Mold mineralization derived manganese nanometer island / porous biochar composite material and preparation method and application thereof

Abstract

This invention discloses a mold-mineralized manganese nano-island / porous biochar composite material, its preparation method, and its application, relating to the field of catalytic materials technology. The preparation method of this invention's mold-mineralized manganese nano-island / porous biochar composite material includes the following steps: S1. Adding a manganese source to a bacterial solution containing mold mycelial pellets and culturing at 26–32°C for 2–5 days to obtain mycelial pellets containing biogenic manganese oxides; S2. Carbonizing the mycelial pellets containing biogenic manganese oxides obtained in step S1 in an inert gas atmosphere to obtain the mold-mineralized manganese nano-island / porous biochar composite material. The mold-mineralized manganese nano-island / porous biochar composite material of this invention accelerates electron transfer in the catalyst, combining the biological structure and physicochemical properties of biological cells and Mn-based metal oxides to achieve synergistic ozone decomposition catalytic function, with an ozone decomposition catalytic removal efficiency of up to 90% under high humidity.

Description

Technical Field

[0001] This invention relates to the field of catalytic materials technology, and more specifically, to a mold-mineralized manganese nano-island / porous biochar composite material, its preparation method, and its application. Background Technology

[0002] In daily life, low concentrations of ozone are widely used in healthcare, food preservation, and water treatment due to their disinfection and sterilization properties. However, ground-level ozone, as a greenhouse gas and secondary air pollutant, poses serious threats to ecosystems and human health. Long-term exposure to low concentrations of ozone (~100 ppb, World Health Organization guidelines) can damage the lungs and cardiovascular system, and even lead to shortened life expectancy and death. Therefore, ozone control and remediation in areas where ozone levels exceed standards are crucial for environmental protection and public health.

[0003] Currently, common ozone control methods include activated carbon adsorption, thermal decomposition, dilution, and catalytic decomposition. The first few methods have limitations such as high energy consumption and the generation of secondary pollutants, while catalytic decomposition of ozone can effectively overcome these limitations, achieving complete ozone decomposition and making it a more ideal and feasible method. Currently, the catalysts used for ozone decomposition are mainly manganese-containing catalysts, including transition metal catalysts and noble metal catalysts. However, existing common ozone decomposition catalysts typically suffer from complex preparation processes, low yields, high costs, poor moisture resistance, and low ozone decomposition efficiency, thus limiting their widespread application. Therefore, constructing a catalyst with a simple preparation process, low cost, good environmental adaptability, and high efficiency in treating ozone under high humidity conditions is the current mainstream trend and is of great significance for mitigating ozone hazards.

[0004] Existing technology discloses a microbial char-supported manganese-cobalt catalyst, its preparation method, and its application. The preparation method includes the following steps: 1) mixing manganese chloride solution and cobalt chloride solution separately with microbial residue, and adsorbing the mixture to obtain manganese-supported microbial precursors and cobalt-supported microbial precursors; 2) calcining the manganese-supported microbial precursors, cobalt-supported microbial precursors, and an activator to obtain microbial char-supported manganese-cobalt powder; 3) mixing the microbial char-supported manganese-cobalt powder with a binder and granulating the mixture, then calcining the resulting microbial char-supported manganese-cobalt particles a second time to obtain the microbial char-supported manganese-cobalt catalyst. However, this microbial char-supported manganese-cobalt catalyst only maintains an ozone removal efficiency of 70% at a relative humidity of 60%, failing to solve the technical challenge of efficient ozone treatment under high humidity conditions. Summary of the Invention

[0005] The technical problem to be solved by this invention is to overcome the defects and shortcomings of existing ozone decomposition catalysts in efficiently decomposing ozone under high humidity conditions, especially high humidity conditions. This invention provides a mold-mineralized manganese nano-islands / porous biochar composite material, which uses mold mycelium balls formed by mold entanglement as the carbon source precursor for biochar. The manganese source is loaded by the biomineralization of mold, and then carbonization is carried out to obtain a composite biochar material loaded with bio-manganese oxides. This enhances electron transfer and effectively improves the catalytic degradation efficiency of the catalyst for ozone under high humidity conditions, especially high humidity conditions.

[0006] Another objective of this invention is to provide a method for preparing a mold-mineralized manganese nanoisland / porous biochar composite material.

[0007] Another object of the present invention is to provide an application of a mold-mineralized manganese nanoisland / porous biochar composite material in the catalytic degradation of ozone.

