photogenerated charge carriers and adsorbed O\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO molecules on the material surface\u003csup\u003e47\u003c/sup\u003e. This leads to the generation of highly oxidative free radicals, primarily reactive oxygen species (ROS).\u0026nbsp;The generated ROS penetrate bacterial cell membranes, degrade nucleic acids and proteins, disrupt cellular integrity, and ultimately cause metabolic dysfunction leading to bacterial death.\u0026nbsp;Furthermore, the strong electrostatic attraction generated at the heterogeneous interface of the material firmly adsorbs bacteria onto the fiber surfaces, prolonging their exposure to ROS and thereby enhancing bactericidal efficacy\u003csup\u003e48\u003c/sup\u003e.\u0026nbsp;Simultaneously, electrostatic interactions can disrupt the\u0026nbsp;electrochemical potential balance across bacteria membranes, inhibit nutrient active transport and key metabolic enzyme activities, thereby effectively hindering bacterial proliferation (Fig. 6d).\u0026nbsp;The constructed heterogeneous interface not only expands the light absorption range but also enhances electrostatic field stability\u003csup\u003e49\u003c/sup\u003e. Electrostatic adsorption acts to prolong bacterial residence time on the fiber surface, thereby synergistically enhancing the efficacy of the photocatalytic ROS generation.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe widespread use of personal protective equipment, such as surgical gowns and isolation suits, has intensified waste management challenges and environmental burdens.\u0026nbsp;Biodegradable materials can be progressively broken down by microorganisms in natural environments such as soil and compost, ultimately mineralizing into carbon dioxide and water (Supplementary Fig. 14).\u0026nbsp;To assess the degradation behavior of membranes with heterogeneous interface structures, P-PLA and MRSD-PLA6 were subjected to burial experiments in moist soil at 40 \u0026deg;C. This environment simulated naturally warm, humid conditions to accelerate polymer chains scission through enhanced microbial metabolism and enzymatic catalysis\u003csup\u003e14,50\u003c/sup\u003e.\u0026nbsp;After 84 days of burial, both P-PLA and MRSD-PLA6 underwent significant degradation and lost their structural integrity (Fig. 6e).\u0026nbsp;The menbranes exhibited considerable degradation processes, providing direct experimental evidence for assessing the environmental lifecycle of such biodegradable protective materials and for regulating their degradation behavior via HHIS strategy.\u0026nbsp;SEM images revealed abundant colonization by microorganisms capable of secreting PLA-degrading enzymes on the surfaces of both P-PLA and MRSD-PLA6 (Supplementary Fig. 15). Enzymatic hydrolysis cleaves the PLA molecular chains into small, environmentally benign molecules\u003csup\u003e51\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn vitro biodegradation kinetics showed that the membranes exhibited significant fiber fracture and embrittlement within 14 days, followed by extensive structural disintegration by day 28, and further fragmentation into millimeter-scale debris between days 42 and 56 (Supplementary Fig. 16). The quantitative degradation analysis confirmed the biodegradability of MRSD-PLA, showing a mass loss exceeding 75% over 84 days.\u0026nbsp;Although the interfacial modifications in MRSD-PLA6 partially suppressed initial microbial attachment, the inherent biodegradability of the PLA ultimately dominated the degradation process under prolonged environmental stress.\u0026nbsp;The HHIS strategy enables dual regulation of material performance and degradability: During service life, the heterogeneous interfaces formed by ZIF-8 and F-TiO\u003csub\u003e2\u003c/sub\u003e synergistically maintains mechanical properties and functional stability of the material. After disposal, the material undergoes orderly degradation through microbial enzymatic hydrolysis, achieving functional integration from efficient protection to minimal environmental impact\u003csup\u003e52\u003c/sup\u003e\u003csup\u003e,53\u003c/sup\u003e. This strategy provides a sustainable solution for the structural design and functional customization of disposable medical protective equipment.