A graphene / Hf6Ta2O with wide environmental adaptability 17 Hierarchical porous composite aerogels, their preparation methods and applications

Abstract

The application discloses a graphene / Hf6Ta2O 17 The application relates to a hierarchical porous composite aerogel, a preparation method thereof and application, and relates to the technical field of functional porous materials. In the application, hafnium sources and tantalum sources are dissolved in acid, then transferred and mixed by using an alcohol solvent to prepare a precursor, and then the precursor is combined with an oxidized graphene dispersion liquid to construct a sol system, and finally, the product is prepared through hydrothermal self-assembly, solvent replacement and freeze drying. The aerogel obtained in the application has a hierarchical porous structure, and has excellent adsorption capacity and catalytic degradation efficiency for toxic agents. The material is stable in performance under extreme environments of high humidity (10%-95% RH) and variable air pressure (0.5-2 atm), overcomes the defects that traditional materials are easily disturbed by environments, and has a wide application prospect in the fields of efficient air purification and complex environment protection.

Description

Technical Field

[0001] This invention relates to the field of functional porous materials technology, and in particular to a graphene / Hf6Ta2O with wide environmental adaptability. 17 Hierarchical porous composite aerogels, their preparation methods, and applications. Background Technology

[0002] With the acceleration of industrialization and the continuous increase in the demand for safety protection in complex environments, efficient and stable porous adsorption and degradation materials have become the research focus in the field of air purification and protective filtration. In particular, in special application scenarios with high humidity and frequent air pressure fluctuations, higher requirements are placed on the environmental adaptability of materials.

[0003] In existing technologies, porous materials such as activated carbon, porous metal oxides, and pure graphene aerogels have been widely used in the field of adsorption, but they all have significant performance shortcomings: Although activated carbon has a high specific surface area, its pore structure is mainly micropores, which limits its mass transfer efficiency. Moreover, in high humidity environments, water molecules tend to preferentially occupy adsorption sites, leading to a significant decrease in the adsorption capacity for target harmful aerosols; Although porous metal oxide materials have certain catalytic degradation activity, they generally suffer from problems such as easy aggregation of nanoparticles, limited specific surface area, and poor structural stability, making it difficult to achieve efficient and long-lasting pollutant treatment; Pure graphene aerogels rely on a three-dimensional porous carbon structure and have excellent mechanical strength and high-flux mass transfer channels, but their adsorption mechanism is mainly physical adsorption. In high humidity environments, they are easily affected by water competition adsorption, and their own catalytic degradation capacity is insufficient, failing to achieve synergistic adsorption and degradation functions, making it difficult to meet the needs of use in complex environments.

[0004] Hafnium-tantalum composite oxides have shown potential application value in the field of pollutant degradation due to their excellent chemical stability and catalytic activity. However, when used alone, these materials suffer from problems such as easy agglomeration of nanoparticles, uncontrollable pore structure, and low mass transfer efficiency, making them difficult to apply directly to practical adsorption and degradation scenarios.

[0005] In summary, existing porous adsorption and degradation materials generally suffer from poor adaptability to a wide range of environments, difficulty in synergistic adsorption and degradation functions, and insufficient structural stability. Under conditions of wide humidity (10%–95%) and atmospheric pressure fluctuations (0.5–2 atm), they are prone to significant performance degradation, failing to meet the practical application requirements of emergency protection, high-level filtration, and air purification in special environments. Therefore, developing a novel composite aerogel material that combines a hierarchical porous structure, synergistic adsorption-degradation effect, and wide environmental adaptability to solve the performance degradation problem of existing materials in complex environments has become an urgent technical challenge in this field. Summary of the Invention

[0006] The purpose of this invention is to provide a graphene / Hf6Ta2O with wide environmental adaptability. 17 Hierarchical porous composite aerogels, their preparation methods, and applications are proposed to address the problems existing in the aforementioned technologies. This is achieved by directionally constructing a three-dimensional graphene network framework and forming Hf6Ta2O on this framework. 17 The stable interfacial structure between nanoparticles enables the prepared composite aerogel to possess both the high mechanical strength of graphene and the advantages of a three-dimensional hierarchical porous structure formed through process control, while also incorporating Hf6Ta2O 17 The high catalytic activity against the target pollutant can solve the problem of performance degradation of existing porous materials under high humidity and pressure change environments.

[0007] To achieve the above objectives, the present invention provides the following solution: This invention provides a graphene / Hf6Ta2O 17 A method for preparing hierarchical porous composite aerogels includes the following steps: (1) Preparation of precursor solution: Hafnium source and tantalum source were added to acidic solvent and mixed by transfer with alcohol solvent to obtain Hf6Ta2O 17 Precursor solution; (2) Preparation of sol system: The graphene oxide dispersion was mixed with the Hf6Ta2O 17 The precursor solutions are mixed to obtain a sol system; (3) Hydrothermal self-assembly: The sol system is subjected to a hydrothermal reaction to obtain a hydrogel; (4) Solvent replacement: The hydrogel is subjected to solvent replacement; (5) Drying and shaping: The hydrogel after solvent replacement was freeze-dried to obtain graphene / Hf6Ta2O with a three-dimensional hierarchical porous structure of macropore-mesopore-micropore. 17 Hierarchical porous composite aerogel.

[0008] Furthermore, the hydrothermal reaction is carried out at a temperature of 120-140 °C for a duration of 12-14 h.

[0009] Furthermore, the hafnium source is n-butoxide hafnium, and the tantalum source is ethanol tantalum.

[0010] This invention effectively suppresses the violent hydrolysis and aggregation of hafnium and tantalum metal alkoxides in acidic environments through an "alcohol solvent transfer mixing" method, achieving uniform mixing of bimetallic precursors at the molecular level. This facilitates the formation of Hf6Ta2O. 17 Nanoparticles can be uniformly loaded onto the surface of a three-dimensional graphene framework.

[0011] Furthermore, the solvent used for solvent replacement is tert-butanol.

[0012] Furthermore, the freeze-drying process further includes a calcination step: calcination is carried out in an inert gas atmosphere at a temperature of 750-1200 ℃ for 1-6 h.

[0013] Furthermore, the total molar ratio of graphene oxide to hafnium and tantalum is 1.34:1 to 1:3.72 (graphene oxide is expressed according to the empirical formula C). 10 The molar mass of O4H2 is calculated to be 186.12 g / mol; Hf6Ta2O 17 (Molar mass is 1999.84 g / mol), corresponding to graphene oxide and the theoretically generated Hf6Ta2O. 17 The mass ratio is 1:1 to 1:5, and the molar ratio of hafnium n-butoxide to tantalum ethoxide is 3:1.

