Sulfur-doped mycelium bamboo composite material and preparation method thereof

Abstract

The application belongs to the technical field of composite materials, and specifically provides a sulfur-doped mycelium bamboo-based composite material and a preparation method thereof. The application prepares a potato glucose agar culture medium first, then carries out the propagation of white rot fungi based on the potato glucose agar culture medium, then cultures the bamboo powder carbon powder prepared under specific conditions and the white rot fungi in a liquid culture medium to obtain white rot fungi bamboo powder spheres, finally carries out a dipping reaction of the obtained white rot fungi bamboo powder spheres and sodium thiosulfate, collects the solid material after the reaction is completed, and dries the solid material, finally carries out a heating treatment under a nitrogen atmosphere, and finally the sulfur-doped mycelium bamboo-based composite material is prepared, which has high adsorption of heavy metal ions and can effectively remove heavy metal ions when used for treating mercury-containing wastewater.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a sulfur-doped mycelium bamboo-based composite material and its preparation method. Background Technology

[0002] Adsorption is a common method for wastewater treatment, offering advantages such as high efficiency, strong regeneration capacity, and low cost. However, the choice of adsorbent determines the application potential of the adsorption technology, including adsorbent cost, adsorption efficiency, and regeneration capacity. Materials used in adsorption mainly include natural inorganic adsorbents, synthetic adsorbents, and biomass materials.

[0003] Biomass, as organic matter produced by natural organisms, is characterized by low pollution, wide distribution, and abundant resources. Compared with other adsorbents, biomass adsorbents are renewable, easily degradable, low-cost, and environmentally friendly. Currently used biomass adsorbents mainly come from agricultural and forestry waste and microorganisms, such as peanut shells, rice straw, corn cobs, sugarcane bagasse, fungi, and algae. The concentration of heavy metals in industrial wastewater often far exceeds environmental standards, and excessive emissions not only directly affect the sustainable development of the surrounding environment but also exacerbate the scarcity of Earth's resources. Furthermore, heavy metals can accumulate in soil over long periods, affecting the quality and safety of agricultural products and posing potential health risks in the food chain. With the acceleration of industrialization, heavy metal pollution has become increasingly prominent, thus urgently requiring effective treatment methods to remove heavy metal pollutants from industrial wastewater.

[0004] Biochar (BC), a biomass material made from inexpensive organic waste, has attracted widespread attention from researchers both domestically and internationally in recent years due to its low cost and simple preparation methods. The preparation of biochar not only solves the problem of recycling large amounts of urban and agricultural waste, but also, due to the unique structure formed during pyrolysis (porosity, abundant surface groups, and deposition of various inorganic salts), it has broad application prospects in the removal of environmental pollutants. However, current technologies mostly use chemical methods to prepare biochar materials, which poses environmental pollution problems, and the adsorption performance of the prepared biochar materials for heavy metals is not ideal. Summary of the Invention

[0005] To address the aforementioned problems in existing technologies, this invention provides a sulfur-doped mycelium-based bamboo composite material and its preparation method. The sulfur-doped mycelium-based bamboo composite material of this invention is prepared using a microbial method, which can effectively regulate porosity and improve adsorption efficiency. Simultaneously, sulfur doping can form coordination with mercury, further enhancing the adsorption effect. The sulfur-doped mycelium-based bamboo composite material of this invention exhibits high adsorption capacity for heavy metal ions, effectively removing heavy metal ions when used for treating mercury-containing wastewater.

[0006] The technical solution adopted in this invention is as follows: A method for preparing a sulfur-doped mycelium bamboo-based composite material includes the following steps: (1) Preparation of potato dextrose agar medium; (2) Propagate the white rot fungus based on the potato dextrose agar medium described in step (1); (3) Take bamboo material and steam it first, then perform high temperature and high pressure micro-explosion to crush the bamboo material into bamboo powder, and then carbonize the bamboo powder to obtain bamboo powder carbon powder. (4) After culturing bamboo powder and carbon powder with white-rot fungi in a liquid culture medium, the culture medium is removed to obtain white-rot fungi bamboo powder spheres; (5) The white rot fungus bamboo powder spheres obtained in step (4) are first dried, and then mixed and impregnated with sodium thiosulfate. After the reaction is completed, the solid material is collected and dried. Finally, the mixture is heated under a nitrogen atmosphere to obtain the sulfur-doped mycelium bamboo-based composite material.