\u0026nbsp;\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn summary, we fabricate meta-membranes (MRSD-PLA) that integrate adaptive microenvironment-regulating and self-decontaminating capabilities via a hierarchical heterogeneous interface structuring strategy. The embedding of highly electroactive, porous ZIF-8 nanocrystals within the fibers creates efficient molecular transport pathways. Consequently, the MRSD-PLA exhibit high moisture permeability (4018 g\u0026middot;m⁻\u003csup\u003e2\u003c/sup\u003e\u0026middot;d⁻\u003csup\u003e1\u003c/sup\u003e) and air breathability (\u0026gt;60 mm\u0026middot;s⁻\u003csup\u003e1\u003c/sup\u003e), facilitating rapid\u0026nbsp;sweat and heat dissipation for real-time microenvironment regulation. Meanwhile, surface-anchored F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks, characterized by low surface energy and high electronegativity, enable self-decontamination through combined hydrophobicity and photocatalytic activity. The synergistic effect between the internally embedded and surface modification constructs heterogeneous fiber interface. This architecture generates micro-nano roughness and deep charge traps, which promote directional electron transfer and spatial charge redistribution. Consequently, performance degradation under fluctuating environmental conditions is effectively mitigated. Even under high-humidity conditions, MRSD-PLA maintain a stable surface potential, reliable electrical signal transmission and high PM filtration efficiency. The hierarchical heterogeneous structures synergistically inhibit bacterial proliferation through multiple mechanisms, while also balancing mechanical strength during use with biodegradability post-disposal. This work establishes a paradigm for the rational design of next-generation, high-performance personal protective membranes.\u0026nbsp;\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cstrong\u003eMaterials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePoly(lactic acid) (PLA) with a molecular weight of 1.63 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e g\u0026middot;mol⁻\u003csup\u003e1\u003c/sup\u003e was procured from Total Corbion PLA Co., Ltd., Thailand. Non-woven cellulose fabrics (60 g\u0026middot;m⁻\u003csup\u003e2\u003c/sup\u003e) was bought by Sateri Fiber Co. Ltd., China. N, N-dimethylformamide (DMF, purity \u0026gt; 98.0%) and dichloromethane (DCM, purity \u0026gt; 98.0%) were supplied by Sinopharm Chemical Reagent Co., Ltd. (China). Zinc acetate dihydrate (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eZn), 2-methylimidazole, titanium(IV) isopropoxide (TTIP), isopropyl alcohol (IPA), ethanol (EtOH), and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) were obtained from Macklin Biochemical Co., Ltd.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of ZIF-8 nanocrystals\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eZinc acetate dihydrate (0.55 g) and 2-methylimidazole (4.1 g) were separately dissolved in deionized water (60 mL). The resulting mixture was transferred to a microwave reactor and heated at 140 \u0026deg;C for 10 minutes. The product was collected by centrifugation and vacuum-dried at 80 \u0026deg;C for 12 h to remove solvent, yielding ZIF-8 nanocrystals with high electroactivity and porosity.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA mixture of 10 mL TTIP and 40 mL IPA was vigorously stirred and then added dropwise to a 1:1 (v/v) solution of deionized water and IPA to initiate hydrolysis.. The resulting mixture was transferred to a microwave reactor and heated at 180 \u0026deg;C for 1 h. The product was collected by centrifugation, vacuum-dried and then calcined in a tube furnace at 500 \u0026deg;C for 1 h to obtain anatase-phase titanium dioxide (TiO\u003csub\u003e2\u003c/sub\u003e). Subsequently, the TiO\u003csub\u003e2\u003c/sub\u003e (2.0 g) was dispersed into a mixture containing (5.0 g) and ethanol (45.0 g) for surface fluorination. This treatment yielded fluorinated TiO\u003csub\u003e2\u003c/sub\u003e (F-TiO\u003csub\u003e2\u003c/sub\u003e) nanoblocks with low surface energy and high electronegativity.