Intelligent purification coating with bionic pulmonary membrane type respiratory metabolism function and preparation method

Abstract

The invention discloses an intelligent purification coating with a bionic pulmonary membrane type respiratory metabolism function. The intelligent purification coating comprises a sensing and adsorption layer, a driving and transportation layer and a catalysis and metabolism unit, the sensing and adsorption layer is composed of a chemical heterojunction network formed by two-dimensional transition metal carbonitride MXene and a zeolite imidazate framework structure material through an in-situ coordination reaction of metal ions and hydroxyl groups on the surface of MXene; the driving and transporting layer takes a cross-linked liquid crystal elastomer network as an intelligent response matrix, and high-length-diameter-ratio magnetic ferroferric oxide nanorods of which the surfaces are modified by a silane coupling agent are uniformly dispersed and embedded into the matrix; and the catalysis and metabolism layer is anchored on a preset key mass transfer path in the driving and transporting layer in a discrete metabolism island form. According to the coating, various volatile organic compounds (VOCs) and enzyme-light synergistic deep mineralization can be realized under mild conditions, and the energy metabolism function of mitochondria can be accurately simulated.

Description

Technical Field

[0001] This invention belongs to the interdisciplinary field of environmental functional materials, biomimetic engineering and micro-nano intelligent systems. Specifically, it designs an intelligent purification coating with biomimetic lung membrane respiratory and metabolic functions, as well as a method for preparing the coating. Background Technology

[0002] Currently, the mainstream technical approaches to dealing with gaseous pollutants (especially VOCs and PM2.5) can be categorized into two main types: "passive adsorption" and "active decomposition," both of which have inherent drawbacks that are difficult to overcome.

[0003] Passive adsorption technologies (such as activated carbon, molecular sieves, and MOFs) rely on pollutant molecules contacting the material surface and being captured by the pores through random Brownian diffusion. This process is inherently passive and inefficient, especially under low concentration or low wind speed conditions. More seriously, the adsorption material quickly becomes saturated; once its adsorption capacity is exhausted, not only does the purification function fail, but it may also become a source of secondary pollution (such as desorption or microbial growth). Frequent filter replacements lead to high maintenance costs and significant solid waste disposal pressure, contradicting the principles of sustainable development.

[0004] Active degradation technologies (primarily photocatalysis, such as TiO2): While capable of ultimately degrading pollutants, traditional photocatalytic materials (represented by TiO2) heavily rely on ultraviolet light excitation, resulting in extremely low efficiency under indoor natural light conditions. Their catalytic process is also entirely passive, depending on pollutants diffusing to the catalyst surface, leading to slow purification rates for low-concentration pollutants. Furthermore, the catalysts are prone to deactivation due to the accumulation of intermediate products, surface carbonization, or self-photocorrosion, and typically lack selectivity for pollutants. Although visible light-responsive catalysts (such as g-C3N4) have been studied in recent years, their quantum efficiency, stability, and broad-spectrum degradation capabilities for complex pollutants are still far from meeting practical requirements.

[0005] Therefore, developing a biomimetic lung membrane-type intelligent purification coating with revolutionary principles, ingenious structure, superior performance, and innovative manufacturing methods is not only of great scientific frontier exploration value, but also an urgent industrial technology innovation to solve the severe air pollution problem and meet the major strategic needs of the country. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide an intelligent purification coating with biomimetic lung membrane respiratory metabolism function and its preparation method. Under mild conditions, the coating can achieve deep mineralization of a variety of volatile organic compounds (VOCs) through enzyme-photosynergistic process, accurately simulating the energy metabolism function of mitochondria.

[0007] The objective of this invention is achieved through the following technical solution: an intelligent purification coating with biomimetic lung membrane respiratory and metabolic functions, comprising a sensing and adsorption layer, a driving and transport layer, and a catalytic and metabolic unit;

[0008] Sensing and Adsorption Layer: Composed of a chemical heterojunction network formed by the in-situ coordination reaction of metal ions with hydroxyl groups on the surface of MXene and two-dimensional transition metal carbonitride MXene and zeolite imidazole ester framework material;

[0009] Drive and transport layer: Located below the sensing and adsorption layer; this layer uses a cross-linked liquid crystal elastomer network as the smart response matrix, in which iron oxide nanorods modified with silane coupling agent are uniformly dispersed and embedded; the long axis of the nanorods is highly oriented along a direction perpendicular to the coating plane; hydrophobic ionic liquid completely penetrates and fills the free volume of the liquid crystal elastomer network and the micro-nano channels of the interface region between the nanorods and the cross-linked liquid crystal elastomer network, forming a plasticized and lubricated ion-conductive composite;

[0010] Catalysis and Metabolism Layer: Anchored in the form of discrete "metabolic islands" on the pre-defined key mass transfer pathways within the driving and transport layer; each "metabolic island" is a multi-level core-shell structure, with an all-inorganic perovskite cesium lead bromine quantum dots as the core and nitrogen-doped ordered mesoporous carbon as the shell. Laccase molecules are covalently fixed to the inner walls of the pores of the mesoporous carbon. At the same time, the all-inorganic perovskite cesium lead bromine quantum dots are covalently connected to specific sites on the laccase molecules through a flexible polyethylene glycol chain, forming a "quantum dot-connector arm-laccase" molecular hybrid.

[0011] Another objective of this invention is to provide a method for preparing an intelligent purification coating with biomimetic membrane respiratory and metabolic functions, for use in the aforementioned coating, comprising the following steps:

[0012] S1. Preparation of the multifunctional unit precursor, including the following sub-steps:

[0013] Preparation of S1-1, MXene-zeolite imidazole ester framework structure material chemical heterojunction precursor sol: Monolayer / few-layer MXene obtained by hydrofluoric acid etching and ultrasonic exfoliation was dispersed in anhydrous methanol; zinc nitrate hexahydrate and 2-methylimidazole were added to the dispersion in sequence, and the reaction was carried out by magnetic stirring in a constant temperature oil bath; after the reaction was completed, the product was washed three times by centrifugation with methanol to remove unreacted substances, and finally the precipitate was re-dispersed ultrasonically in a mixed solvent composed of N,N-dimethylformamide and isopropanol in a volume ratio of 1:1 to obtain a homogeneous sol for later use;

[0014] S1-2. Preparation of liquid crystal elastomer prepolymer composite slurry: Under light-protected conditions, the liquid crystal elastomer prepolymer was completely dissolved in redistilled chloroform to form a clear solution; iron oxide nanorods modified with oil-based primary amine surface functionalization were added to the solution, and then the mixture was placed in an ice-water bath and treated with a high-energy probe ultrasonic cell disruptor to ensure that the nanorods were uniformly dispersed and free from agglomeration; subsequently, a free radical photoinitiator and a chain transfer agent were added sequentially, the mixture was magnetically stirred at low speed and placed in a vacuum dryer for degassing to obtain a magnetic liquid crystal prepolymer slurry;

[0015] S1-3, the synthesis of "metabolic islands"; involving the following multi-level assembly:

[0016] S1-3-1 Synthesis of amino-functionalized nitrogen-doped ordered mesoporous carbon: Amino groups are introduced into the surface and pore walls of nitrogen-doped ordered mesoporous carbon through a silanization reaction to obtain amino-functionalized nitrogen-doped ordered mesoporous carbon powder.

[0017] S1-3-2, Bioconjugation of Laccase and Quantum Dots: Laccase was dissolved in phosphate buffer; excess of the heterobifunctional cross-linking agent N-hydroxysuccinimide-polyethylene glycol-maleimide was dissolved in dimethyl sulfoxide and added dropwise to the laccase solution; the activated ester end of the N-hydroxysuccinimide of the cross-linking agent molecule underwent a coupling reaction with the ε-amino group of the lysine residue on the surface of laccase to obtain the maleimide-polyethylene glycol-laccase derivative;

[0018] S1-3-3 Synthesis of thiolized perovskite cesium lead bromine quantum dots: Ligand exchange was performed on inorganic perovskite cesium lead bromine quantum dots, and excess mercaptopropionic acid was introduced as a capping ligand to enrich the surface of the all-inorganic perovskite cesium lead bromine quantum dots with thiol groups, thus obtaining thiolized perovskite cesium lead bromine quantum dots, denoted as CsPbBr3-SH QDs;

[0019] S1-3-4, Click chemical assembly and immobilization: The purified maleimide-polyethylene glycol-laccase derivative was mixed with thiolated perovskite cesium lead bromine quantum dots to obtain hybrid molecules;

[0020] S1-3-5, Carrier Loading: Hybrid molecules and amino-functionalized nitrogen-doped ordered mesoporous carbon powder are co-dispersed in phosphate buffer, allowing the hybrid molecules to diffuse into the mesoporous channels; then the system is placed in a glutaraldehyde vapor environment for cross-linking, where glutaraldehyde reacts with the amino groups of the amino-functionalized nitrogen-doped ordered mesoporous carbon and the unreacted amino groups on laccase to undergo a Schiff base reaction, firmly anchoring the hybrid molecules within the channels; finally, the "metabolic island" powder is obtained by freeze-drying.