[0007] In step (1), the preparation method of the potato dextrose agar medium is as follows: Add 200g of fresh potato chunks to deionized water, boil and stir continuously for 30 min, filter the solids, and bring the solution to a final volume of 1 L; add 20 g of glucose, 20 g of agar powder, 3 g of KH2PO4, 1.5 g of MgSO4·7H2O and 5 mg of thiamine to the solution, stir until completely dissolved, autoclave, and allow the culture medium to cool naturally to prepare the potato glucose agar medium.

[0008] In step (2), the specific operation of the white rot fungus expansion culture is as follows: take a small piece of white rot fungus slant culture medium, put it into the potato dextrose agar medium, and then place it in a biochemical incubator at 28℃ for 5-7 days to complete the white rot fungus expansion culture.

[0009] In step (3), the specific operation of the high temperature and high pressure micro-explosion is to bring the temperature to 80°C, pressurize it to 0.4MPa, maintain it for 10 minutes, and release the pressure instantly. The material completes the compressed air micro-explosion process under the action of the internal and external pressure difference. The bamboo powder carbon powder is prepared by the following method: the cleaned bamboo powder is dried in an oven at 60°C until the moisture is completely removed; the bamboo powder is heated to 600°C in a tube furnace at a heating rate of 5°C / min and held for 1 hour, and then heated to 800°C at a heating rate of 5°C / min and held for 2 hours. The entire process is carried out under nitrogen atmosphere to obtain the bamboo powder carbon powder.

[0010] In step (4), the liquid culture medium is prepared by the following method: 200g of fresh potato chunks are added to deionized water, boiled and stirred continuously for 30 min, the solid is filtered, and the solution is brought to a final volume of 1 L; 20g of glucose, 3g of KH2PO4, 1.5g of MgSO4·7H2O and 5mg of thiamine are added to the solution, stirred until completely dissolved, and after autoclaving, the culture medium is cooled naturally to prepare the liquid culture medium.

[0011] In step (4), bamboo powder and carbon powder are cultured with white rot fungi in a liquid culture medium for 5 days.

[0012] In step (5), the white-rot fungus bamboo powder spheres are dried at 40-60℃; In step (5), the mass ratio of the white-rot fungus bamboo powder spheres to sodium thiosulfate is 1:1-1:3.

[0013] In step (5), the conditions for the impregnation reaction are: reaction at 40-50℃ and 1000rpm-1500rpm for 1.5-2 hours; The heating treatment is as follows: heat to 800°C at 5°C / min and hold for 2 hours.

[0014] The sulfur-doped mycelium bamboo-based composite material was prepared by the method described above.

[0015] The present invention has the following beneficial effects: (1) This invention provides a method for preparing a sulfur-doped mycelium bamboo-based composite material. First, potato dextrose agar medium is prepared, and then white-rot fungi are expanded and cultured on the potato dextrose agar medium. Then, bamboo powder and carbon powder prepared under specific conditions are cultured with white-rot fungi in a liquid culture medium to obtain white-rot fungi bamboo powder spheres. Finally, the obtained white-rot fungi bamboo powder spheres are mixed with sodium thiosulfate for impregnation reaction. After the reaction is completed, the solid material is collected and dried. Finally, the material is heated under a nitrogen atmosphere to obtain the sulfur-doped mycelium bamboo-based composite material. The composite material has high adsorption capacity for heavy metal ions and can effectively remove heavy metal ions when used to treat mercury-containing wastewater.

[0016] (2) The preparation method of the sulfur-doped mycelium bamboo-based composite material of the present invention involves impregnating with sodium thiosulfate and heat-treating with nitrogen to firmly anchor active sulfur groups (such as -SH, -S=O) onto the three-dimensional framework of mycelium-bamboo powder, and reacting them with mercury ions (Hg). 2+ The process forms a highly specific mercury-sulfur bond (Hg-S) with no risk of sulfur leaching, thus avoiding secondary pollution. Nitrogen atmosphere heat treatment promotes the doping of sulfur in a thermally stable form, preventing sulfur leaching during operation. The resulting sulfur-doped mycelium bamboo-based composite material has an adsorption capacity and selectivity far exceeding that of conventional materials.