[0014] Furthermore, the concentration of the graphene oxide dispersion is 4~6 mg / mL.

[0015] This invention also provides graphene / Hf6Ta2O prepared by the above preparation method. 17 Hierarchical porous composite aerogel.

[0016] The composite aerogel of this invention comprises a three-dimensional graphene network framework and Hf6Ta2O uniformly loaded on the surface of the framework. 17 Nanoparticles have a hierarchical porous structure consisting of macropores, mesopores, and micropores.

[0017] The composite aerogel of this invention has a specific surface area ≥450m² / g, a total pore volume ≥1.2 cm³ / g, and an adsorption capacity fluctuation of no more than 10% within an environmental range of relative humidity 10%–95% and air pressure 0.5–2 atm.

[0018] The composite aerogel of this invention has an adsorption capacity of ≥300 mg / g for toxic agent simulant aerosols and a degradation efficiency of ≥90%.

[0019] This invention also provides the above-mentioned graphene / Hf6Ta2O 17 Applications of hierarchical porous composite aerogels in air purification, remediation of environments contaminated by toxic agents, or preparation of protective filter products.

[0020] The present invention also provides an adsorbent for protective filtration or environmental remediation, the effective component of which includes the above-mentioned graphene / Hf6Ta2O. 17 Hierarchical porous composite aerogel.

[0021] The graphene / Hf6Ta2O prepared by this invention 17 A hierarchical porous composite aerogel material was successfully constructed with a three-dimensional hierarchical porous structure, which not only effectively improved the mass transfer efficiency but also significantly enhanced the utilization rate of adsorption sites, laying a structural foundation for the efficient adsorption of target pollutants.

[0022] The material of this invention exhibits excellent adaptability to a wide range of environments, solving the technical problem of performance degradation of existing porous materials under complex environments. Within a wide relative humidity range of 10%-95%, the adsorption capacity fluctuation of the material is less than 10%, significantly better than the 20%-50% performance degradation of conventional porous materials under high humidity environments. In an atmospheric pressure environment of 0.5-2 atm, the material's structure remains stable, with no significant fluctuation in adsorption performance, demonstrating good resistance to atmospheric pressure changes and adaptability to various complex application environments. Furthermore, this material also exhibits good performance under high humidity and high pressure, high humidity and low pressure, and low humidity and high pressure conditions.

[0023] The material of this invention also possesses excellent structural and performance stability. Even after accelerated aging tests, it maintains a high adsorption capacity and intact structural morphology, demonstrating good long-term service stability and effectively extending the material's actual service life. In summary, the graphene / Hf6Ta2O of this invention... 17 Hierarchical porous composite aerogels have outstanding comprehensive performance and can be widely used in high-performance air purification, protective filtration and other fields, with high practical application value and industrialization potential.

[0024] The present invention discloses the following technical effects: The aerogel prepared by this invention has a complete three-dimensional hierarchical porous structure of macropores, mesopores, and micropores. Among them, macropores serve as material transport channels, reducing diffusion resistance, while mesopores and micropores provide abundant adsorption sites and a huge specific surface area. This multi-level pore synergy enables the material to exhibit excellent adsorption capacity and efficient degradation ability when facing toxic agent aerosols, solving the technical bottleneck of slow mass transfer and low capacity of traditional adsorption materials.

[0025] The composite material of this invention exhibits excellent environmental adaptability, thanks to the hydrophobic modification effect of the graphene network and Hf6Ta2O. 17 The material exhibits excellent chemical stability; even under extreme fluctuations in relative humidity (10%-95%) and air pressure (0.5-2 atm), its adsorption capacity fluctuates by no more than 10%. This characteristic overcomes the shortcomings of existing aerogel materials, which are susceptible to a sharp drop in performance due to environmental humidity. This makes it highly valuable and reliable in complex and ever-changing scenarios such as air purification, protective filtration, and emergency environmental pollution remediation. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 Graphene / Hf6Ta2O prepared in Example 1 17 Scanning electron microscope image of hierarchical porous composite aerogel; Figure 2 Graphene / Hf6Ta2O prepared in Example 1 17 Pore ​​size distribution curve of hierarchical porous composite aerogel; Figure 3 Graphene / Hf6Ta2O prepared in Example 1 17 Thermal stability curves of hierarchical porous composite aerogels in a nitrogen atmosphere; Figure 4 shows the graphene / Hf6Ta2O prepared in Examples 1-3. 17 Adsorption performance of hierarchical porous composite aerogels and materials prepared in comparative examples 1-4 under different humidity conditions (25℃, 1 atm, initial DMMP concentration 1000 mg / m³). Figure 5 shows the graphene / Hf6Ta2O prepared in Example 1. 17 Adsorption performance of hierarchical porous composite aerogel at different initial DMMP concentrations (25℃, 1 atm, 50% RH); Figure 6 shows the graphene / Hf6Ta2O prepared in Examples 1-3. 17 DMMP adsorption performance of hierarchical porous composite aerogels and materials prepared in comparative examples 1-4 under different pressure conditions (25℃, 50% RH, initial DMMP concentration 1000mg / m³). Figure 7 shows the graphene / Hf6Ta2O prepared in Examples 1-3. 17 Adsorption-regeneration cycle DMMP adsorption performance of hierarchical porous composite aerogels and materials prepared in comparative examples 1-4 (25℃, 1 atm, 50% RH, initial DMMP concentration 1000 mg / m³). Figure 8 shows the graphene / Hf6Ta2O prepared in Examples 1-3. 17 Comparison of DMMP adsorption and degradation performance of hierarchical porous composite aerogels and materials prepared in comparative examples 1-4 after accelerated aging under high temperature and high humidity (80℃, 95% RH, 1 atm, aging for 30 days, initial DMMP concentration of 1000 mg / m³). Figure 9 shows the graphene / Hf6Ta2O prepared in Examples 1-3. 17 Comparison of DMMP adsorption performance of hierarchical porous composite aerogel and materials prepared by comparative examples 1-4 after accelerated aging under high pressure, high temperature and high humidity (80℃, 95% RH, 2atm / 5atm, aging for 30 days, initial DMMP concentration of 1000mg / m³). Detailed Implementation

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0029] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0030] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0031] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0032] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0033] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0034] Unless otherwise specified, room temperature and normal temperature in the specific embodiments of this invention refer to 20-30℃.