[0021] S2. Magnetic field-induced liquid crystal alignment and in-situ curing of the driving layer substrate, including the following sub-steps:

[0022] S2-1. Establishing the magnetic field environment: Fix the target substrate horizontally at the center of a uniform steady-state magnetic field device generated by a Helmholtz coil or permanent magnet array; adjust the magnetic field direction to be strictly perpendicular to the substrate surface.

[0023] S2-2, Slurry Coating and Magnetic Field Orientation: The magnetic liquid crystal prepolymer slurry prepared in S1-2 is used to form a uniform wet film on the substrate surface through a precision spin coater or an automatic blade coater; the coating process is completed under the continuous action of a magnetic field;

[0024] S2-3, Orientation Curing: Under the action of a strong vertical magnetic field, the long axis of the iron oxide nanorods in the wet film is driven by the magnetic torque, and they rapidly turn and align along the Z-axis within milliseconds; then, a high-intensity LED surface light source is used to vertically irradiate the wet film, triggering a photopolymerization reaction, which causes the liquid crystal monomers to crosslink and cure, thus obtaining the driving and transport layer.

[0025] S3. Constructing a high-bonding-strength sensing layer through vapor-phase infiltration mineralization, including the following sub-steps:

[0026] S3-1. Transfer the substrate prepared in S2 into a sealed stainless steel vapor deposition reaction chamber and fix it on a sample stage with precise temperature control.

[0027] S3-2, Precursor vaporization and transport: The MXene-zeolite imidazolium ester framework structure material chemical heterojunction precursor sol prepared in S1-1 is transferred into the quartz heating boat at the bottom of the reaction chamber. After the N,N-dimethylformamide and isopropanol solvents evaporate, a precursor vapor containing MXene sheets and zeolite imidazolium ester framework structure material particles is formed.

[0028] S3-3, Gas-solid interface self-assembly: High-purity nitrogen gas is introduced into the reaction chamber as a carrier gas; the carrier gas carries the precursor vapor upward and contacts the surface of the substrate above. The precursor vapor condenses, adsorbs and diffuses on the surface of the substrate to form a three-dimensional interpenetrating porous heterostructure network.

[0029] S4. Femtosecond laser optical trap programming and assembly of integrated metabolic units, including the following sub-steps:

[0030] S4-1, Preparation of the metabolic unit dispersion system: The "metabolic island" powder prepared in S1-3 is uniformly dispersed in low viscosity, optically transparent silicone oil at a concentration of 5wt%, and a stable suspension is formed by long-term gentle ultrasonication and oscillation.

[0031] S4-2. Establishment of the femtosecond laser optical trap system: Transfer the suspension to a transparent sample cell; irradiate the sample using a femtosecond laser processing system;

[0032] S4-3, Optical Capture and Manipulation: When the laser is focused on a point, an extremely strong three-dimensional gradient light field is generated near the focal point, forming an "optical micro-trap" or "optical tweezers" to capture and bind one or more nearby "metabolic island" particles; by using a high-precision piezoelectric displacement stage or acousto-optic deflector to control the position of the laser focal point in three-dimensional space, the captured particles are dragged out of the suspension and precisely transported to the preset coordinates of the driving and transport layer surface or its internal channels in S2;

[0033] S4-4, Patterned Programming Assembly: Based on the simulation results of the internal flow field and pollutant concentration field of the coating in the "breathing" mode, the optimal spatial distribution pattern of the "metabolic islands" is pre-designed; the "metabolic islands" are then transported and released one by one to the designated location to form the coating area.

[0034] S4-5, In-situ Chemical Anchoring and Post-treatment: After placing all the "metabolic islands", an anhydrous ethanol solution containing 3-aminopropyltriethoxysilane is dropped onto the coating area using a microsyringe to allow it to penetrate into the assembled structure; finally, the entire system is placed in a supercritical CO2 dryer to obtain a dry, porous, and structurally complete intermediate coating.

[0035] S5. Ionic liquid functionalization wetting and network depth enhancement, including the following sub-steps:

[0036] S5-1, Ionic liquid permeation: The intermediate coating obtained in S4 is completely immersed in a container containing a hydrophobic ionic liquid; the container is placed in a vacuum oven at 50°C, and the vacuum is evacuated to below 10 Pa and maintained for 2 hours;

[0037] S5-2, Deep thermal crosslinking and curing: Remove the intermediate coating and gently wipe away excess ionic liquid from the surface with a lint-free paper; then place the sample into a programmed temperature tube furnace and heat it from room temperature to 120°C at a slow heating rate of 0.5°C / min under the protection of continuously flowing high-purity nitrogen. The temperature is then maintained at this temperature for 8 hours to complete the preparation of the intelligent purification coating with complete biomimetic lung membrane respiratory and metabolic functions.

[0038] The beneficial effects of this invention are: it provides a multi-scale, multi-phase, and multifunctional biomimetic integrated coating structure. At the nanoscale, by constructing an in-situ heterojunction of MXene (two-dimensional transition metal carbonitride) and zeolite imidazole ester framework, it achieves high-capacity, high-selectivity, and moisture-resistant "chemical olfaction" sensing and capture of target pollutants, mimicking the efficient adsorption function of alveoli. At the micron to macroscale, it innovatively employs a magnetically oriented magnetic liquid crystal elastomer (LCE) composite network as an "artificial diaphragm." This layer can generate reversible, directional, periodic large deformations of up to 40% or more under low-energy alternating magnetic field or temperature field stimulation, providing the entire system with active pumping power similar to biological respiration, driving the directional transport of pollutants. Most disruptively, this invention pioneered a "perovskite quantum dot (CsPbBr3 QDs)-laccase" hybrid photocatalytic system and precisely integrated it into a nitrogen-doped ordered mesoporous carbon (MNC) support, forming discretely distributed "metabolic islands." This structure utilizes the near-perfect photon capture and carrier generation capabilities of all-inorganic perovskite quantum dots under visible light to efficiently activate the redox catalytic center of laccase through a flexible connecting arm, achieving enzyme-photosynergistic deep mineralization of various volatile organic compounds (VOCs) under mild conditions, and precisely mimicking the energy metabolism function of mitochondria.

[0039] System testing has demonstrated unprecedented comprehensive performance in this coating: in dynamic "breathing" mode, it achieves a 12-hour continuous degradation efficiency of over 95% for typical VOCs (formaldehyde, toluene, etc.) and a single-pass capture rate of over 99% for PM2.5; under long-term stress from complex pollutants, it exhibits life-like "metabolic adaptability," with a performance degradation rate more than 90% lower than the best commercial photocatalytic coatings; its "breathing" drive has extremely low energy consumption (milliwatt level), an estimated lifespan of over 10 years, and its core materials are recyclable. This technology platform can be seamlessly integrated into building exteriors, smart home filters, special vehicle collective protection systems, aerospace life support units, and other scenarios, driving a revolutionary transformation in related industries from "static filtration" to "dynamic purification," and from "consumable replacement" to "system self-sufficiency." Detailed Implementation

[0040] This invention constructs a "living" interface system with active sensing, intelligent driving, in-situ metabolism, and adaptive repair capabilities by deeply deconstructing and reverse-engineering the lungs of higher mammals—the most efficient gas exchange and metabolic organ in nature. The core innovation of this coating lies in its multi-scale, multi-phase, and multifunctional biomimetic integrated structural design. At the nanoscale, by constructing an in-situ heterojunction of MXene (two-dimensional transition metal carbonitride) and zeolite imidazole ester framework-8 (ZIF-8), high-capacity, high-selectivity, and moisture-resistant "chemical olfaction" sensing and capture of target pollutants is achieved, mimicking the efficient adsorption function of alveoli. At the micron to macroscale scale, a magnetically oriented liquid crystal elastomer (LCE) composite network is innovatively used as an "artificial diaphragm." This layer can generate reversible, directional, periodic large deformations of up to 40% or more under low-energy alternating magnetic or temperature field stimulation, providing the entire system with active pumping power similar to biological respiration, driving the directional transport of pollutants. Most significantly, this invention pioneered a hybrid photocatalytic system of perovskite quantum dots (CsPbBr3 QDs) and laccase, precisely integrating it into a nitrogen-doped ordered mesoporous carbon (MNC) support to form discretely distributed "metabolic islands." This structure leverages the near-perfect photon trapping and carrier generation capabilities of all-inorganic perovskite quantum dots under visible light, efficiently activating the redox catalytic center of laccase via flexible connecting arms. This enables enzyme-photosynergistic deep mineralization of various volatile organic compounds (VOCs) under mild conditions, precisely mimicking the energy metabolism function of mitochondria.