[0008] Another object of the present invention is to provide an ozone decomposition air filter.

[0009] The above-mentioned objective of this invention is achieved through the following technical solution:

[0010] A method for preparing a mold-mineralized manganese nanoislands / porous biochar composite material, characterized by comprising the following steps:

[0011] S1. Add the manganese source to the bacterial solution containing mold mycelial balls and culture at 26-32℃ for 2-5 days to obtain mycelial balls containing biogenic manganese oxide;

[0012] S2. The mycelial balls containing biogenic manganese oxide obtained in step S1 are carbonized in an inert gas to obtain a mold-mineralized manganese nano-island / porous biochar composite material. The carbonization temperature is 500–900℃, the carbonization time is 0.5–2h, and the heating rate is 5–20℃ / min. -1 .

[0013] The mold mineralization-derived manganese nano-islands / porous biochar composite material prepared by this invention contains mold mycelium balls, on which manganese oxide materials formed by biomineralization are loaded.

[0014] The preparation method of this invention is simple and easy to implement. The prepared ozone decomposition catalyst is green, inexpensive, and has excellent performance. It has superior water resistance, is easy to recycle and reuse, and is easy to scale up for production.

[0015] The mold of this invention can oxidize metal ions in the environment and produce biomineralized metal oxides. The metal biomaterial prepared using the mold as a carrier combines the properties of two functional nanomaterials: firstly, the unique characteristic of mold in easily forming self-adhesive biofilms gives its system a larger surface area than traditional carriers; secondly, the strong interaction between the metal nanoparticles formed by mold mineralization and the carrier enhances electron transfer and exhibits unique catalytic properties. Furthermore, the mold has strong reproductive capacity, high manganese tolerance, abundant hyphae, and is a natural nitrogen- and phosphorus-doped biomass that is easy to obtain, has high yield, and is inexpensive, making it an ideal biomass carrier material.

[0016] Compared with chemically synthesized metal oxides, bio-metal oxides have the advantages of large specific surface area, excellent adsorption capacity and strong reactivity, showing good application prospects in the field of pollution control.

[0017] In a specific embodiment, the preparation process of the bacterial solution containing mold mycelial balls of the present invention can refer to the following steps:

[0018] After inoculating the mold into a solid culture medium for seed culture, the mold spore suspension is obtained by washing with sterile deionized water. The mold spore suspension is then inoculated into a liquid culture medium and cultured in a constant temperature and speed shaker.

[0019] Preferably, the rotation speed of the thermostatic shaker is 120-160 rpm.

[0020] More preferably, the specific conditions for the carbonization treatment are: carbonization temperature of 700℃, carbonization time of 1 hour, and heating rate of 10℃ / min. -1 .

[0021] In a specific embodiment, preferably, the mold is one or more of Trichoderma, Aspergillus niger, Cladosporium, Sterculia vesicularis, and Penicillium. More preferably, it is Trichoderma, and the liquid culture medium is a mold liquid culture medium.

[0022] Aspergillus niger can produce MnC2O4, Trichoderma and Cladosporium can produce δ-MnO2, and Sterculia robusta can produce MnCO3 and other biogenic manganese oxide minerals. This invention utilizes different strains, different manganese sources, and other experimental conditions to regulate the morphology, crystal form, and types of biogenic manganese oxide minerals, providing multiple possibilities for their application in ozone decomposition catalysis.

[0023] In a specific embodiment, preferably, the manganese source is one or more of manganese chloride, manganese sulfate, potassium manganate, and potassium permanganate. More preferably, it is manganese chloride.

[0024] In a specific embodiment, the mass ratio of the mold mycelium balls to the manganese source in S1 is 1 to 25:1.

[0025] More preferably, the mass ratio of the mold mycelium balls to the manganese source in S1 is 1.5 to 5:1.

[0026] In a specific embodiment, the manganese source in S1 is preferably added in the form of a manganese source solution, and the molar concentration of manganese ions in the manganese source solution is 0.05 to 2 mol / L.

[0027] The present invention also specifically protects a method for preparing the aforementioned mold mineralization-derived manganese nano-islands / porous biochar composite material, resulting in the mold mineralization-derived manganese nano-islands / porous biochar composite material.

[0028] The composite biomass material of this invention can be applied to ozone decomposition catalysis, and has the characteristics of good decomposition effect, simple operation, easy material recycling, low cost, and green environmental protection.