[0035] Performance testing methods and standards: The material properties of all embodiments and comparative examples in this invention were tested according to the following methods. The adsorption capacity was calculated based on the mass of the material dried to constant weight. The target adsorbate was aerosol of a poison agent simulant (dimethyl methylphosphonate, DMMP, sarin poison agent simulant). The degradation efficiency was measured for DMMP. The specific test methods are as follows: 1. Adsorption capacity test: Static adsorption method was used, with test conditions of 25℃, 50% RH, and 1 atm; a mass of... m 0 g of dry composite aerogel was placed in a sealed test chamber, and an initial concentration of [missing information] was introduced. C 0 (mg / m 3 After adsorption of DMMP aerosol to equilibrium, the concentration of DMMP in the chamber at equilibrium was determined by gas chromatography-FID. C 1 (mg / m 3 The test chamber volume is V (m) 3 Then the adsorption capacity Q The formula for calculating (mg / g) is: .

[0036] 2. Degradation efficiency test: Dynamic catalytic degradation test was adopted, and the test conditions were 25℃, 50% RH, and 1 atm; the mass of m 0 g of composite aerogel was placed in a reaction tube, and an initial concentration of 0 g was introduced. C 0 (mg / m 3 DMMP aerosol was reacted at a flow rate of 100 mL / min for 2 hours. The concentration of DMMP in the gas after the reaction was then determined by gas chromatography-fiber spectroscopy (GC-FID). C t (mg / m 3 Degradation efficiency η The formula for calculating (%) is: .

[0037] 3. Humidity gradient performance test: The test environment temperature was controlled at 25℃ and the air pressure at 1 atm. The relative humidity was set at three gradients: 10%, 50%, and 95%. The initial concentration of DMMP aerosol was 1000 mg / m³ and the particle size distribution was 0.3~2.5 μm. The adsorption capacity was tested according to the static adsorption method described above, and the fluctuation range of the adsorption capacity was calculated.

[0038] 4. Pressure gradient performance test: The test environment temperature was controlled at 25℃ and the relative humidity at 50%. Three pressure gradients were set: 0.5 atm, 1 atm, and 2 atm. The initial concentration of DMMP aerosol was 1000 mg / m³ and the particle size distribution was 0.3~2.5 μm. The adsorption capacity was tested according to the static adsorption method described above.

[0039] 5. Accelerated aging performance test (1) High temperature and high humidity aging: The material was placed in an environment of 80℃, 95% RH and 1atm for 30 days. After aging, the adsorption capacity and degradation efficiency of DMMP aerosol (initial concentration 1000mg / m³, particle size 0.3~2.5μm) were tested under the conditions of 25℃, 50% RH and 1atm, and the performance degradation rate was calculated. (2) High pressure, high temperature and high humidity aging: The material was placed in an environment of 80℃ and 95% RH, and the air pressure was set to 2 atm and 5 atm respectively. The aging was continued for 30 days. After aging, the DMMP adsorption capacity and degradation efficiency were tested under the above conditions, and the performance degradation range was calculated.

[0040] 6. Cyclic Regeneration Performance Test: The material after adsorption saturation was regenerated by vacuum heating at 120℃. The adsorption-regeneration operation was repeated 10 times under the conditions of 25℃, 1 atm, and 50% RH. Each adsorption used DMMP aerosol with an initial concentration of 1000 mg / m³ and a particle size of 0.3~2.5 μm. The adsorption capacity of each cycle was tested, and the capacity retention rate was calculated.

[0041] 7. Concentration adaptability test: The test environment was controlled at 25℃, 1 atm, and 50% relative humidity. Four initial concentrations of DMMP aerosol were set at 500mg / m³, 1000mg / m³, 1500mg / m³, and 2000mg / m³, with a particle size distribution of 0.3~2.5μm. The adsorption capacity was tested according to the static adsorption method described above.

[0042] 8. Coupled Environment Performance Test: The test environment temperature was controlled at 25℃. Three typical extreme coupled environments were set up, with an initial DMMP aerosol concentration of 1000 mg / m³ and a particle size distribution of 0.3~2.5 μm. The adsorption capacity was tested using the static adsorption method, and the degradation efficiency was tested using the dynamic catalytic degradation method. The deviation rate of performance from that of the conventional environment (25℃, 50% RH, 1 atm) was calculated. (1) High humidity and high pressure: 95% RH, 2 atm; (2) High humidity and low pressure: 95% RH, 0.5 atm; (3) Low humidity and high pressure: 10% RH, 2 atm.

[0043] Preparation method of graphene oxide dispersion: Add 4 g of flake graphite and 3 g of sodium nitrate to 150 mL of concentrated sulfuric acid, place the mixture in a 1000 mL beaker, and stir vigorously with a magnetic stirrer under ice-water bath cooling conditions. Add 18 g of potassium permanganate to the suspension in multiple portions. The sample addition process takes about 1 hour. After the sample addition is completed, remove the ice-water bath and place the system at room temperature for 5 days to react. During the reaction, the mixture gradually thickens into a paste-like state, accompanied by the generation of a small amount of gas. After the reaction was completed, 300 mL of deionized water was slowly added to the system. At this time, a large number of bubbles were generated and the system temperature rapidly rose to about 98°C. The suspension turned brown. The temperature was maintained and the reaction was continued for 15 min. Then, 500 mL of 3% hydrogen peroxide was added to convert the remaining potassium permanganate and manganese dioxide in the system into manganese sulfate. After treatment, the suspension turned bright yellow. Add deionized water to the bright yellow suspension and bring the volume to 2 L. Let it stand for 6 h and then pour off the supernatant. Add 5% HCl solution to bring the volume to 2 L and stir for 10 min. Repeat this acid washing operation 4 times. Replace the 5% HCl solution with deionized water and repeat the above dilution, standing, pouring off the supernatant, and stirring water washing operation 3 times. After the last water washing, bring the volume of the system to 1.2 L, pour off the supernatant, and centrifuge the precipitate. The precipitate after centrifugation was transferred to a dialysis bag and dialyzed four times with deionized water. The dialyzed graphite oxide was diluted with water to 1200 mL, and then ultrasonically dispersed using an ultrasonic cleaner to obtain a yellowish-brown, uniformly dispersed 5 mg / mL graphene oxide aqueous dispersion. Further detailed explanation is provided below with reference to examples: Example 1 This embodiment provides a graphene / Hf6Ta2O 17 The preparation steps for hierarchical porous composite aerogel are as follows: S1. Using the above-mentioned method for preparing graphene oxide dispersion, prepare a 5 mg / mL aqueous dispersion of graphene oxide. S2, Preparation of Hf6Ta2O 17 Precursor solution: Take 3 mmol of hafnium n-butoxide and 1 mmol of tantalum ethoxide in a molar ratio of 3:1, add 2 mL of glacial acetic acid to each and mix well; then transfer both materials to the same container with 5 mL of anhydrous ethanol, stir at 25 °C for 5 min to obtain homogeneous Hf6Ta2O. 17 Precursor solution; S3. Preparation of composite aerogel: Take 50 mL of the above 5 mg / mL graphene oxide dispersion, add 1 mL of glacial acetic acid to adjust the pH to 3, and ultrasonically disperse for 10 min; mix the graphene oxide dispersion with the Hf6Ta2O obtained in S2. 17The precursor solutions were mixed at a 1:1 volume ratio and stirred homogenously for 10 min to form a uniform sol system. The sol system was subjected to a hydrothermal reaction at 130℃ for 12 h, resulting in a hydrogel. The hydrogel was then subjected to solvent replacement in tert-butanol, with the tert-butanol being replaced every 12 h for 4 days. The solvent-replaced gel was then freeze-dried at -55℃ for 36 h to obtain a preliminary graded porous composite aerogel. Finally, the preliminary aerogel was calcined at 900℃ for 1 h under an argon atmosphere to obtain graphene / Hf6Ta2O. 17 Hierarchical porous composite aerogel.