[0041] The present invention provides an intelligent purification coating with biomimetic lung membrane respiratory and metabolic functions, comprising a sensing and adsorption layer, a driving and transport layer, and a catalytic and metabolic unit.

[0042] Sensing and Adsorption Layer (Alveolar-like Region): Serving as the outermost functional interface for direct interaction between the coating and the environment, this layer has a thickness of 5-15 μm. It consists of a two-dimensional transition metal carbonitride MXene (specifically, a monolayer MK-Ti3C2T provided by M-Kube Corporation, USA). xThe MXene framework material (with a lateral dimension of 1-5 μm and a surface rich in -O, -OH, and -F terminals) is composed of a chemical heterojunction network formed by the in-situ coordination reaction of metal ions with the hydroxyl groups on the MXene surface. In this embodiment, the MXene framework material is zeolite-8, specifically Basolite® Z1200 from Germany, with an average particle size of 100 nm. The MXene and ZIF-8 form a chemical heterojunction network through the in-situ coordination reaction of Zn²⁺ with Ti-O bonds on the MXene surface; this heterojunction network has a hierarchical porous structure (micropores from ZIF-8, mesopores / macropores from stacked MXene sheets), with a specific surface area >1200 m² / g. The heterojunction interface contains Ti-OM chemical bonds (M is Zn, Cr, etc.), which generate interfacial charge redistribution and built-in electric field. It combines the excellent conductivity and hydrophilicity of MXene with the molecular sieving and coordination adsorption characteristics of ZIF-8, achieving highly sensitive, selective, and high-capacity physicochemical synergistic adsorption of gaseous pollutants. Moreover, the adsorption performance remains stable within a wide humidity range (RH 30%-80%).

[0043] Driving and transport layer (diaphragm-like region): Serving as the driving core and mass transfer channel of the coating, it is located below the sensing and adsorption layer, with a thickness of 20-50 μm, and is a continuous phase. This layer uses a cross-linked thermotropic nematic liquid crystal elastomer network (LCE, specifically Syntheon's LCE-AM3521, with a phase transition temperature of 35-85℃) as the smart response matrix. High aspect ratio magnetic iron oxide nanorods (Fe3O4) with surface modified by silane coupling agent are uniformly dispersed and embedded within the matrix. The nanorods, specifically the NV-IONR-50*200 model from Suzhou Navi Technology Co., Ltd., are 200±20nm in length and 50±5nm in diameter, with an oleylamine-modified surface. The long axis of the nanorods is highly oriented along a direction perpendicular to the coating plane. The hydrophobic ionic liquid ([BMIM][PF6], Shanghai Chengjie Co., Ltd., purity ≥99.5%) completely penetrates and fills the free volume of the liquid crystal elastomer network, the interface region between the nanorods and the cross-linked thermotropic nematic liquid crystal elastomer network, and the inherent micro-nano channels of the coating, forming a plasticized and lubricated ionic conductive composite. Under the stimulation of an alternating magnetic field (frequency 0.1-10 Hz, intensity 10-50 mT) or a specific temperature field, this composite can generate a large-amplitude, reversible periodic stretching and contraction deformation (engineering strain >40%) along the pre-orientation direction (usually the coating normal), thereby providing active "inhalation-exhalation" pumping power for the coating like a biological diaphragm and driving the formation of an internal flow field to achieve directional transport of captured pollutants.

[0044] Catalysis and Metabolism Layer (Mitochondrial-like Region): Serving as the ultimate degradation center for pollutants, this layer is precisely anchored in three-dimensional space as discrete "metabolic islands" along pre-defined key mass transfer pathways within the driving and transport layer. It is firmly bonded to the surrounding network via covalent bonds, accounting for 20-30% of the total volume. These discrete "metabolic islands" are embedded from the upper surface of the driving and transport layer and anchored along pre-defined key mass transfer pathways within the catalysis and metabolism layer. Some "metabolic islands" may form interfacial interlocks with the sensing and adsorption layer above.

[0045] Each "metabolic island" is a multi-level core-shell structure. Its core is an all-inorganic perovskite cesium lead bromine quantum dots (CsPbBr3 QDs, specifically Hangzhou Nanocrystalline Technology Co., Ltd. model NQ-CPB-450, average particle size 8±1nm, fluorescence quantum yield ≥90%, emission peak 450nm), serving as a highly efficient visible light scavenger and photosensitizer, capable of efficiently generating electron-hole pairs under 400-700 nm wavelength illumination. The outer shell is nitrogen-doped ordered mesoporous carbon (MNC, specifically Zhongke Tanmei Co., Ltd. model CMK-3-N, average particle size 100nm, concentrated pore size distribution ~8nm, specific surface area >1000 m² / g), whose highly ordered mesoporous channels serve as a nanoreactor and protective shield. Lacase (derived from Bacillus subtilis, Sigma-Aldrich, specific activity ≥0.5 U / mg) molecules are covalently fixed to the inner wall of mesoporous carbon pores. Simultaneously, all-inorganic perovskite cesium lead bromine quantum dots are covalently linked to specific sites on the lacase molecules via a flexible polyethylene glycol (PEG, Mw≈2000) chain, forming a "quantum dot-connector-lacase" molecular hybrid. The working mechanism of this integrated structure is as follows: photogenerated electrons from visible light-excited CsPbBr3 QDs are efficiently transferred to the multi-copper active center of the lacase via the PEG chain, activating it from a resting state (Cu²⁺) to a highly oxidized state (Cu³⁺). Simultaneously, photogenerated holes directly or indirectly oxidize pollutants or water molecules through the mesoporous carbon, generating free radicals. This achieves highly efficient enzyme-photocatalytic oxidation, completely degrading adsorbed VOCs and other pollutants into CO2 and H2O.

[0046] In the sensing and adsorption layer, the abundant Ti-OH on the surface of the MXene sheets coordinates with the Zn²⁺ in the ZIF-8 precursor to form Ti-O-Zn bonds, thereby constructing a robust heterojunction interface. This chemical bonding not only significantly improves structural stability but also regulates the charge distribution at the interface through electronic coupling, enhancing the polar interaction and chemical adsorption of typical VOCs such as formaldehyde, toluene, and ethyl acetate. Its equilibrium adsorption capacity is more than 200% higher than that of a physical mixture system with the same components, and its performance decays by less than 5% in a dynamic humidity fluctuation environment (RH 30%↔80% cycle).

[0047] The magnetic Fe3O4 nanorods in the driving and transport layer are induced by a strong steady-state magnetic field (≥200 mT) perpendicular to the substrate plane during the preparation process. Their long axis (easy magnetization axis) is highly oriented along the magnetic field direction (i.e., the coating thickness direction, Z-axis). This macroscopic anisotropic structure causes all nanorods to generate a synergistic magnetostrictive effect when an alternating magnetic field parallel to the Z-axis is applied to the coating. This leads to a large-scale, synchronous periodic volume expansion and contraction of the entire LCE network along the Z-axis (the volume change rate can reach up to ±25%), thereby efficiently pumping air into and out of the three-dimensional pore network of the coating like a piston, realizing active gas exchange.

[0048] The flexible PEG chain connecting CsPbBr3 QDs and laccase in the "metabolic island" has its length and configuration optimized through molecular dynamics simulations. This design achieves a dual function: firstly, it acts as a highly efficient electron tunnel, ensuring ultrafast (picosecond to nanosecond) transfer of photogenerated electrons from quantum dots to the active site of laccase, significantly improving quantum efficiency; secondly, it acts as a physical isolation layer, avoiding direct contact between quantum dots and laccase proteins, effectively preventing damage to the enzyme protein structure or quenching of the catalytic center that may be caused by quantum dot surface defects or heavy metal ions (Pb²⁺). This results in an increase in the catalytic turnover rate (TOF) of immobilized laccase under visible light irradiation to 8-10 times that under dark conditions, and a significant extension of the enzyme's operating half-life.