[0029] Preferably, the nitrogen content of the mold-mineralized manganese nano-islands / porous biochar composite material is 5.97–6.73 wt%, the phosphorus content is 3.57–6.42 wt%, and the manganese content is 0.80–5.76 wt%. This invention also specifically protects the application of a mold-mineralized manganese nano-islands / porous biochar composite material in the catalytic degradation of ozone.

[0030] In specific applications, the mold mineralization-derived manganese nano-islands / porous biochar composite material of the present invention can be adapted to ozone efficient catalytic degradation under various humidity conditions, especially high humidity conditions. The application humidity range of the present invention is 0% to 90%, for example, 0%, 60%, and 90%.

[0031] The present invention also specifically protects an ozone decomposition air filter, wherein the ozone decomposition air filter uses the mold mineralization-derived manganese nano-island / porous biochar composite material as a catalytic degradation material.

[0032] The mold-mineralized manganese nano-islands / porous biochar composite material of the present invention can be used to prepare the filter membrane of an ozone decomposition air filter.

[0033] The preparation process of ozone decomposition air filter membrane includes:

[0034] The mold-mineralized manganese nano-island / porous biochar composite material was prepared according to steps S1-2, except that step S2 was replaced with:

[0035] S2: After thoroughly washing the mycelium balls containing bio-manganese oxides obtained in step S1, press them into sheets of appropriate diameter in a mold, freeze-dry them, and carbonize them in an inert gas to obtain a mold-mineralized manganese nano-island / porous biochar composite material.

[0036] Compared with the prior art, the beneficial effects of the present invention are:

[0037] (1) The preparation method of the mold mineralization-derived manganese nano island / porous biochar composite material of the present invention is simple, requires mild conditions, can achieve mass production, and has low raw material cost.

[0038] (2) The precursor fungal hyphae of the mold mineralization-derived manganese nano-island / porous biochar composite material of the present invention are regenerable and grow rapidly. The abundant hyphae cross-link to form a porous carbon material with a large specific surface area, which has a fast mass transfer capacity and promotes gas molecule transport. Moreover, its natural doping of nitrogen and phosphorus enhances the electrical conductivity of the carbon material, which is beneficial to electron transfer in catalytic reactions. It also has excellent mechanical properties. Its good plasticity helps to make it into a whole bio-air filter membrane, which is conducive to practical application and recycling.

[0039] (3) The preparation method of the present invention uses mold mycelium balls as a carrier, and loads bio-manganese oxide through the biomineralization of the mold itself. The biomineralized metal oxide is tightly bound to the carrier, and the doping of manganese oxide further accelerates the electron transfer of the catalyst. Combining the biological structure and physicochemical properties of the biological cells and Mn-based metal oxides, the synergistic ozone decomposition catalytic function is achieved.

[0040] (4) The nitrogen, phosphorus and manganese content of the self-doped nitrogen and phosphorus mold mineralization-derived manganese nano island / porous biochar composite material of the present invention can reach up to 6.73wt%, 6.42wt% and 5.76wt%, respectively, and the ozone removal efficiency can reach 90% under high humidity. Attached Figure Description

[0041] Figure 1 The Trichoderma mycelium balls were cultured in Example 1.

[0042] Figure 2 This is a SEM image of the mold-mineralized manganese nanoisland / porous biochar composite material obtained in Example 2.

[0043] Figure 3 The images show the XRD patterns of the mold-mineralized manganese nanoisland / porous biochar composite material obtained in Example 2 and the porous biochar material obtained in Comparative Example 1.

[0044] Figure 4 This is a TEM image of the mold-mineralized manganese nanoisland / porous biochar composite material obtained in Example 2.

[0045] Figure 5 This is a photograph of the appearance of the mold-mineralized manganese nanoisland / porous biochar air filter prepared in Example 4.

[0046] Figure 6 The image shows a SEM image of the porous biochar material obtained in Comparative Example 1.

[0047] Figure 7 The CV diagrams are of the mold-mineralized manganese nano-island / porous biochar composite material obtained in Example 2 and the porous biochar material obtained in Comparative Example 1.

[0048] Figure 8 The graph shows the performance of the mold-mineralized manganese nano-island / porous biochar composite materials obtained in Examples 1-3 and the porous biochar material obtained in Comparative Example 1 in ozone decomposition catalysis.