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePreparation of P-PLA nanofiber membranes\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePLA granules (1.0 g) were dissolved in a mixed solvent of DMF and DCM (3:7, v/v) under continuous stirring for 12 h to form a homogeneous electrospinning solution. Electrospinning was conducted at an applied voltage of 30 kV and a feed rate of 1.0 mL\u0026middot;min⁻\u003csup\u003e1\u003c/sup\u003e. The process was carried out for 1.5 h under ambient conditions (25 \u0026deg;C, 35 \u0026plusmn; 5% RH). The resulting nanofiber membranes were vacuum-dried at 40 \u0026deg;C for 12 h to obtain the pristine PLA membrane, denoted as P-PLA.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePreparation of MRSD-PLA meta-membranes\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePLA (1.0 g) and ZIF-8 (0.4 g) nanocrystals were dissolved in a mixed solvent of DMF and DCM (3:7, v/v) under vigorous stirring to form a homogeneous spinning solution. Hydrophobic F-TiO\u003csub\u003e2\u003c/sub\u003e nanoblocks (0.2, 0.4 and 0.6 g) were individually dispersed in ethanol (10 mL) by ultrasonication to obtain stable F-TiO\u003csub\u003e2\u003c/sub\u003e suspensions. The spinning solution was electrospun using the previously described parameters. Simultaneously, the F-TiO\u003csub\u003e2\u003c/sub\u003e suspensions were deposited onto the forming fibers via electrospray. This co-axial process fabricated the microenvironment-regulating and self-decontaminating meta-membranes (MRSD-PLA). The electrospray process was conducted under the following conditions: an applied voltage of 30 kV, a feed rate of 1.0 mL\u0026middot;min⁻\u003csup\u003e1\u003c/sup\u003e and a duration of 15 min. All processes were performed under ambient conditions (25 \u0026deg;C, 35 \u0026plusmn; 5% RH). The resulting membranes were designated as MRSD-PLA2, MRSD-PLA4, and MRSD-PLA6, corresponding to the different mass fractions of F-TiO\u003csub\u003e2\u003c/sub\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCharacterization and test analysis\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe molecular structure of MRSD-PLA was characterized by Fourier transform infrared spectroscopy (FTIR, PerkinElmer Spectrum 3) and X-ray diffraction (XRD, Bruker D8 Advance). The specific surface area was determined by applying the Brunauer-Emmett-Teller (BET) model, and the pore size distribution (PSD) was calculated using non-local density functional theory (NLDFT). The electroactivity and triboelectric properties were evaluated in contact-separation mode using an MCE-3G servo-electric cylinder system. The output current, voltage and charge were recorded using a Keithley 6514 electrometer and a Keithley 2400 source meter. Additional characterization parameters are detailed in the Supplementary Information.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMoisture permeability and air breathability tests\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe gas permeation properties were evaluated using a differential pressure method. A membrane sample with an effective area of 20 cm\u003csup\u003e2\u003c/sup\u003e was sealed between two chambers. The upstream chamber was filled with high-purity test gases at a constant pressure of 100 kPa, and the downstream chamber was evacuated \u0026nbsp;and maintained under a dynamic vacuum. The steady-state gas flux was quantified with a soap-film flowmeter and the permeability was calculated based on Fick\u0026rsquo;s law of diffusion. The water vapor transmission rate (WVTR) was determined using the standard cup method (gravimetric method) under controlled conditions (25 \u0026deg;C, 90 \u0026plusmn; 2% RH). The cited threshold of \u0026gt;2000 g\u0026middot;m⁻\u003csup\u003e2\u003c/sup\u003e\u0026middot;d⁻\u003csup\u003e1\u003c/sup\u003e is based on industry standards for protective textiles (ISO 15496 and ASTM F1868), which also specify comparable testing environments to ensure consistent performance evaluation across materials. The membrane was securely sealed over a cup containing a desiccant (e.g., anhydrous calcium chloride) to create a constant humidity gradient. The mass change of the cup was periodically measured using a high-precision electronic balance. The WVTR was calculated from the steady-state mass change per unit time and normalized to the effective membrane area. Commercial counterparts include: Mask: activated carbon mask, Bao Weikang Co., China; PP: PurCotton\u0026reg; Everyday Non-medical Mask, Winner Medical Co., China; Cotton: PurCotton\u0026reg; Cotton Facial Mask, Winner Medical Co., China.