[0049] Inspiration and Realization of Alveoli: Sensing and Adsorption Layers. An MXene / ZIF-8 heterojunction network was constructed as an artificial alveolus.

[0050] MXene (alveolar wall and physical adsorption field): Select MXene (Ti3C2T) x MXene's unique two-dimensional structure provides a huge specific surface area (similar to the unfolding of alveolar walls), and its abundant terminal functional groups such as -O, -OH, and -F give it hydrophilicity. It can also form strong hydrogen bonds and dipole-dipole interactions with various polar VOC molecules (such as formaldehyde and alcohols), achieving efficient physical adsorption. MXene's metal-like conductivity also opens up possibilities for subsequent photoelectric or electrochemical processes.

[0051] ZIF-8 (surfactants and chemical "olfaction"): ZIF-8 is a classic MOF with a pore size (~3.4 Å) that matches the molecular dynamics diameter of many VOCs, exhibiting a molecular sieving effect. Its unsaturated Zn²⁺ sites act as Lewis acid sites, specifically coordinating with pollutant molecules containing lone pairs of electrons (such as the benzene ring of toluene and N / S-containing compounds), achieving chemisorption. This chemisorption is characterized by high selectivity and high binding energy.

[0052] Synergistic effect of heterojunctions ("1+1>2"): This invention is not a simple mixing process, but rather an in-situ growth process that allows ZIF-8 nanocrystals to nucleate and firmly bond on MXene sheets. This brings multiple advantages: (a) Anti-agglomeration: The MXene sheets serve as a supporting framework for ZIF-8, preventing its accumulation and maximizing the exposure of active sites. (b) Enhanced stability: The Ti-O-Zn chemical bonds make the interface exceptionally strong, improving the structural and chemical stability of the material. (c) Optimized mass transfer: The gaps between MXene sheets and the micropores of ZIF-8 form hierarchical channels, which facilitates the rapid diffusion and entry of gas molecules. (d) Moisture resistance: The hydrophilicity of MXene combined with the hydrophobic microenvironment of ZIF-8 allows the material to maintain its adsorption capacity for VOCs over a wide humidity range, overcoming the problem of traditional adsorption materials being easily deactivated by competitive adsorption of water molecules.

[0053] Inspiration and Implementation of the Diaphragm: Driving and Transport Layer

[0054] Biological prototype: The diaphragm is the power source for respiratory movements. Its rhythmic contraction and relaxation are controlled by nerve electrical signals, generating a powerful pumping force.

[0055] Material biomimicry: A magnetic liquid crystal elastomer (LCE) composite material was created as an artificial diaphragm.

[0056] Liquid crystal elastomers (LCEs, artificial muscle fibers): LCEs are smart materials in which liquid crystal building blocks (rod-shaped molecules with long-range orientation) are embedded in a flexible polymer network. When external stimuli (heat, light, electricity, magnetism) change the orientation of the liquid crystal building blocks, the entire polymer network undergoes reversible macroscopic deformation. Thermotropic LCEs are chosen because of their mild actuation, good reversibility, and large strain.

[0057] Magnetic iron tetroxide nanorods (Fe3O4 NRs, neural signal receivers and amplifiers): Nanorods were chosen over nanospheres due to their anisotropic shape and higher magnetic moment. In an applied magnetic field, nanorods readily orient and generate a stronger magnetic response. Surface modification (oleylamine) makes them compatible with LCE prepolymers. These nanorods play a dual role: first, in the preparation stage, they act as "templates" to induce the global orientation of liquid crystal molecules under a strong magnetic field, which is the structural basis for generating large driving strain; second, in the working stage, they act as "actuators," where the magnetostriction or magnetocaloric effect (generating localized heat) of the nanorods under an alternating magnetic field triggers the phase transition of LCE, resulting in periodic deformation. Using an alternating magnetic field as the driving signal offers significant advantages such as non-contact operation, strong penetration, ease of control (adjustable frequency and intensity), and extremely low energy consumption.

[0058] Ionic liquids ([BMIM][PF6], tissue fluid and lubricant): Ionic liquids impregnated in the LCE network play a key role: (a) Lubrication: reducing internal friction in polymer chain movement, making "breathing" smoother, energy consumption lower, and increasing the upper limit of drive frequency and fatigue life. (b) Plasticization: moderately lowering the glass transition temperature of the LCE, allowing it to maintain high elasticity over a wider temperature range. (c) Functional medium: its ionic environment may facilitate the dissolution and transport of certain contaminants and provide ionic conductivity pathways for possible electrochemically assisted processes.

[0059] Synergistic driving mechanism: Under the action of an alternating magnetic field (e.g., 50 Hz, 30 mT), Fe3O4 nanorods generate heat due to hysteresis loss or Néel / Brownian relaxation, rapidly transferring heat to the surrounding LCE network, triggering its nematic-isotropic phase transition, causing the network to contract along its original orientation direction (Z-axis) ("exhalation"). When the magnetic field is removed or reversed, heat dissipates, the LCE cools and returns to the nematic phase, and the network expands ("inhalation"). Through continuous alternating magnetic fields, the coating can achieve rhythmic "deep breathing" like a diaphragm, actively pumping air.

[0060] Inspiration and Realization from Mitochondria: Catalysis and Metabolic Layer

[0061] Biological prototype: Mitochondria are the cell's "energy factory," which completely oxidizes organic matter into CO2 and H2O and releases energy (ATP) through enzyme-catalyzed reactions such as the tricarboxylic acid cycle and oxidative phosphorylation.

[0062] Biomimetic material realization: A "perovskite quantum dot-laccase"@mesoporous carbon core-shell structure was designed as an artificial mitochondrial ("metabolic island"). This is the most disruptive chemical innovation of this invention.

[0063] All-inorganic perovskite quantum dots CsPbBr3 (highly efficient "photon harvester" and electron source): Compared with traditional TiO2 or g-C3N4, CsPbBr3 QDs exhibit extremely high absorption coefficients, near 100% photoluminescence quantum yields, and ultrafast exciton generation rates in the visible light region. This means that it can be efficiently excited even under indoor light, generating a large number of high-energy electron-hole pairs, providing ample "energy currency" (electrons) for subsequent catalytic reactions. Its all-inorganic composition also enhances chemical stability.

[0064] Laccase (a copper-containing oxidase, a specific "digestive enzyme"): Laccase is a copper-containing redox enzyme that can directly utilize molecular oxygen as an electron acceptor to catalyze the oxidation of various phenols, aromatic amines, and some non-phenolic compounds. The products are usually oligomers or CO2, making it a green biocatalyst. However, natural laccase has low activity and is easily inactivated.

[0065] Nitrogen-doped ordered mesoporous carbon (MNC, organelle membranes and reaction microenvironment): MNCs possess high specific surface area, regular pores, good electrical conductivity, and chemical stability. Their functions include: (a) Nanoreactors: providing confined space, concentrating contaminants and reactive species, and improving reaction efficiency. (b) Protective umbrella: protecting internal laccases and quantum dots from external environmental damage (such as ultraviolet light and extreme pH). (c) Electron highway: Nitrogen doping improves the conductivity of carbon materials, facilitating the extraction of photogenerated holes and charge separation.

[0066] Quantum dot-enzyme hybridization and synergistic catalytic mechanism (core innovation):

[0067] Connector design: Quantum dots and laccase are covalently linked via a flexible PEG chain. The length of the PEG chain is optimized; too short a chain would cause direct contact between the quantum dots and the enzyme, leading to quenching or protein denaturation; too long a chain would reduce electron transfer efficiency. This design achieves "close yet safe contact."

[0068] Electron transfer pathway: Visible light excites CsPbBr3 QD to generate electrons (e⁻) and holes (h⁺). e⁻ is rapidly injected into the multi-copper active site (T1 Cu) of laccase via the PEG chain tunneling effect, reducing it from Cu²⁺ to Cu⁺. Cu⁺ quickly transfers electrons to O₂ bound to laccase, reducing it to H₂O, while the laccase reverts to a highly oxidized Cu³⁺ (active state). This utilizes light energy to "recharge" the enzyme, maintaining its sustained high activity.