[0049] Figure 9 The graph shows the performance of the mold-mineralized manganese nano-island / porous biochar composite material obtained in Example 2 in ozone decomposition catalysis under different humidity conditions. Detailed Implementation

[0050] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0051] Example 1

[0052] The preparation of a mold-mineralized manganese nanoisland / porous biochar composite material includes the following steps:

[0053] S1. Dissolve 0.9896g MnCl2·4H2O in 10mL of sterile water. Add the solution to the bacterial culture containing Trichoderma mycelial balls (5g dry weight) using a pipette in a clean bench. Incubate at 27℃ and 150rpm for 4 days. Filter the solution through double-layered gauze to remove the mold culture medium. Wash the solution three times with deionized water.

[0054] The mass ratio of the mold mycelium balls to the manganese source in S1 is 5:1.

[0055] S2. The reaction product in S1 was freeze-dried. An appropriate amount of freeze-dried sample was placed in a corundum boat and placed in a tube furnace. Under a nitrogen atmosphere with a gas flow rate of 100 mL min-1, the temperature was increased to 700 °C for 1 h at a rate of 10 °C min-1 to obtain a mold-mineralized manganese nano-island / porous biochar composite material.

[0056] The mold-mineralized manganese nanoisland / porous biochar composite material was found to contain 5.97 wt% nitrogen, 4.57 wt% phosphorus, and 0.80 wt% manganese.

[0057] The cultivation steps for Trichoderma mycelium balls are as follows:

[0058] 1. Trichoderma culture: Prepare DRBC solid medium, sterilize in an autoclave at 121℃ for 30 min, sterilize in a clean bench with UV for 30 min, ventilate (with sterile air) for 10 min, pour into plates, cool and solidify, pick Trichoderma spores and inoculate onto the plates, place them in a constant temperature incubator at 28℃ for 2 days, and store the spores grown at 4℃ for later use.

[0059] 2. Preparation of spore suspension: In a clean bench, pour 20 ml of sterile water into a plate covered with spores, scrape spores with an inoculation loop, rinse twice with sterile water, pour into an Erlenmeyer flask, shake for 2 min to distribute the spores evenly, and the spore suspension is obtained. Store at 4℃ for later use.

[0060] 3. Cultivation of Trichoderma mycelium: Prepare a liquid culture medium for the fungus, sterilize it in an autoclave at 121℃ for 30 min, cool it to room temperature, and then add 10 μL of spores at a concentration of 10 μg / mL using a pipette in a clean bench. 4 A spore suspension of 1 spore / mL was cultured at 27℃ and 150 rpm for 3 days to obtain Trichoderma mycelial balls, which were then stored at 4℃ for later use.

[0061] See the image of the Trichoderma mycelium obtained from the culture. Figure 1 .

[0062] Example 2

[0063] The preparation of a mold-mineralized manganese nanoisland / porous biochar composite material includes the following steps:

[0064] S1. Dissolve 1.9791g MnCl2·4H2O in 10mL of sterile water. Using a pipette, add the solution to the culture medium containing Trichoderma mycelial balls (5g dry weight) in a laminar flow hood. Incubate at 27℃ and 150rpm for 4 days. Filter the solution through double-layered gauze to remove the mold culture medium. Wash the solution three times with deionized water.

[0065] The mass ratio of the mold mycelial balls to the manganese source in S1 is 2.5:1;

[0066] S2. Freeze-dry the reaction product from S1. Place an appropriate amount of the freeze-dried sample in a corundum boat, and then place it in a tube furnace at a gas flow rate of 100 mL / min. -1 Under nitrogen atmosphere protection, at 10℃ min -1 The temperature was increased to 700℃ and carbonized for 1 hour to obtain a mold-mineralized manganese nano-island / porous biochar composite material.

[0067] The mold-mineralized manganese nanoisland / porous biochar composite material was found to contain 6.21 wt% nitrogen, 6.42 wt% phosphorus, and 1.54 wt% manganese.

[0068] SEM images of the mold-mineralized manganese nanoisland / porous biochar composite material prepared in Example 2 above are shown below. Figure 2 .

[0069] The XRD pattern of the mold-mineralized manganese nanoisland / porous biochar composite material prepared in the above embodiments is shown in the figure. Figure 3 .

[0070] TEM images of the mold-mineralized manganese nanoislands / porous biochar composite material prepared in the above embodiments are shown below. Figure 4 .