[0044] Figure 1 Graphene / Hf6Ta2O prepared in Example 1 17 Scanning electron microscope image of the hierarchical porous composite aerogel. It can be seen that this composite aerogel material possesses a rich porous structure.

[0045] Figure 2 Graphene / Hf6Ta2O prepared in Example 1 17 The pore size distribution curves of the hierarchical porous composite aerogel show that the sample exhibits a typical hierarchical porous structure, with pore sizes covering micropores, mesopores, and macropores. Significant pore volume contributions are observed in the region with pore sizes less than 2 nm, indicating the presence of microporous structures. Multiple significant peaks appear in the 2–50 nm range, corresponding to a rich mesopore distribution, which is the main contributor to the sample's pore volume. Observable pore volume signals are still present in the region with pore sizes greater than 50 nm, indicating the simultaneous presence of macroporous structures in the sample. The synergistic existence of these multi-level channels provides multidimensional pathways for mass transport and reactions, which is beneficial for improving the material's mass transfer efficiency and active site utilization.

[0046] Figure 3 Graphene / Hf6Ta2O prepared in Example 1 17 Thermal stability curves of hierarchical porous composite aerogels in a nitrogen atmosphere. Within a temperature range of 40℃ to 800℃, the material maintains a mass retention rate close to 100%, exhibiting only very slight mass fluctuations and no obvious weight loss steps or rapid decline trend. This demonstrates that the material possesses excellent high-temperature thermal stability and is not prone to decomposition, volatilization, or other reactions leading to mass loss under high-temperature environments.

[0047] Graphene / Hf6Ta2O prepared in Example 1 17 The specific surface area of ​​the hierarchical porous composite aerogel is 512 m². 2 g -1 The total pore volume is 1.36 cm³. 3 g -1 .

[0048] Material performance test results: The graphene / Hf6Ta2O prepared in this embodiment was subjected to conditions of 25°C, 50% RH, and 1 atm. 17 The hierarchical porous composite aerogel exhibited an adsorption capacity of 332 mg / g for DMMP aerosol and a degradation efficiency of 94%. Concentration adaptability testing showed that the degradation efficiency was 94% at initial DMMP concentrations of 500, 1000, 1500, and 2000 mg / m³. 3 At RH, the adsorption capacities were 285, 332, 368, and 392 mg / g, respectively (Figure 5). Humidity gradient tests showed that under RH conditions of 10%, 50%, and 95%, the adsorption capacities were 335, 332, and 318 mg / g, respectively, with a fluctuation range of only 4.2% (Figure 4). Pressure gradient tests showed that under RH conditions of 0.5, 1, and 2 atm, the adsorption capacities were 325, 332, and 339 mg / g, respectively, with no significant performance fluctuation (Figure 6).

[0049] In accelerated aging performance testing, after aging for 30 days at 80℃, 95% RH, and 1 atm, the material's adsorption capacity was 289 mg / g, and the degradation efficiency was 89% (Figure 8). After aging for 30 days at 80℃ and 95% RH, the adsorption capacity after 2 atm aging was 295 mg / g, the degradation efficiency was 88%, and the performance degradation was 11%. After 5 atm aging, the adsorption capacity was 282 mg / g, the degradation efficiency was 86%, and the performance degradation was 14%. After aging, the pore structure remained intact without collapse, and the nanoparticles did not agglomerate. Figure 9 ).

[0050] Cyclic regeneration performance tests showed that after 10 adsorption-regeneration cycles, the adsorption capacities in the 1st, 5th, and 10th cycles were 332, 315, and 301 mg / g, respectively, with a capacity retention rate of 90.7% (Figure 7). Coupled environment performance tests indicated that the material's adsorption and degradation performance remained stable under three extreme coupled environments, with deviation rates less than 8% compared to conventional environments: under high humidity and high pressure (95% RH, 2 atm), the adsorption capacity was 326 mg / g, the degradation efficiency was 91%, and the performance deviation rate was 5.4%; under high humidity and low pressure (95% RH, 0.5 atm), the adsorption capacity was 321 mg / g, the degradation efficiency was 90%, and the performance deviation rate was 6.6%; under low humidity and high pressure (10% RH, 2 atm), the adsorption capacity was 330 mg / g, the degradation efficiency was 93%, and the performance deviation rate was 2.4%.

[0051] Example 2 The only difference from Example 1 is that in step S3, the hydrothermal reaction temperature is 140°C and the time is 14 hours.

[0052] Graphene / Hf6Ta2O prepared in Example 2 17 The specific surface area of ​​the hierarchical porous composite aerogel is 485 m². 2 g -1 The total pore volume is 1.28 cm³ / g.

[0053] Material performance test results: The graphene / Hf6Ta2O prepared in this embodiment was subjected to conditions of 25°C, 50% RH, and 1 atm. 17 The hierarchical porous composite aerogel exhibited an adsorption capacity of 315 mg / g for DMMP and a degradation efficiency of 92%. Humidity gradient performance testing (25℃, 1 atm, initial DMMP concentration 1000 mg / m³) showed adsorption capacities of 320, 315, and 300 mg / g under 10%, 50%, and 95% RH conditions, with a fluctuation range of 4.8% (Figure 4). Pressure gradient performance testing (25℃, 50% RH, initial DMMP concentration 1000 mg / m³) indicated adsorption capacities of 308, 315, and 322 mg / g under 0.5, 1, and 2 atm conditions, with a fluctuation range of 4.4% (Figure 6).