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAir purification performance evaluation\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe filtration performance against indoor PM was evaluated using a homemade air filtration testing system. The airflow rates were set to specific gradients of 10, 32, 65, and 85 L\u0026middot;min⁻\u003csup\u003e1\u003c/sup\u003e using a high-precision flow pump, corresponding to the face velocities of 2.2, 6.9, 14.1, and 18.0 cm\u0026middot;s⁻\u003csup\u003e1\u003c/sup\u003e (Supplementary Table 2).\u0026nbsp;Sodium chloride (NaCl) aerosol particles, generated by a nebulizer, were employed as the test challenge. The filtration efficiency was measured simultaneously upstream and downstream of the membrane using two laser particle counters. The pressure drop across the membrane was monitored in real-time with high-precision differential pressure sensors.\u0026nbsp;To evaluate washing durability, the membranes were immersed in deionized water to remove surface-accumulated PM and then recovered through a standard drying process Their filtration performance was re-tested post-recovery.\u0026nbsp;The environmental humidity was controlled by the saturated salt solution method and continuously monitored with a digital humidity sensor. This setup enabled the evaluation of filtration performance under high-humidity conditions.\u0026nbsp;For each membrane sample, measurements were replicated at three separate locations to ensure data representativeness and reliability. The values are reported as the mean \u0026plusmn; standard deviation.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAntibacterial performance test\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe MRSD-PLA were sectioned into 7 \u0026times; 7 cm\u003csup\u003e2\u003c/sup\u003e samples for antibacterial testing. \u003cem\u003eEscherichia coli\u003c/em\u003e ATCC 25922 and \u003cem\u003eStaphylococcus aureus\u003c/em\u003e ATCC 6538 were selected as model Gram-negative and Gram-positive bacterial strains, respectively. After culture and serial dilution in nutrient broth, 500 \u0026mu;L aliquots of the bacterial suspension were spread evenly onto agar plates. The inoculated plates were then incubated at 37 \u0026deg;C for 24 h under constant illumination. The antibacterial activity was quantitatively assessed using the standard plate count method, and the bacterial reduction rate was calculated. The antibacterial tests under simulated sunlight were designed to evaluate the photocatalytic component of the antibacterial mechanism. The performance under dark or low-light conditions, relevant to real-use scenarios, is supported by the synergistic effects of electrostatic adsorption and ion release.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDegradation behavior analysis\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe biodegradation of the membrane specimens was evaluated using a natural soil burial test. A natural soil burial method was employed to assess specimen degradation. Membrane samples (5 \u0026times; 5 cm\u003csup\u003e2\u003c/sup\u003e) were buried at a depth of 5 cm in vessels filled with a standard test soil. The vessels were then placed in an outdoor environment, thereby exposing the samples to natural weathering factors, including solar radiation and precipitation. To sustain microbial activity, fresh soil was supplemented at 7-day intervals. The surface morphology of the samples was regularly examined by optical microscopy to assess the degradation progression based on visual criteria such as cracking, discoloration, or fragmentation.\u0026nbsp;\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData Availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data supporting the findings of this study are included within the Article and its Supplementary Information. Source data are provided with this paper.\u0026nbsp;\u003c/p\u003e\u003cp\u003e\u003cstrong\u003eAcknowledgements\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe research work was supported by the National Key R\u0026amp;D Program of China (Nos. 2024YFC3015003 and 2023YFC3011704), the National Natural Science Foundation of China (Nos. 52573054, 52174222 and 52003292), the China Postdoctoral Science Foundation (2024M763565), the Opening Project of State Key Laboratory of Polymer Materials Engineering (Sichuan University) (No. sklpme2023-3-6).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eH.X. and X.J.H. conceived the idea and designed the experiments. S.