[0071] Example 3

[0072] The preparation of a mold-mineralized manganese nanoisland / porous biochar composite material includes the following steps:

[0073] S1. Dissolve 2.9687g MnCl2·4H2O in 10mL of sterile water. Using a pipette, add the solution to the bacterial culture containing Trichoderma mycelial balls (5g dry weight) in a clean bench. Incubate at 27℃ and 150rpm for 4 days. Filter the solution through double-layered gauze to remove the mold culture medium. Wash the solution three times with deionized water.

[0074] The mass ratio of the mold mycelial balls to the manganese source in S1 is 1.7:1;

[0075] S2. Freeze-dry the reaction product from S1. Place an appropriate amount of the freeze-dried sample in a corundum boat, and then place it in a tube furnace at a gas flow rate of 100 mL / min. -1 Under nitrogen atmosphere protection, at 10℃

[0076] min -1 The temperature was increased to 700℃ and carbonized for 1 hour to obtain a mold-mineralized manganese nano-island / porous biochar composite material.

[0077] The mold-mineralized manganese nanoisland / porous biochar composite material was found to contain 6.73 wt% nitrogen, 3.57 wt% phosphorus, and 5.76 wt% manganese.

[0078] Example 4

[0079] Preparation of a mold-mineralized manganese nanoisland / porous biochar air filter

[0080] S1 dissolved 1.9791g MnCl2·4H2O in 10mL of sterile water and added it to the bacterial culture containing Trichoderma mycelial balls (dry weight of mycelial balls was 5g) using a pipette in a laminar flow hood. The culture was incubated at 27℃ and 150rpm for 4 days. The liquid culture medium containing the mold was removed by filtration through double-layer gauze, and the sample was washed three times with deionized water.

[0081] The mass ratio of the mold mycelial balls to the manganese source in S1 is 2.5:1;

[0082] S2: The reaction product from S1 was placed in a mold with a diameter of 30 mm and a thickness of 8 mm and compacted, then frozen at -20°C for 2 h. The resulting cylinder was freeze-dried for 48 h to obtain a white film-like precursor.

[0083] S3: The reaction products from S2 are placed in a corundum boat and then placed in a tube furnace at a gas flow rate of 100 mL / min. -1 Under nitrogen atmosphere protection, at 10℃ min -1 The temperature was increased to 700℃ and carbonized for 1 hour to obtain a manganese nano-island / porous biochar air filter derived from mold mineralization.

[0084] The image of the mold-mineralized manganese nanoislands / porous biochar air filter prepared in Example 4 is shown below. Figure 5 .

[0085] Example 5

[0086] Preparation of a mold-mineralized manganese nanoisland / porous biochar composite material

[0087] S1. Dissolve 1.9791g MnCl2·4H2O in 10mL of sterile water. Using a pipette, add the solution to the culture medium containing Aspergillus niger mycelial balls (5g dry weight) in a laminar flow hood. Incubate at 27℃ and 150rpm for 4 days. Filter the solution through double-layered gauze to remove the moldy liquid culture medium. Wash three times with deionized water.

[0088] The mass ratio of the mold mycelial balls to the manganese source in S1 is 2.5:1;

[0089] S2. Freeze-dry the reaction product from S1. Place an appropriate amount of the freeze-dried sample in a corundum boat, and then place it in a tube furnace at a gas flow rate of 100 mL / min. -1 Under nitrogen atmosphere protection, at 10℃ min -1 The temperature was increased to 700℃ and carbonized for 1 hour to obtain a mold-mineralized manganese nano-island / porous biochar composite material.

[0090] The cultivation steps for Aspergillus niger mycelial balls are as follows:

[0091] Aspergillus niger culture: Prepare DRBC solid medium, sterilize in an autoclave at 121℃ for 30 min, sterilize in a clean bench with UV for 30 min, ventilate (with sterile air) for 10 min, pour into plates, cool and solidify, pick Aspergillus niger spores and inoculate onto the plates, place them in a constant temperature incubator at 28℃ for 2 days, and store the spores grown at 4℃ for later use.

[0092] Preparation of spore suspension: In a clean bench, pour 20 ml of sterile water into a plate covered with spores, scrape spores with an inoculation loop, rinse twice with sterile water, pour into an Erlenmeyer flask, shake for 2 min to distribute the spores evenly, and the spore suspension is obtained. Store at 4℃ for later use.