[0054] In accelerated aging performance testing, after aging for 30 days at 80℃, 95% RH, and 1 atm, the material adsorption capacity was 278 mg / g and the degradation efficiency was 89% (Figure 8); after aging for 30 days at 80℃ and 95% RH, the adsorption capacity at 2 atm was 285 mg / g and the degradation efficiency was 88%, with a performance degradation of 9.5%; at 5 atm, the adsorption capacity was 275 mg / g and the degradation efficiency was 87%, with a performance degradation of 12.7%. The material structure remained intact and undamaged after aging (Figure 9).

[0055] Cyclic regeneration performance tests (25℃, 1 atm, 50% RH, 10 cycles) showed that the adsorption capacities at the 1st, 5th, and 10th cycles were 315, 305, and 298 mg / g, respectively, with a capacity retention rate of 94.6% (Figure 7). Coupled environment performance tests (25℃, initial DMMP concentration 1000 mg / m³) indicated that the material was stable under three extreme coupled environments: under high humidity and high pressure (95% RH, 2 atm), the adsorption capacity was 308 mg / g, the degradation efficiency was 90%, and the performance deviation rate was 2.2%; under high humidity and low pressure (95% RH, 0.5 atm), the adsorption capacity was 302 mg / g, the degradation efficiency was 89%, and the performance deviation rate was 4.1%; under low humidity and high pressure (10% RH, 2 atm), the adsorption capacity was 312 mg / g, the degradation efficiency was 91%, and the performance deviation rate was 0.95%.

[0056] Example 3 The only difference from Example 1 is that in step S3, the calcination temperature is 1100°C and the time is 1 hour.

[0057] Graphene / Hf6Ta2O prepared in Example 3 17 The specific surface area of ​​the hierarchical porous composite aerogel is 455 m². 2 / g, with a total pore volume of 1.21cm³ / g.

[0058] Material performance test results: The graphene / Hf6Ta2O prepared in this embodiment was subjected to conditions of 25°C, 50% RH, and 1 atm. 17 The hierarchical porous composite aerogel exhibited an adsorption capacity of 305 mg / g for DMMP and a degradation efficiency of 91%. Humidity gradient performance testing (25℃, 1 atm, initial DMMP concentration 1000 mg / m³) showed adsorption capacities of 310, 305, and 290 mg / g under 10%, 50%, and 95% RH conditions, with a fluctuation range of 4.9% (Figure 4). Pressure gradient performance testing (25℃, 50% RH, initial DMMP concentration 1000 mg / m³) indicated adsorption capacities of 300, 305, and 310 mg / g under 0.5, 1, and 2 atm conditions, with a fluctuation range of 3.3% (Figure 6).

[0059] In accelerated aging performance testing, after aging for 30 days at 80℃, 95% RH, and 1 atm, the material adsorption capacity was 270 mg / g and the degradation efficiency was 86% (Figure 8); after aging for 30 days at 80℃ and 95% RH, the adsorption capacity at 2 atm was 278 mg / g and the degradation efficiency was 85%, with a performance degradation of 8.8%; at 5 atm, the adsorption capacity was 265 mg / g and the degradation efficiency was 84%, with a performance degradation of 13.1%. After aging, the material's pore structure remained intact, with no particle agglomeration (Figure 9).

[0060] Cyclic regeneration performance tests (25℃, 1 atm, 50% RH, 10 cycles) showed that the adsorption capacities at the 1st, 5th, and 10th cycles were 305, 298, and 290 mg / g, respectively, with a capacity retention rate of 95.1% (Figure 7). Coupled environment performance tests (25℃, initial DMMP concentration 1000 mg / m³) indicated that the material was stable under three extreme coupled environments: under high humidity and high pressure (95% RH, 2 atm), the adsorption capacity was 298 mg / g, the degradation efficiency was 89%, and the performance deviation rate was 2.3%; under high humidity and low pressure (95% RH, 0.5 atm), the adsorption capacity was 295 mg / g, the degradation efficiency was 88%, and the performance deviation rate was 3.3%; under low humidity and high pressure (10% RH, 2 atm), the adsorption capacity was 302 mg / g, the degradation efficiency was 90%, and the performance deviation rate was 0.98%.

[0061] Comparative Example 1: Pure Graphene Oxide Aerogel This comparative example provides a graphene oxide aerogel, and the preparation steps are as follows: S1. Using the above method for preparing graphene oxide dispersion, prepare a 5 mg / mL aqueous dispersion of graphene oxide. S2. Preparation of graphene oxide aerogel: Take 50 mL of the above 5 mg / mL graphene oxide dispersion, add 1 mL of glacial acetic acid to adjust the pH to 3, and ultrasonically disperse for 10 min to directly form a sol system; place the sol system at 130℃ for hydrothermal reaction for 12 h, and a hydrogel is formed after the reaction is completed; place the hydrogel in tert-butanol for solvent replacement, replacing the tert-butanol every 12 h for 4 days; freeze-dry the gel after solvent replacement at -55℃ for 36 h to obtain the initial aerogel; finally, place the initial aerogel in an argon atmosphere and calcine at 900℃ for 1 h to obtain graphene oxide aerogel.

[0062] The graphene oxide aerogel prepared in Comparative Example 1 had a specific surface area of ​​420 m². 2 g-1 The total pore volume is 0.98 cm³ / g.

[0063] Material performance test results Under conditions of 25℃, 50% RH, and 1 atm, the graphene oxide aerogel prepared in this comparative example exhibited an adsorption capacity of 285 mg / g for DMMP aerosol and a degradation efficiency of 65%. Humidity gradient performance testing (25℃, 1 atm, initial DMMP concentration of 1000 mg / m³) showed that the adsorption capacity fluctuated by 18% under 10%, 50%, and 95% RH conditions (Figure 4). Pressure gradient performance testing (25℃, 50% RH, initial DMMP concentration of 1000 mg / m³) indicated that the adsorption capacity at 0.5, 1, and 2 atm conditions was 278, 285, and 292 mg / g, respectively. Although the pressure adaptability was good, the adsorption capacity was lower than that of the embodiment of this invention (Figure 6).

[0064] In accelerated aging performance tests, after aging at 80℃, 95% RH, and 1 atm for 30 days, the material adsorption capacity was 212 mg / g and the degradation efficiency was 52% (Figure 8); after aging at 80℃ and 95% RH for 30 days, the adsorption capacity after 2 atm aging was 235 mg / g and the degradation efficiency was 58%, with a performance degradation of 17.5%; after aging at 5 atm, the adsorption capacity was 208 mg / g and the degradation efficiency was 50%, with a performance degradation of 27% (Figure 9).