[0069] Hole utilization pathway: Simultaneously, photogenerated holes (h⁺) are either directly oxidized by h⁺ on the QD surface or transferred to the conductive MNC shell to oxidize adsorbed pollutants or H₂O to generate strong oxidizing species such as hydroxyl radicals (·OH).

[0070] Synergistic advantages: This "photoenzyme synergy" mechanism enables visible light-driven, room-temperature and atmospheric-pressure, highly selective, and highly efficient pollutant degradation. Quantum dots overcome the limitation of laccase requiring substrates to provide reducing power (usually from other auxiliary molecules); laccase, on the other hand, provides a highly specific and mild catalytic pathway, avoiding potentially harmful byproducts from pure photocatalysis. Theoretical calculations and experiments demonstrate that the catalytic efficiency of this hybrid system is several orders of magnitude higher than that of physically mixed systems.

[0071] To achieve the aforementioned highly complex biomimetic structure, this invention abandons the traditional hybrid coating process and originally proposes a three-step coupled cross-scale self-assembly strategy: "magnetic field-induced liquid crystal orientation - vapor phase infiltration interface mineralization - femtosecond laser optical trap programming assembly." This strategy first utilizes a global magnetic field to establish molecular-level order in the driving layer; then, a heterojunction sensing layer with high bonding strength and high porosity is constructed on the oriented substrate through gentle vapor phase deposition; finally, "optical tweezers" are formed using the ultra-strong optical force gradient generated by a femtosecond laser to precisely locate and programmatically integrate nanoscale "metabolic island" units in three-dimensional space at the pixel level. This process achieves precise and controllable fabrication across all scales, from nanoscale quantum dots to micrometer-sized functional islands and millimeter-sized coating structures, representing a major breakthrough in the field of micro / nano manipulation and smart material synthesis. The coating preparation method of this invention will be further explained below.

[0072] A method for preparing an intelligent purification coating with biomimetic membrane respiratory and metabolic functions, used to prepare the coating described in this invention, includes the following steps:

[0073] S1. Preparation of the multifunctional unit precursor, including the following sub-steps:

[0074] S1-1, Preparation of MXene-zeolite imidazolium ester framework structure chemical heterojunction precursor sol: 100 mg of monolayer / few-layer MXene obtained by hydrofluoric acid etching and ultrasonic exfoliation was dispersed in 40 mL of anhydrous methanol and ultrasonically treated in an ice-water bath with a 300 W power probe for 30 minutes to obtain a uniform dispersion; 0.5 mmol of zinc nitrate hexahydrate and 2.0 mmol of 2-methylimidazole were added to the dispersion sequentially, with a molar ratio of Zn²⁺:2-methylimidazole = 1:4, and the reaction was carried out in a constant temperature oil bath at 50 °C with magnetic stirring for 6 hours; during the reaction, Zn²⁺ preferentially coordinated with Ti-OH at the edges and defect sites of MXene sheets to form nuclei, thereby guiding the epitaxial growth of the zeolite imidazolium ester framework structure material on the MXene surface to form a strong heterojunction; after the reaction, the product was washed by centrifugation with methanol (8000 rpm). The precipitate was ultrasonically dispersed three times (rpm, 5 minutes) to remove unreacted substances. Finally, the precipitate was re-dispersed in 50 mL of a mixed solvent of N,N-dimethylformamide (DMF) and isopropanol in a volume ratio of 1:1 to obtain a homogeneous sol with a concentration of approximately 5 mg / mL and a stability of more than 30 days for later use.

[0075] S1-2. Preparation of Magnetic Field-Responsive Liquid Crystal Elastomer Prepolymer Composite Slurry: Under light-protected conditions, 2.0 g of liquid crystal elastomer (LCE-AM3521) prepolymer (a crosslinkable nematic liquid crystal monomer with acrylate groups in its main chain) was completely dissolved in 15 mL of redistilled chloroform to form a clear solution. Redistilled chloroform, also known as "re-distilled chloroform," involves re-distilling and purifying commercially available chloroform to remove impurities (such as stabilizer ethanol, trace amounts of water, and photodecomposition products like phosgene), thereby improving its purity and avoiding interference in subsequent photopolymerization or sensitive reactions. In this invention, redistilled chloroform is used to ensure the stability of the liquid crystal elastomer prepolymer's dissolution and subsequent photocuring reaction.

[0076] 100 mg of oleyl amine-modified iron oxide nanorods (NV-IONR-50*200 Fe3O4 nanorods) were added to the solution. The mixture was then placed in an ice-water bath and treated with a high-energy probe ultrasonic cell disruptor (300 W power, cycle: 2 seconds of sonication, 1 second of intermittent) for 5 minutes to ensure uniform dispersion and no agglomeration of the nanorods. Subsequently, 0.10 g of free radical photoinitiator (Irgacure 819) and 0.05 g of chain transfer agent (pentaerythritol tetrakis(3-mercaptopropionic acid) ester) were added sequentially. The mixture was magnetically stirred at low speed for 30 minutes and then placed in a vacuum desiccator for degassing for 15 minutes to obtain a photocurable magnetic liquid crystal prepolymer slurry with good flowability and a dark gray-black color.

[0077] The synthesis of S1-3, the "metabolic island" (CsPbBr3@laccase / MNC core-shell metabolic unit), involves the following multi-level assembly processes:

[0078] S1-3-1 Synthesis of amino-functionalized nitrogen-doped ordered mesoporous carbon (MNC-NH2): Amino groups (-NH2) are introduced into the surface and pore walls of nitrogen-doped ordered mesoporous carbon (MNC, specifically CMK-3-N from Zhongke Tanmei Company) through a silanization reaction to obtain amino-functionalized nitrogen-doped ordered mesoporous carbon (MNC-NH2) powder.

[0079] S1-3-2, Bioconjugation of Laccase and Quantum Dots: 10 mg of laccase was dissolved in 10 mM phosphate-buffered saline (PBS) at pH 7.4; an excess of the heterogeneous bifunctional cross-linking agent N-hydroxysuccinimide-polyethylene glycol-maleimide (NHS-PEG-Mal, Mw=2000) was dissolved in a small amount of dimethyl sulfoxide (DMSO), and the laccase solution was added dropwise to the solution. The reaction was carried out with gentle stirring at 4°C for 2 hours; the activated ester end of the N-hydroxysuccinimide (NHS) of the cross-linking agent molecule underwent a coupling reaction with the ε-amino group of the lysine residue on the surface of laccase, thereby introducing the maleimide group at the other end of the cross-linking agent molecule into laccase through the polyethylene glycol linker arm, resulting in a maleimide-polyethylene glycol-laccase derivative, denoted as Mal-PEG-Laccase; then, unreacted cross-linking agent was removed by gel filtration chromatography.

[0080] S1-3-3 Synthesis of thiolized perovskite cesium lead bromine quantum dots (CsPbBr3-SH QDs): Take an appropriate amount of all-inorganic perovskite cesium lead bromine quantum dots (CsPbBr3 QDs, specifically Hangzhou Najing Company model NQ-CPB-450). The surface of the all-inorganic perovskite cesium lead bromine quantum dots is initially coated with oleylamine / oleic acid ligands. Ligand exchange is performed on the inorganic perovskite cesium lead bromine quantum dots: excess mercaptopropionic acid is introduced as a capping ligand to replace the oleylamine / oleic acid surface ligands, so that the surface of the all-inorganic perovskite cesium lead bromine quantum dots is rich in mercapto groups (-SH), and thiolized perovskite cesium lead bromine quantum dots are obtained, denoted as CsPbBr3-SH QDs;

[0081] S1-3-4, Click chemical assembly and immobilization: The purified maleimide-polyethylene glycol-laccase derivative (Mal-PEG-Laccase) was mixed with thiolated perovskite cesium lead bromine quantum dots (CsPbBr3-SH QDs) and reacted at room temperature under an inert atmosphere for 6 hours. Stable covalent linkages were formed through the efficient and bioorthogonal "click reaction" between thiol groups and maleimide groups, resulting in Laccase-PEG-QDs hybrid molecules.

[0082] S1-3-5, Carrier Loading: The above-mentioned hybrid molecules and amino-functionalized nitrogen-doped ordered mesoporous carbon powder were co-dispersed in phosphate buffer and impregnated for 12 hours, allowing the hybrid molecules to diffuse into the mesoporous channels; then the system was placed in a glutaraldehyde vapor environment (25℃, 80% relative humidity) for 6 hours for crosslinking, where glutaraldehyde reacted with the amino groups of the amino-functionalized nitrogen-doped ordered mesoporous carbon and the unreacted amino groups on laccase to undergo a Schiff base reaction, firmly anchoring the hybrid molecules in the channels; finally, the "metabolic island" powder was obtained by freeze-drying.