[0093] Cultivation of Aspergillus niger mycelial balls: Prepare a liquid culture medium for the mold, sterilize it in an autoclave at 121℃ for 30 min, cool it to room temperature, and then add 10 μL of spores with a concentration of 10 μg / mL using a pipette in a clean bench. 4 A spore suspension of 1 spore / mL was cultured at 27℃ and 150 rpm for 3 days to obtain Aspergillus niger mycelial balls, which were then stored at 4℃ for later use.

[0094] Comparative Example 1

[0095] A method for preparing porous biochar materials

[0096] 1) In a clean bench, use a pipette to add 10 mL of sterile water to the bacterial culture containing Trichoderma mycelial balls (dry weight of mycelial balls is 5 g), and incubate at 27℃ and 150 rpm for 4 days. Filter the culture medium with double gauze to remove the mold liquid culture medium, and soak and wash with deionized water 3 times.

[0097] The reaction product from step 1) was freeze-dried. The freeze-dried sample was placed in a corundum boat and then placed in a tube furnace at a gas flow rate of 100 mL / min. -1 Under nitrogen atmosphere protection, at 10℃ min -1 The temperature was increased to 700℃ and carbonized for 1 hour to obtain porous biochar material.

[0098] SEM images of the porous biochar material prepared in Comparative Example 1 are shown below. Figure 6 .

[0099] Result detection

[0100] 1. Scanning Electron Microscope (SEM)

[0101] The morphology of the mold-mineralized manganese nanoisland / porous biochar composite material prepared in Example 2 and the porous biochar material prepared in Comparative Example 1 was characterized. The tests were performed using a Zeiss Sigma 500 scanning electron microscope.

[0102] See Figure 2 and Figure 6SEM characterization revealed that the surface of the fungal hyphae-based material was smooth; the surface of the hyphae in the mold mineralization-derived manganese nano-island / porous biochar composite material became rough, with granular protrusions on the hyphae surface, indicating that in the mold mineralization-derived manganese nano-island / porous biochar composite material, the manganese oxides generated by biomineralization were loaded onto the fungal hyphae.

[0103] 2. X-ray diffraction (XRD) characteristics

[0104] XRD analysis was performed on the mold-mineralized manganese nanoisland / porous biochar composite material prepared in Example 2 and the porous biochar material prepared in Comparative Example 1. The tests were conducted on a Japanese RIGAKU X-ray powder diffractometer under the following conditions: Cu Ka target, scanning speed of 2.0° / s, and scanning range of 5.0°–80.0°.

[0105] See Figure 3 XRD characterization showed that the mold-mineralized manganese nano-island / porous biochar composite material obtained in Example 2 had consistent XRD characteristic diffraction peaks with β-MnO2 and δ-MnO2, namely (110)(101) for β-MnO2 and (001)(002) for δ-MnO2. However, the porous biochar material obtained in Comparative Example 1 did not have characteristic diffraction peaks in XRD. This indicates that Trichoderma mycelium successfully loaded bio-manganese oxide through biomineralization, thus preparing the mold-mineralized manganese nano-island / porous biochar composite material obtained in Example 2.

[0106] 3. Transmission electron microscope (TEM)

[0107] The mold-mineralized manganese nanoisland / porous biochar composite material prepared in Example 2 was characterized by TEM. Testing was performed using a JEM-2010HR transmission electron microscope with a maximum accelerating voltage of 300 kV.

[0108] See Figure 4 TEM characterization showed that the mold-mineralized manganese nano-islands / porous biochar composite material obtained in Example 2 had lattice fringes of 0.24 nm and 0.35 nm, which corresponded well to the (101) and (002) crystal planes of β-MnO2 and were consistent with the XRD characterization results. This further demonstrated that Trichoderma mycelium successfully loaded bio-manganese oxide through biomineralization to prepare the mold-mineralized manganese nano-islands / porous biochar composite material obtained in Example 2.

[0109] Electrochemical characterization

[0110] Electrochemical characterization was performed on the mold-mineralized manganese nanoisland / porous biochar composite material obtained in Example 2 and the porous biochar material obtained in Comparative Example 1. The tests were conducted using a CHI660E electrochemical workstation with a 1.0 mol / L electrolyte solution. -1 Na2SO4 electrolysis solution.