[0065] Cyclic regeneration performance tests (25℃, 1 atm, 50% RH, 10 cycles) showed that the adsorption capacities at the 1st, 5th, and 10th cycles were 285, 262, and 241 mg / g, respectively, with a capacity retention rate of 84.6% (Figure 7). Coupled environment performance tests (25℃, initial DMMP concentration 1000 mg / m³) indicated that the material's performance significantly degraded under three extreme coupled environments, with deviations exceeding 20% ​​compared to conventional environments: under high humidity and high pressure (95% RH, 2 atm), the adsorption capacity was 221 mg / g, the degradation efficiency was 52%, and the performance deviation rate was 22.5%; under high humidity and low pressure (95% RH, 0.5 atm), the adsorption capacity was 215 mg / g, the degradation efficiency was 50%, and the performance deviation rate was 24.6%; under low humidity and high pressure (10% RH, 2 atm), the adsorption capacity was 258 mg / g, the degradation efficiency was 58%, and the performance deviation rate was 9.5%.

[0066] Comparative Example 2: Pure Hf6Ta2O 17 aerogel This comparative example provides a pure Hf6Ta2O 17 Aerogel, the preparation steps are as follows: (1) Take 3 mmol of hafnium butoxide and 1 mmol of tantalum ethoxide, dissolve them in 20 mL of anhydrous ethanol, add 5 mL of deionized water to hydrolyze, and stir at room temperature for 30 min; (2) Add 2 mL of propylene oxide as a coagulant and let it stand at 100 °C for 6 h to form a wet gel; (3) The wet gel was placed in anhydrous ethanol for solvent replacement. The ethanol was replaced every 12 hours for a total of 4 times. (4) The wet gel was dried using supercritical carbon dioxide to obtain Hf6Ta2O. 17 Aerogel precursors; (5) The precursor was heat-treated at 900℃ in an argon atmosphere for 1 h to obtain pure Hf6Ta2O. 17 Aerogel.

[0067] Pure Hf6Ta2O prepared in Comparative Example 2 17 The aerogel has a specific surface area of ​​320 m² / g and a total pore volume of 0.85 cm³ / g.

[0068] Material performance test results The pure Hf6Ta2O prepared in this comparative example was obtained under the conditions of 25℃, 50% RH, and 1 atm. 17 The aerogel exhibited an adsorption capacity of 185 mg / g for DMMP aerosol, with a degradation efficiency of 62%. Humidity gradient performance testing (25℃, 1 atm, initial DMMP concentration 1000 mg / m³) showed that the adsorption capacity decreased to 122 mg / g under 95% RH high humidity conditions, with a fluctuation range of 34% (Figure 4). Pressure gradient performance testing (25℃, 50% RH, initial DMMP concentration 1000 mg / m³) indicated that the adsorption capacities at 0.5, 1, and 2 atm were 172, 185, and 190 mg / g, respectively, significantly lower than those in the embodiment of this invention (Figure 6).

[0069] In the accelerated aging performance test, after aging for 30 days at 80℃, 95% RH and 1 atm, the adsorption capacity of the material was 142 mg / g and the degradation efficiency was 55% (Figure 8); after aging for 30 days at 80℃ and 95% RH, the adsorption capacities after aging at 2 atm and 5 atm were 155 mg / g and 138 mg / g, respectively, with degradation efficiencies not exceeding 50% and performance degradation greater than 20% (Figure 9).

[0070] Cyclic regeneration performance tests (25℃, 1 atm, 50% RH, 10 cycles) showed that the adsorption capacities at the 1st, 5th, and 10th cycles were 185, 162, and 145 mg / g, respectively, with a capacity retention rate of 78.4% (Figure 7). Coupled environment performance tests (25℃, initial DMMP concentration 1000 mg / m³) indicated that the material's performance significantly degraded under three extreme coupled environments, with performance deviation rates exceeding 35% in high-humidity coupled environments: under high humidity and high pressure (95% RH, 2 atm), the adsorption capacity was 118 mg / g, degradation efficiency was 50%, and performance deviation rate was 36.2%; under high humidity and low pressure (95% RH, 0.5 atm), the adsorption capacity was 112 mg / g, degradation efficiency was 48%, and performance deviation rate was 39.5%; under low humidity and high pressure (10% RH, 2 atm), the adsorption capacity was 168 mg / g, degradation efficiency was 58%, and performance deviation rate was 9.2%.

[0071] Comparative Example 3: Graphene / hafnium tantalum oxide composite aerogel with a hafnium-tantalum molar ratio of 2:1 This comparative example prepared graphene-supported hafnium tantalum oxide composite aerogel (without forming the target compound Hf6Ta2O). 17 The preparation steps are as follows: (1) Take 2 mmol of hafnium n-butoxide and 1 mmol of tantalum ethoxide, dissolve them in 20 mL of anhydrous ethanol, add 5 mL of deionized water for hydrolysis, and stir at room temperature for 30 min; (2) Add 50 mL of graphene oxide dispersion with a concentration of 5 mg / mL to the above solution, adjust the pH to 4, and ultrasonically disperse for 30 min; (3) Transfer to a hydrothermal reactor and react at 160°C for 12 hours to obtain a wet gel; (4) After solvent replacement and freeze-drying, graphene-supported hafnium tantalum oxide composite aerogel (without the target compound Hf6Ta2O) was obtained. 17 ).

[0072] The aerogel material prepared in Comparative Example 3 had a specific surface area of ​​380 m² / g and a total pore volume of 0.92 cm³ / g.

[0073] Material performance test results Under conditions of 25℃, 50% RH, and 1 atm, the graphene / hafnium tantalum oxide composite aerogel prepared in this comparative example exhibited an adsorption capacity of 225 mg / g for DMMP aerosol and a degradation efficiency of 72%. Humidity gradient performance testing (25℃, 1 atm, initial DMMP concentration 1000 mg / m³) was also performed. 3The results showed that the adsorption capacity of the material under high humidity (95% RH) was 185 mg / g, with a fluctuation range of 17.8% (Figure 4). Pressure gradient performance tests (25℃, 50% RH, initial DMMP concentration 1000 mg / m³) showed that the adsorption capacities of the material under conditions of 0.5, 1, and 2 atm were 210, 225, and 230 mg / g, respectively, which were lower than those in the embodiments of this invention (Figure 6).