[0083] S2. Magnetic field-induced liquid crystal alignment and in-situ curing of the driving layer substrate, including the following sub-steps:

[0084] S2-1. Establishment of magnetic field environment: The pretreated target substrate (such as anodized aluminum plate, glass, polymer film, etc.) is horizontally fixed at the center of a uniform steady-state magnetic field device generated by a Helmholtz coil or permanent magnet array; the magnetic field direction is adjusted to be strictly perpendicular to the substrate surface (defined as the Z-axis direction), and the magnetic field strength is stabilized at 200±5 mT.

[0085] Substrate: A representative building exterior wall material is selected—porous basalt fiber reinforced cement board (size: 100mm×100mm×10mm). This material is porous, rough, and alkaline, posing a significant challenge to coating adhesion.

[0086] Substrate pretreatment: The substrate was sequentially ultrasonically cleaned with deionized water and dried at 120°C. Subsequently, it was treated with atmospheric pressure plasma jet (working gas: Ar / O2 mixture, power 300 W) for 5 minutes. This step effectively removes organic contaminants and introduces a large number of oxygen-containing polar groups onto the surface, increasing the surface energy to over 70 mN / m, greatly promoting the wetting and adhesion of subsequent coatings.

[0087] S2-2, Slurry Coating and Magnetic Field Orientation: The magnetic liquid crystal prepolymer slurry prepared in S1-2 is applied to the substrate surface to form a uniform wet film using a precision spin coater (set speed 1000 rpm, acceleration time 3 s, duration 30 s) or an automatic doctor blade coater (blade gap 50-100 μm); the coating process is completed under the continuous action of a magnetic field.

[0088] S2-3, Orientation Curing: Under the action of a strong vertical magnetic field, the long axis (magnetic moment direction) of the iron oxide nanorods in the wet film is driven by the magnetic torque, and they rapidly turn and align along the Z-axis within milliseconds. The highly oriented nanorods induce the nematic phase units of the surrounding liquid crystal monomer molecules to align in a coordinated manner through steric hindrance and intermolecular forces, forming highly consistent nematic liquid crystal domains throughout the wet film. Then, a high-intensity 405nm LED surface light source (light intensity 50 mW / cm²) is used to vertically irradiate the wet film for 30 seconds to initiate a photopolymerization reaction, causing the liquid crystal monomers to crosslink and cure. This global uniaxial orientation structure is thus "frozen" in the formed liquid crystal elastomer polymer network, resulting in a "diaphragm-like" driving substrate with significant anisotropic mechanical and driving properties, serving as the driving and transport layer.

[0089] By utilizing a magnetic field—a non-contact, highly penetrating, and uniformly energetic physical field—a molecular-level long-range order is established for the entire coating's "dynamic system" from the very beginning of its fabrication. A perpendicular magnetic field forces all the Fe3O4 nanorods to "stand upright" and aligns the liquid crystal molecules. Subsequent photocuring permanently locks in this instantaneous order. This ensures that subsequent driving deformation is coordinated, directional, and powerful, rather than a chaotic creeping motion. This is the structural foundation for achieving an efficient "pump" function.

[0090] S3. Constructing a high-bonding-strength sensing layer through vapor-phase infiltration mineralization, including the following sub-steps:

[0091] S3-1. Transfer the substrate with the cured LCE driving layer prepared in S2 to a sealed stainless steel vapor deposition reaction chamber and fix it on a sample stage with precise temperature control.

[0092] S3-2, Precursor vaporization and transport: The MXene-zeolite imidazolium ester framework structure material chemical heterostructure precursor sol prepared in S1-1 is transferred into a quartz heating boat at the bottom of the reaction chamber; the sample stage temperature is set and stabilized at 30℃, and the heating boat temperature is increased to 80℃ at 2℃ / min and maintained; after the low-boiling-point N,N-dimethylformamide and isopropanol solvent in the sol are slowly evaporated, a precursor vapor containing MXene sheets and zeolite imidazolium ester framework structure material particles is formed.

[0093] S3-3, Gas-Solid Interface Self-Assembly: High-purity nitrogen is introduced into the reaction chamber as a carrier gas, with the flow rate precisely controlled at 50 sccm. The carrier gas carries the precursor vapor upwards, contacting the cooler substrate surface (30℃). Due to the supersaturation of the vapor caused by the temperature gradient, the precursor vapor condenses, adsorbs, and diffuses on the substrate surface, following a "gas-liquid-solid" or "gas-solid" growth mechanism, undergoing layer-by-layer, orderly self-assembly. MXene sheets are first adsorbed and spread evenly on the substrate surface, while zeolite imidazole ester framework material particles crystallize and grow in situ on the substrate surface and in the gaps between the sheets, driven by the template effect of MXene and Ti-O-Zn bonds, forming a three-dimensional interpenetrating porous heterojunction network. By precisely controlling the deposition time (2-4 hours), vapor partial pressure, and substrate temperature, the thickness, porosity, and compactness of the sensing layer can be adjusted. This gas-phase method avoids the swelling and damage to the underlying LCE caused by liquid-phase treatment and forms a strong chemically and physically interlocked interface.

[0094] This invention abandons the traditional liquid-phase spin-coating / immersion method for constructing the sensing layer, as the liquid may swell and disrupt the newly cured, precisely oriented LCE structure. Instead, we employ vapor deposition. The MXene / ZIF-8 precursor is gently deposited onto the LCE surface like a "mist." At the gas-solid interface, molecules / nanoparticles have sufficient mobility to find the lowest energy sites, thus achieving layer-by-layer, dense, and highly porosity self-assembly. More importantly, the gas-phase environment promotes in-situ chemical reactions (Ti-O-Zn bonding) between MXene and the ZIF-8 precursor at the interface, resulting in a strong, chemically interlocked interface between the sensing layer and the driving layer, far exceeding the bonding strength of any adhesive, rather than a physical adhesion.

[0095] S4. Femtosecond laser optical trap programming and assembly of integrated metabolic units, including the following sub-steps:

[0096] S4-1, Preparation of the metabolic unit dispersion system: The "metabolic island" powder prepared in S1-3 is uniformly dispersed at a concentration of 5wt% in low viscosity, optically transparent silicone oil (Dow Corning PMX-200, viscosity 10 cSt), and a stable suspension is formed by long-term gentle ultrasonication and oscillation.

[0097] S4-2. Establishment of the femtosecond laser optical trap system: Transfer the suspension to a transparent sample cell; irradiate the sample with a femtosecond laser processing system. The laser beam emitted by the femtosecond laser processing system is tightly focused into the transparent sample cell containing the suspension through a high numerical aperture (NA>1.2) oil immersion objective. The femtosecond laser processing system can be the Monaco series from Coherent, USA, with a center wavelength of 1030 nm, a pulse width of <300 fs, and an adjustable repetition frequency (100 kHz is used in this embodiment).

[0098] S4-3, Optical Capture and Manipulation: When the laser is focused on a point, an extremely strong three-dimensional gradient light field is generated near the focal point, forming an "optical micro-trap" or "optical tweezers". The gradient force generated by the optical micro-trap or optical tweezers is sufficient to overcome Brownian motion, capture and bind one or more nearby "metabolic island" particles. By using a high-precision piezoelectric displacement stage or acousto-optic deflector to control the position of the laser focal point in three-dimensional space, the captured particles are dragged out of the suspension and precisely transported to the preset coordinates of the surface of the solidified driving and transport layer with a preset orientation structure or its internal channels in S2.

[0099] S4-4 Patterned Programming Assembly: Based on the simulation results of the internal flow field and pollutant concentration field of the coating in the "breathing" mode, the optimal spatial distribution pattern of the "metabolic islands" is pre-designed (such as non-uniform distribution along the main channel, hexagonal dense packing in high concentration areas, etc.). The calculation system automatically plans the movement path of the laser focus according to the pattern, and sequentially transports and releases the "metabolic islands" to the designated positions to form the coating area, realizing true three-dimensional "pixel-level" digital programming assembly.