[0111] See Figure 7 Cyclic voltammetry analysis results show that the mold-mineralized manganese nano-island / porous biochar composite material obtained in Example 2 has more surface charge and better redox cycling ability than the porous biochar material obtained in Comparative Example 1, which is beneficial to the continuous and efficient ozone decomposition catalytic process.

[0112] Application of mold-mineralized manganese nanoislands / porous biochar air filter membranes in ozone decomposition catalysis

[0113] The performance of the ozone decomposition catalysts prepared in Examples 1-3 and Comparative Example 1 was tested. Specific test conditions were as follows: the ambient temperature was controlled at 24±2℃ using air conditioning; an ozone generator produced a certain concentration of ozone, which was diluted and divided into two streams. One stream was fed into a gas washing bottle containing pure water, where the diluted ozone gas bubbled to achieve a relative humidity of 100%; the other stream of diluted ozone gas was dried in a silica gel-filled drying tower to achieve a relative humidity of 0%. All pipelines were equipped with glass rotor flow meters to regulate the flow rate. The two gas streams were combined and connected to a catalytic reactor, with the relative humidity of the incoming gas controlled at 0%, 60%, and 90%, respectively, and the ozone concentration controlled at approximately 1 ppm to simulate the high concentration of ozone gas that might be encountered in daily life; the catalyst space velocity was 10000 h⁻¹. -1 The performance test results of the ozone decomposition catalyst are shown below:

[0114] Table 1. Performance test results of the ozone decomposition catalysts prepared in Examples 1-3 and Comparative Example 1 of the present invention.

[0115] Sample number Example 1 Example 2 Example 3 Comparative Example 1 Removal efficiency % 66 91 77 35

[0116] See Figure 8 As shown in Table 1, under the same humidity conditions, the mold-mineralized manganese nano-island / porous biochar composite materials obtained in Examples 1-3 and the porous biochar material obtained in Comparative Example 1 both have different degrees of ozone decomposition catalytic effects. The catalysts prepared in Examples 1-3 have higher ozone purification and decomposition rates, with Example 2 achieving an ozone removal efficiency of 91%, while the porous biochar obtained in Comparative Example 1 has a relatively lower ozone purification and decomposition rate.

[0117] Table 2. Performance test results of the ozone decomposition catalyst of Example 2 of the present invention under different humidity conditions.

[0118]

[0119]

[0120] See Figure 9 As shown in Table 2, the ozone decomposition catalyst performance test results indicate that the ozone purification and decomposition rate of the mold mineralization-derived manganese nano-island / porous biochar composite material obtained in Example 2 is minimally affected by different ambient humidity levels. It exhibits the highest removal efficiency under atmospheric humidity of 60%, demonstrating its excellent moisture resistance.

[0121] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a mold-mineralized manganese nanoislands / porous biochar composite material, characterized in that, Includes the following steps: S1. Add the manganese source to the bacterial solution containing mold mycelial balls and incubate at 26~32℃ for 2~5 days to obtain mycelial balls containing biogenic manganese oxide; S2. The mycelial balls containing biogenic manganese oxide obtained in step S1 are freeze-dried and carbonized in an inert gas to obtain a mold-mineralized manganese nano-island / porous biochar composite material. The carbonization temperature was 700 ℃, the carbonization time was 0.5~2 h, and the heating rate was 5~20 ℃·min. -1 ; The mold is Trichoderma; The mass ratio of the mold mycelial balls to the manganese source in S1 is 1.5~5:1; The mold-mineralized manganese nanoislands / porous biochar composite material contains δ-MnO2.

2. The preparation method of the mold mineralization-derived manganese nanoislands / porous biochar composite material as described in claim 1, characterized in that, In S1, the manganese source is added in the form of a manganese source solution, and the molar concentration of manganese ions in the manganese source solution is 0.05~2 mol / L.

3. A mold mineralization-derived manganese nano-island / porous biochar composite material prepared by any one of claims 1 to 2.

4. The mold-mineralized manganese nanoislands / porous biochar composite material as described in claim 3, characterized in that, The mold-mineralized manganese nanoisland / porous biochar composite material has a nitrogen content of 5.97~6.73 wt%, a phosphorus content of 3.57~6.42 wt%, and a manganese content of 0.80~5.76 wt%.

5. The application of the mold mineralization-derived manganese nanoisland / porous biochar composite material as described in claim 3 or 4 in the catalytic degradation of ozone.

6. The application as described in claim 5, characterized in that, The relative humidity of the application is 0% to 90%.

Images