[0074] In the accelerated aging performance test, after aging at 80℃, 95% RH and 1 atm for 30 days, the adsorption capacity of the material was 198 mg / g and the degradation efficiency was 65% (Figure 8); after aging at 80℃ and 95% RH for 30 days, the adsorption capacities after aging at 2 atm and 5 atm were 205 mg / g and 182 mg / g, respectively, and the degradation efficiency was no higher than 60% (Figure 9).

[0075] Cyclic regeneration performance tests (25℃, 1 atm, 50% RH, 10 cycles) showed that the adsorption capacities for the 1st, 5th, and 10th cycles were 225, 201, and 188 mg / g, respectively, with a capacity retention rate of 83.6% (Figure 7). Coupled environment performance tests (25℃, initial DMMP concentration 1000 mg / m³) 3 The results showed that the material's performance degraded significantly under three extreme coupling environments, with performance deviation rates exceeding 15% in the high-humidity coupling environment: under high humidity and high pressure (95% RH, 2 atm), the adsorption capacity was 182 mg / g, the degradation efficiency was 65%, and the performance deviation rate was 19.1%; under high humidity and low pressure (95% RH, 0.5 atm), the adsorption capacity was 178 mg / g, the degradation efficiency was 63%, and the performance deviation rate was 20.9%; under low humidity and high pressure (10% RH, 2 atm), the adsorption capacity was 210 mg / g, the degradation efficiency was 69%, and the performance deviation rate was 7.1%.

[0076] Comparative Example 4: Hf6Ta2O supported on activated carbon 17 aerogel This comparative example prepared activated carbon supported on Hf6Ta2O. 17 Aerogel, replacing the graphene carrier of this invention, is prepared as follows: (1) Take 3 mmol of hafnium n-butoxide and 1 mmol of tantalum ethoxide, dissolve them in 20 mL of anhydrous ethanol, add 5 mL of deionized water to hydrolyze, and stir at room temperature for 30 min; (2) Add 0.16g of activated carbon to the above solution, adjust the pH to 4, and ultrasonically disperse for 30min; (3) Transfer to a hydrothermal reactor and react at 160°C for 12 hours to obtain a wet gel; (4) Hf6Ta2O supported on activated carbon was obtained by solvent replacement and freeze drying. 17 Aerogel.

[0077] The aerogel material prepared in Comparative Example 4 had a specific surface area of ​​420 m² / g and a total pore volume of 1.05 cm³ / g.

[0078] Material performance test results Under conditions of 25℃, 50% RH, and 1 atm, the activated carbon supported on Hf6Ta2O prepared in this comparative example... 17 The aerogel exhibited an adsorption capacity of 285 mg / g for DMMP aerosol, with a degradation efficiency of 75%. Humidity gradient performance testing (25℃, 1 atm, initial DMMP concentration 1000 mg / m³) showed that the material's adsorption capacity was 228 mg / g under 95% RH high humidity conditions, with a fluctuation range of 19.9% ​​(Figure 4). Pressure gradient performance testing (25℃, 50% RH, initial DMMP concentration 1000 mg / m³) indicated that the material's adsorption capacities at 0.5, 1, and 2 atm were 270, 285, and 290 mg / g, respectively, slightly lower than that of Example 1 of this invention (Figure 6).

[0079] In the accelerated aging performance test, after aging for 30 days at 80℃, 95% RH, and 1 atm, the adsorption capacity of the material was 242 mg / g, and the degradation efficiency was 68% (Figure 8). After aging for 30 days at 80℃ and 95% RH, the adsorption capacities after aging at 2 atm and 5 atm were 255 mg / g and 230 mg / g, respectively, with degradation efficiencies not exceeding 65%, and slight pore blockage was observed (Figure 9).

[0080] Cyclic regeneration performance tests (25℃, 1 atm, 50% RH, 10 cycles) showed that the adsorption capacities for the 1st, 5th, and 10th cycles were 285, 245, and 220 mg / g, respectively, with a capacity retention rate of 77.2% (Figure 7). Coupled environment performance tests (25℃, initial DMMP concentration 1000 mg / m³) 3The results showed that the material's performance degraded significantly under three extreme coupling environments, with performance deviation rates exceeding 20% ​​in the high-humidity coupling environment: under high humidity and high pressure (95% RH, 2 atm), the adsorption capacity was 225 mg / g, the degradation efficiency was 62%, and the performance deviation rate was 21.1%; under high humidity and low pressure (95% RH, 0.5 atm), the adsorption capacity was 218 mg / g, the degradation efficiency was 60%, and the performance deviation rate was 23.5%; under low humidity and high pressure (10% RH, 2 atm), the adsorption capacity was 265 mg / g, the degradation efficiency was 72%, and the performance deviation rate was 7.0%.

[0081] As can be seen from the performance comparison between the examples and the comparative examples, the graphene / Hf6Ta2O prepared in Examples 1-3 of this invention... 17 All hierarchical porous composite aerogels possess a three-dimensional hierarchical porous structure consisting of macropores, mesopores, and micropores, with Example 1 exhibiting the best overall performance. The hafnium-tantalum molar ratio is a key parameter determining the material's phase composition and properties; in Comparative Example 3, the target product Hf6Ta2O could not be formed due to the hafnium-tantalum molar ratio deviating from 3:1. 17 This leads to insufficient catalytic active sites and a significant decrease in adsorption and degradation performance, fully demonstrating that a 3:1 ratio is the optimal ratio for the formation of Hf6Ta2O. 17 The core stoichiometric ratio. Graphene has unique advantages as a carrier. Comparative Example 4 uses activated carbon instead of graphene, lacking synergistic catalytic effect. Under high humidity conditions, it easily adsorbs water vapor, causing pore blockage, and its performance stability is far lower than that of the material of this invention. Comparative Example 1 is a pure graphene oxide aerogel, with low degradation efficiency, making it difficult to achieve the synergistic function of adsorption and degradation. This invention utilizes graphene and Hf6Ta2O 17 The composite material achieves multiple effects, including pore structure optimization, hydrophobic modification, and synergistic electron transfer catalysis, resulting in a significant improvement in overall performance. In contrast, pure Hf6Ta2O in Comparative Example 2... 17 Aerogels have low specific surface area and simple pore structure, resulting in poor adsorption and degradation capacity and environmental adaptability. Regarding adaptability to extreme coupled environments, the materials in Examples 1-3 of this invention exhibit adsorption and degradation performance deviation rates of less than 10% under three types of coupled environments: high humidity and high pressure, high humidity and low pressure, and low humidity and high pressure, demonstrating excellent adaptability to complex environments. In contrast, the materials in Comparative Examples 1-4 all showed significant performance degradation in high humidity coupled environments, with performance deviation rates exceeding 15%, among which pure Hf6Ta2O... 17 The deviation rate of the aerogel (Comparative Example 2) even exceeded 35%. This advantage is attributed to the graphene hydrophobic network and Hf6Ta2O. 17 The synergistic effect of chemical stability can effectively suppress the blockage of pores by water vapor under high humidity conditions. At the same time, the hierarchical porous structure and stable heterogeneous interface can ensure mass transfer efficiency and catalytic activity under pressure fluctuations.