-Z.W. and G.Y.Z. performed the experiments. X.H.W., J.-L.G., Z.H., and Y.Z. contributed to materials characterizations. X.-P.L. and G.J.F. joined the discussion of the data and gave helpful suggestions. S.-Z.W. and H.X. wrote the manuscript. All authors participated in drafting the paper, and gave approval to the final version of the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary information\u003c/strong\u003e The online version contains supplementary material available at\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorrespondence\u003c/strong\u003e and requests for materials should be addressed to Xinjian He or Huan Xu.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePeer review information\u003c/strong\u003e \u003cem\u003eNature Communications\u003c/em\u003e thanks the anonymous reviewers for their contribution to the peer review of this work. A peer review file is available.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eReprints and permissions information\u003c/strong\u003e is available at\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePublisher\u0026rsquo;s note\u003c/strong\u003e Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eOpen Access\u003c/strong\u003e This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived fromthis article or parts of it. The images or other third party material in this article are included in the article\u0026rsquo;s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article\u0026rsquo;s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003ePan, Y., Tang, W., Fan, W., Zhang, J. \u0026amp; Chen, X. Development of nanotechnology-mediated precision radiotherapy for anti-metastasis and radioprotection. \u003cem\u003eChem. Soc. Rev.\u003c/em\u003e \u003cstrong\u003e51\u003c/strong\u003e, 9759-9830 (2022).\u003c/li\u003e\n\u003cli\u003eRoberts, K. P. et al. 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Commun.\u003c/em\u003e \u003cstrong\u003e16\u003c/strong\u003e, 2523 (2025).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7509740/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7509740/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Precise functionalization of heterogeneous interfaces in nanofibers is essential for advanced personal protective membranes. Here, we demonstrate a hierarchically heterogeneous interface structuring (HHIS) strategy to fabricate microenvironment-regulating and self-decontaminating meta-membranes (MRSD-PLA) by embedding zeolitic imidazolate framework-8 (ZIF-8) nanocrystals within poly(lactic acid) (PLA) fibers and anchoring F-TiO2 nanoblocks on their surfaces, creating an electronegativity contrast that directs electron migration and charge redistribution. ZIF-8 of porosity and electroactivity could enable charge capture/storage and trans-membrane transport (water vapor transmission rate: 4018 g·m⁻2·d⁻1; air permeability \u003e 60 mm·s⁻1 at 100 Pa). Combined with the hydrophobicity and self-cleaning capability from F-TiO2, a sustained charge migration establishes a closed-loop capture-storage-regeneration cycle. This results in self-powered sensitive monitoring and a high PM0.3 filtration efficiency of 99.3% yet a low pressure drop of 51.9 Pa (quality factor: 0.11 Pa⁻1) Moreover, MRSD-PLA inhibit bacterial growth and balance robust mechanical strength with biodegradability, showcasing great potential for high-performance personal protection.","manuscriptTitle":"Hierarchically heterogeneous interface structuring strategy for microenvironment-regulating and self-decontaminating biodegradable meta-membranes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-06 08:11:53","doi":"10.21203/rs.3.rs-7509740/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"4b9eb62d-196e-4a5a-be8b-8265ede42a7d","owner":[],"postedDate":"January 6th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":60193160,"name":"Physical sciences/Materials science/Soft materials/Polymers"},{"id":60193161,"name":"Physical sciences/Engineering/Chemical engineering"}],"tags":[],"updatedAt":"2026-04-24T12:52:29+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-06 08:11:53","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7509740","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7509740","identity":"rs-7509740","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}