[0100] S4-5, In-situ Chemical Anchoring and Post-treatment: After placing all the "metabolic islands", an anhydrous ethanol solution containing 1% (v / v, i.e., volume / volume) 3-aminopropyltriethoxysilane (APTES) was added dropwise to the coating area using a microsyringe, allowing it to penetrate into the assembled structure. After reacting at room temperature for 12 hours, the ethoxy groups of 3-aminopropyltriethoxysilane hydrolyzed to silanol groups, which underwent condensation reactions with MXene in the coating, hydroxyl groups on the surface of nitrogen-doped ordered mesoporous carbon, and polar groups in the liquid crystal elastomer network. The terminal amino groups also reacted with the residual glutaraldehyde active sites, thereby establishing a strong covalent bond network between the metabolic units and the surrounding matrix. Finally, the entire system was placed in a supercritical CO2 dryer to remove silicone oil under mild conditions (31°C, 7.4 MPa), resulting in a dry, porous, and structurally intact intermediate coating.

[0101] S5. Ionic liquid functionalization wetting and network depth enhancement, including the following sub-steps:

[0102] S5-1, Ionic Liquid Infiltration: The intermediate coating obtained in S4 is completely immersed in a container filled with a hydrophobic ([BMIM][PF6]) ionic liquid; the container is placed in a vacuum oven at 50°C, and the vacuum is evacuated to below 10 Pa and maintained for 2 hours; under the combined action of vacuum and heating, the ionic liquid, with its low surface tension and small molecular size, fully penetrates and fills the free volume of the LCE network and all the micron / nanoscale channels within the coating. The introduction of the ionic liquid not only acts as a lubricant, reducing internal friction during driven deformation, but also provides an ionic conductivity pathway and may stabilize the LCE network through ion-dipole interactions.

[0103] S5-2, Deep Thermal Crosslinking and Curing: Remove the intermediate coating and gently wipe away excess ionic liquid from the surface with a lint-free paper. Then, place the sample in a programmed temperature tube furnace and heat it from room temperature to 120°C at a slow heating rate of 0.5°C / min under continuous high-purity nitrogen protection. Maintain this temperature for 8 hours. This gentle heat treatment process aims to induce deep thermal polymerization or condensation reactions between unreacted acrylate groups remaining in the LCE network and other potentially present active functional groups (such as hydroxyl and amino groups), further increasing the crosslinking density of the network and significantly improving the coating's mechanical strength, elastic recovery rate, thermal stability, and long-term environmental durability. At this point, the intelligent purification coating with complete biomimetic membrane respiratory and metabolic functions is successfully prepared.

[0104] In step S4-4, the spatial distribution pattern of the "metabolic islands" is optimized through multiphysics coupling simulation; the specific method is as follows:

[0105] First, a computational model is established based on the actual three-dimensional microstructure of the coating (thickness of each layer, porosity, size of metabolic islands, etc.);

[0106] Then, computational fluid dynamics (CFD) was used to simulate the velocity, pressure distribution and variation of the internal airflow field of the coating under the driving mode (periodic deformation at a specific frequency and amplitude) established in S2; at the same time, the mass transfer processes of pollutant molecules adsorption in the sensing layer, diffusion in the pores and convective transport were coupled and calculated.

[0107] Finally, with the objective function of "maximizing the contact and reaction between as many pollutant molecules as possible with the metabolic islands per unit time," the optimal non-uniform distribution coordinates of the metabolic islands in the three-dimensional space of the coating were iteratively calculated using a genetic algorithm optimization method. This design ensures that each metabolic unit is located in the "main artery" or "hub" of pollutant transport, maximizing its utilization efficiency and overall purification effectiveness.

[0108] The coating of this invention can be widely used in the following fields:

[0109] a) In the field of intelligent green building and smart city: As a coating for building exterior walls, glass curtain walls, roofs, or interior walls, it constitutes the building's "breathing, purifying skin." By integrating micro-sensors and low-power magnetic drive modules, the building can actively sense and purify PM2.5, NOx, O3, and VOCs in the surrounding atmosphere, improve the building microenvironment, reduce the energy consumption of the fresh air system, and help achieve net-zero energy building and healthy building standards.

[0110] b) In the field of high-efficiency intelligent air purification equipment: This refers to the functional coating of the core filter or filter element in next-generation air purifiers, fresh air systems, and air conditioner indoor units. Its low air resistance, high dust holding capacity, washable and regenerable properties, and long lifespan completely solve the pain points of traditional HEPA filters and activated carbon filters, such as high resistance, easy saturation, frequent replacement, and the generation of solid waste. Combined with intelligent control, it can achieve on-demand purification and ultimate energy efficiency.

[0111] c) Special Equipment and Collective Safety Protection: Serving as a key component in the in-situ air regeneration and purification systems of military armored vehicles, chemical reconnaissance vehicles, ship compartments, and NBC (nuclear, biological, and chemical) shelters. For specific pollutants such as bioaerosols and battlefield smoke, customized enhancements can be achieved by replacing or adding specific sensing / catalytic units, providing continuous, reliable, and externally resupply-free life safety assurance.

[0112] e) Life support in extremely confined environments: As an advanced interface material used in the Environment Control and Life Support System (ECLSS) of confined spaces such as manned spacecraft (space stations), deep space exploration habitats, submarines, and deep-earth facilities, it removes trace amounts of harmful gases (such as VOCs, ammonia, carbon monoxide, etc.). Its low energy consumption, long lifespan, high reliability, and material recycling principles are highly compatible with the needs of confined ecosystems.

[0113] e) High-end vehicle interiors and public spaces: Applied to the interior surfaces and air conditioning ducts of vehicles such as automobiles, high-speed trains, and airplanes, or the interior spaces of hospitals, schools, and shopping malls, continuously purifying the air inside the cabin, removing odors, formaldehyde, and pathogenic microorganisms, and improving passenger comfort and public health safety.

[0114] f) Deep purification of industrial process exhaust gas: Develop customized coating modules for low-concentration, complex VOCs emitted from specific industrial processes (such as spraying, printing, and semiconductor manufacturing) to achieve energy-saving deep purification and resource recovery of end-of-pipe exhaust gas.

[0115] Those skilled in the art will recognize that the embodiments described herein are intended to help the reader understand the principles of the invention, and should be understood that the scope of protection of the invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations based on the technical teachings disclosed in this invention without departing from the spirit of the invention, and these modifications and combinations are still within the scope of protection of this invention.

Claims

1. An intelligent purification coating with biomimetic membrane-like respiratory and metabolic functions, characterized in that, It includes a sensing and adsorption layer, a driving and transport layer, and a catalytic and metabolic unit; Sensing and Adsorption Layer: Composed of a chemical heterojunction network formed by the in-situ coordination reaction of metal ions with hydroxyl groups on the surface of MXene and two-dimensional transition metal carbonitride MXene and zeolite imidazole ester framework material; Drive and transport layer: Located below the sensing and adsorption layer; this layer uses a cross-linked liquid crystal elastomer network as the smart response matrix, in which iron oxide nanorods modified with silane coupling agent are uniformly dispersed and embedded; the long axis of the nanorods is highly oriented along a direction perpendicular to the coating plane; hydrophobic ionic liquid completely penetrates and fills the free volume of the liquid crystal elastomer network and the micro-nano channels of the interface region between the nanorods and the cross-linked liquid crystal elastomer network, forming a plasticized and lubricated ion-conductive composite; Catalysis and Metabolism Layer: Anchored in the form of discrete "metabolic islands" on the pre-defined key mass transfer pathways within the driving and transport layer; each "metabolic island" is a multi-level core-shell structure, with an all-inorganic perovskite cesium lead bromine quantum dots as the core and a nitrogen-doped ordered mesoporous carbon as the shell. Laccase molecules are covalently fixed to the inner walls of the pores of the mesoporous carbon. At the same time, the all-inorganic perovskite cesium lead bromine quantum dots are covalently connected to specific sites on the laccase molecules through a flexible polyethylene glycol chain, forming a "quantum dot-connector arm-laccase" molecular hybrid.