[0082] To further illustrate the graphene / Hf6Ta2O of the present invention 17 The practical application value of hierarchical porous composite aerogels is illustrated below with specific application examples in different scenarios, and the graphene / Hf6Ta2O used in each example is discussed. 17 All graded porous composite aerogels were prepared by the preparation method described in Example 1 of this invention, and the performance tests of each application example were conducted in an environment simulating actual working conditions.

[0083] Application Example 1: Home / Commercial Air Purification Filters The graphene / Hf6Ta2O prepared according to this invention 17 Graded porous composite aerogel is crushed and granulated to obtain aerogel particles with a particle size of 2-5mm. 80g of these aerogel particles are filled into a filter cartridge (filter cartridge specifications: diameter 100mm, height 200mm) encapsulated with polypropylene meltblown cloth. This cartridge is then combined with a pre-filter to create an integrated air purification filter cartridge, which is compatible with conventional household vertical air purifiers.

[0084] The above-mentioned filter element was applied to a post-renovation indoor air purification scenario to treat mixed polluted air containing formaldehyde, benzene-based volatile organic compounds (VOCs), and DMMP aerosol, simulating actual indoor conditions: ambient temperature 25±2℃, relative humidity 40%~85% RH, air velocity 1.5m³ / min, initial formaldehyde concentration 0.8mg / m³, and initial benzene-based VOCs concentration 1.2mg / m³. 3 The initial concentration of DMMP aerosol is 500 mg / m³, with a particle size of 0.3~2.5 μm. Testing showed that the filter element has a filtration efficiency of ≥99.5% for 0.3~2.5 μm DMMP aerosol, a purification efficiency of ≥92% for formaldehyde, and a purification efficiency of ≥90% for benzene-based VOCs. After 300 hours of continuous operation in simulated indoor air with a dust concentration of 0.5 mg / m³, the filter element pressure difference is ≤150 Pa, and the dust holding capacity is ≥12 g / 100 g composite aerogel. After 90 days of continuous operation under the above simulated conditions, the filter element retains ≥85% of its DMMP aerosol adsorption capacity, and there is no significant decrease in the purification efficiency for formaldehyde and VOCs. In dry environments with a relative humidity of 10%~20% RH and high humidity environments with a relative humidity of 80%~95% RH, the overall performance fluctuation of the filter element is ≤8%, and there is no moisture-induced caking or pore blockage of the aerogel particles.

[0085] Application Example 2: Personal Protective Filter Cartridge The graphene / Hf6Ta2O prepared according to this invention 17Graded porous composite aerogel is freeze-molded and precision-cut to obtain a 5mm thick aerogel porous sheet with a porosity of 85%. 15g of this aerogel sheet is then laminated with non-woven fabric and activated carbon cloth in sequence and pressed into a cylindrical filter cartridge (filter cartridge specifications: diameter 40mm, height 60mm). This filter cartridge is compatible with self-priming filter gas masks.

[0086] The above-mentioned filter cartridges were applied to personal respiratory protection in chemical industrial park operations and sudden toxic gas leak scenarios. They were used to treat toxic aerosols containing DMMP, a toxic agent simulant, and 2-chloroethyl ethyl sulfide, a mustard gas simulant, simulating actual protective conditions: ambient temperature -5~40℃, relative humidity 10%~95% RH, air pressure 0.8~1.2 atm, adult standard breathing flow rate 30L / min, initial DMMP aerosol concentration 1000mg / m³, and particle size 0.3~2.5μm. Tests showed that the filter cartridge has a filtration efficiency of ≥99.9% for toxic aerosols of 0.3~2.5μm and a catalytic degradation efficiency of ≥90% for DMMP aerosols. In an industrial environment with a dust concentration of 1.0mg / m³, after continuous use for 8 hours, the filter cartridge resistance is ≤250Pa and the dust holding capacity is ≥15g / 100g composite aerogel. In a polluted environment with an initial DMMP aerosol concentration of 1000mg / m³, the filter cartridge provides continuous protection for the human body for ≥12 hours. In extreme environments with 95% RH high humidity, 0.8atm low pressure at high altitude, and 40℃ high temperature, the protection duration of the filter cartridge fluctuates by ≤10%, and the aerogel sheet shows no problems such as moisture absorption failure or structural deformation.

[0087] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A graphene / Hf6Ta2O 17 A method for preparing hierarchical porous composite aerogels, characterized in that, Includes the following steps: The precursor solution was prepared by dissolving the hafnium source and the tantalum source separately in an acid solvent and then transferring and mixing them in an alcohol solvent. The precursor solution was mixed with graphene oxide dispersion to construct a sol system, and then the sol system was subjected to a hydrothermal reaction to obtain a hydrogel. The hydrogel was subjected to solvent replacement and freeze-drying processes sequentially to obtain a composite aerogel with a three-dimensional hierarchical porous structure of macropores-mesopores-micropores, which is the graphene / Hf6Ta2O. 17 Hierarchical porous composite aerogel.

2. The preparation method according to claim 1, characterized in that, The hydrothermal reaction is carried out at a temperature of 120-140 °C for 12-14 h.

3. The preparation method according to claim 1, characterized in that, The hafnium source is n-butanol hafnium, and the tantalum source is ethanol tantalum.

4. The preparation method according to claim 3, characterized in that, The molar ratio of hafnium n-butoxide to tantalum ethoxide is 3:

1.

5. The preparation method according to claim 1, characterized in that, The solvent used for solvent replacement is tert-butanol.

6. The preparation method according to claim 1, characterized in that, The freeze-drying process further includes a calcination step: calcination is carried out in an inert gas atmosphere at a temperature of 750-1200 ℃ for 1-6 h.

7. Graphene / Hf6Ta2O prepared by the preparation method according to any one of claims 1-6 17 Hierarchical porous composite aerogel.

8. The graphene / Hf6Ta2O as described in claim 7 17 Applications of hierarchical porous composite aerogels in air purification, remediation of environments contaminated by toxic agents, or preparation of protective filtration products.

9. An adsorbent for protective filtration or environmental remediation, characterized in that, Its active ingredient includes the graphene / Hf6Ta2O described in claim 7. 17 Hierarchical porous composite aerogel.

Images