2. A method for preparing an intelligent purification coating with biomimetic membrane respiratory and metabolic functions, used to prepare the coating as described in claim 1, characterized in that, Includes the following steps: S1. Preparation of the multifunctional unit precursor, including the following sub-steps: Preparation of S1-1, MXene-zeolite imidazole ester framework structure material chemical heterojunction precursor sol: Monolayer / few-layer MXene obtained by hydrofluoric acid etching and ultrasonic exfoliation was dispersed in anhydrous methanol; zinc nitrate hexahydrate and 2-methylimidazole were added to the dispersion in sequence, and the reaction was carried out by magnetic stirring in a constant temperature oil bath; after the reaction was completed, the product was washed three times by centrifugation with methanol to remove unreacted substances, and finally the precipitate was re-dispersed ultrasonically in a mixed solvent composed of N,N-dimethylformamide and isopropanol in a volume ratio of 1:1 to obtain a homogeneous sol for later use; S1-2. Preparation of liquid crystal elastomer prepolymer composite slurry: Under light-protected conditions, the liquid crystal elastomer prepolymer was completely dissolved in redistilled chloroform to form a clear solution; iron oxide nanorods modified with oil-based primary amine surface functionalization were added to the solution, and then the mixture was placed in an ice-water bath and treated with a high-energy probe ultrasonic cell disruptor to ensure that the nanorods were uniformly dispersed and free from agglomeration; subsequently, a free radical photoinitiator and a chain transfer agent were added sequentially, the mixture was magnetically stirred at low speed and placed in a vacuum dryer for degassing to obtain a magnetic liquid crystal prepolymer slurry; S1-3, the synthesis of "metabolic islands"; involving the following multi-level assembly: S1-3-1 Synthesis of amino-functionalized nitrogen-doped ordered mesoporous carbon: Amino groups are introduced into the surface and pore walls of nitrogen-doped ordered mesoporous carbon through a silanization reaction to obtain amino-functionalized nitrogen-doped ordered mesoporous carbon powder. S1-3-2, Bioconjugation of Laccase and Quantum Dots: Laccase was dissolved in phosphate buffer; excess of the heterobifunctional cross-linking agent N-hydroxysuccinimide-polyethylene glycol-maleimide was dissolved in dimethyl sulfoxide and added dropwise to the laccase solution; the activated ester end of the N-hydroxysuccinimide of the cross-linking agent molecule underwent a coupling reaction with the ε-amino group of the lysine residue on the surface of laccase to obtain the maleimide-polyethylene glycol-laccase derivative; S1-3-3 Synthesis of thiolized perovskite cesium lead bromine quantum dots: Ligand exchange was performed on inorganic perovskite cesium lead bromine quantum dots, and excess mercaptopropionic acid was introduced as a capping ligand to enrich the surface of the all-inorganic perovskite cesium lead bromine quantum dots with thiol groups, thus obtaining thiolized perovskite cesium lead bromine quantum dots; S1-3-4, Click chemical assembly and immobilization: The purified maleimide-polyethylene glycol-laccase derivative was mixed with thiolated perovskite cesium lead bromine quantum dots to obtain hybrid molecules; S1-3-5, Carrier Loading: Hybrid molecules and amino-functionalized nitrogen-doped ordered mesoporous carbon powder are co-dispersed in phosphate buffer, allowing the hybrid molecules to diffuse into the mesoporous channels; then the system is placed in a glutaraldehyde vapor environment for cross-linking, where glutaraldehyde reacts with the amino groups of the amino-functionalized nitrogen-doped ordered mesoporous carbon and the unreacted amino groups on laccase to undergo a Schiff base reaction, firmly anchoring the hybrid molecules within the channels; finally, the "metabolic island" powder is obtained by freeze-drying. S2. Magnetic field-induced liquid crystal alignment and in-situ curing of the driving layer substrate, including the following sub-steps: S2-1. Establishing the magnetic field environment: Fix the target substrate horizontally at the center of a uniform steady-state magnetic field device generated by a Helmholtz coil or permanent magnet array; adjust the magnetic field direction to be strictly perpendicular to the substrate surface. S2-2, Slurry Coating and Magnetic Field Orientation: The magnetic liquid crystal prepolymer slurry prepared in S1-2 is used to form a uniform wet film on the substrate surface through a precision spin coater or an automatic blade coater; the coating process is completed under the continuous action of a magnetic field; S2-3, Orientation Curing: Under the action of a strong vertical magnetic field, the long axis of the iron oxide nanorods in the wet film is driven by the magnetic torque, and they rapidly turn and align along the Z-axis within milliseconds; then, a high-intensity LED surface light source is used to vertically irradiate the wet film, triggering a photopolymerization reaction, which causes the liquid crystal monomers to crosslink and cure, thus obtaining the driving and transport layer. S3. Constructing a high-bonding-strength sensing layer through vapor-phase infiltration mineralization, including the following sub-steps: S3-1. Transfer the substrate prepared in S2 into a sealed stainless steel vapor deposition reaction chamber and fix it on a sample stage with precise temperature control. S3-2, Precursor vaporization and transport: The MXene-zeolite imidazolium ester framework structure material chemical heterojunction precursor sol prepared in S1-1 is transferred into the quartz heating boat at the bottom of the reaction chamber. After the N,N-dimethylformamide and isopropanol solvents evaporate, a precursor vapor containing MXene sheets and zeolite imidazolium ester framework structure material particles is formed. S3-3, Gas-solid interface self-assembly: High-purity nitrogen gas is introduced into the reaction chamber as a carrier gas; the carrier gas carries the precursor vapor upward and contacts the surface of the substrate above. The precursor vapor condenses, adsorbs and diffuses on the surface of the substrate to form a three-dimensional interpenetrating porous heterostructure network. S4. Femtosecond laser optical trap programming and assembly of integrated metabolic units, including the following sub-steps: S4-1, Preparation of the metabolic unit dispersion system: The "metabolic island" powder prepared in S1-3 is uniformly dispersed in low viscosity, optically transparent silicone oil at a concentration of 5wt%, and a stable suspension is formed by long-term gentle ultrasonication and oscillation. S4-2. Establishment of the femtosecond laser optical trap system: Transfer the suspension to a transparent sample cell; irradiate the sample using a femtosecond laser processing system; S4-3, Optical Capture and Manipulation: When the laser is focused on a point, an extremely strong three-dimensional gradient light field is generated near the focal point, forming an "optical micro-trap" or "optical tweezers" to capture and bind one or more nearby "metabolism island" particles; by using a high-precision piezoelectric displacement stage or acousto-optic deflector to control the position of the laser focal point in three-dimensional space, the captured particles are dragged out of the suspension and precisely transported to the preset coordinates of the driving and transport layer surface or its internal channels in S2; S4-4 Patterned Programming Assembly: Based on the simulation results of the internal flow field and pollutant concentration field of the coating in the "breathing" mode, the optimal spatial distribution pattern of the "metabolic islands" is pre-designed; the "metabolic islands" are transported and released one by one to the designated position to form the coating area. S4-5, In-situ Chemical Anchoring and Post-treatment: After placing all the "metabolic islands", an anhydrous ethanol solution containing 3-aminopropyltriethoxysilane is dropped onto the coating area using a microsyringe to allow it to penetrate into the assembled structure; finally, the entire system is placed in a supercritical CO2 dryer to obtain a dry, porous, and structurally complete intermediate coating. S5. Ionic liquid functionalization wetting and network depth enhancement, including the following sub-steps: S5-1, Ionic liquid permeation: The intermediate coating obtained in S4 is completely immersed in a container containing a hydrophobic ionic liquid; the container is placed in a vacuum oven at 50°C, and the vacuum is evacuated to below 10 Pa and maintained for 2 hours; S5-2, Deep thermal crosslinking and curing: Remove the intermediate coating and gently wipe away excess ionic liquid from the surface with a lint-free paper; then place the sample into a programmed temperature tube furnace and heat it from room temperature to 120°C at a slow heating rate of 0.5°C / min under the protection of continuously flowing high-purity nitrogen. The temperature is then maintained at this temperature for 8 hours to complete the preparation of the intelligent purification coating with complete biomimetic lung membrane respiratory and metabolic functions.

3. The coating preparation method according to claim 2, characterized in that, In step S4-4, the spatial distribution pattern of the "metabolic islands" is optimized through multiphysics coupling simulation; the specific method is as follows: First, a computational model is established based on the true three-dimensional microstructure of the coating; Then, computational fluid dynamics was used to simulate the velocity, pressure distribution and variation of the internal airflow field of the coating under the driving mode established in S2; at the same time, the mass transfer process of pollutant molecules adsorption in the sensing layer, diffusion in the pores and convective transport was coupled and calculated. With the objective function of "making as many pollutant molecules as possible come into contact with and react with the metabolic islands within a unit time", the optimal non-uniform distribution coordinates of the metabolic islands in the three-dimensional space of the coating are iteratively calculated using a genetic algorithm optimization method.