[0017] (3) The method for preparing the sulfur-doped mycelium bamboo-based composite material of the present invention uses bamboo powder, an agricultural waste, as a substrate, combined with the biological culture of white-rot fungi to form a porous spherical carrier, thereby realizing the resource utilization of solid waste and reducing raw material costs by more than 60%. The three-dimensional porous structure formed by the self-assembly of mycelium does not require additional pore-forming agents, reducing process energy consumption; the mycelial network provides an ultra-large specific surface area, and the carbonized micropores of bamboo powder work synergistically with sulfur active sites to achieve physical enrichment-chemical chelation dual-mode mercury removal. The method of the present invention effectively combines biological carrier design, chemical doping, and thermal stabilization, possessing both targeted adsorption, environmental compatibility, and engineering applicability, providing an efficient and low-consumption solution for the treatment of industrial mercury-containing wastewater. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art 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.

[0019] Figure 1 The images shown are scanning electron microscope images of different biochar composite materials; where (a) is the original bamboo powder carbon powder, (b) is the material SBC2-1 obtained in Example 4, (c) is the material SBC1-1 obtained in Example 1, and (d) is the composite material SBC1-1 (H) after adsorption is completed. Figure 2 The image shows the surface morphology of the mycelium bamboo-based biomass composite material after adsorption and the elemental mapping diagram of the material surface; where (a) is an enlarged view of the surface morphology of the composite material (SBC1-1(H)) after adsorption, and (b)-(e) are elemental mapping diagrams of different elements (C, O, S, Hg) on ​​the surface of the composite material after adsorption. Figure 3 The images show the FTIR spectra of different biochar composite materials. Figure 4 The XPS spectra of different biochar composites are shown below; (a) is the full spectrum of SBC2-1; (b) is the full spectrum of SBC1-1; (c) is the C1s spectrum of SBC2-1; (d) is the O1s spectrum of SBC2-1; (e) is the S2p spectrum of SBC2-1; (f) is the C1s spectrum of SBC1-1; (g) is the O1s spectrum of SBC1-1; and (h) is the S2p spectrum of SBC1-1.

[0020] Figure 5 The images show the crystal structure characterization spectra of the original biochar and sodium thiosulfate modified biochar samples, where (a) is the X-ray diffraction spectrum and (b) is the Raman spectrum. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0022] Unless otherwise specified, all reagents involved in the specific embodiments of this invention are commercially available products and can be purchased through commercial channels.

[0023] Example 1 This embodiment provides a method for preparing a sulfur-doped mycelium bamboo-based composite material, comprising the following steps: (1) Preparation of potato dextrose agar medium (PDA medium): Wash and peel fresh potatoes, and weigh out 200 g of potato chunks. Add the potatoes to deionized water, boil and stir constantly for 30 min, filter out the solids, and bring the solution to a final volume of 1 L. Add 20 g of glucose, 20 g of agar powder, 3 g of KH₂PO₄, 1.5 g of MgSO₄·7H₂O, and 5 mg of thiamine to the solution, stir until completely dissolved, and maintain the natural pH. Then dispense the solution into 300 mL Erlenmeyer flasks and seal the mouths with sealing film. Finally, place the Erlenmeyer flasks in an autoclave at 121°C for 20 minutes to complete the sterilization process. After sterilization, pour the culture medium into plastic petri dishes in a laminar flow hood and allow it to cool naturally to prepare PDA culture medium.

[0024] (2) Propagation of white-rot fungi: Prepare 4-5 PDA culture plates as described above, and wipe the plates containing white rot fungi with 75% alcohol. (white rot fungi To ensure aseptic technique, open the test tube in a clean bench and flame the opening with an alcohol lamp. After autoclaving, repeatedly flame the inoculation spatula in an alcohol lamp flame. Once cooled, cut a small piece of white rot fungus slant culture medium with the spatula and place it into PDA medium. Then, incubate the PDA medium in a 28°C biochemical incubator for 5-7 days to complete the propagation of the white rot fungus.

[0025] (3) Take bamboo material and steam it first, then perform high temperature and high pressure micro-explosion to crush the bamboo material into bamboo powder, and then carbonize the bamboo powder to obtain bamboo powder carbon powder. The specific operation of the high temperature and high pressure micro-explosion is as follows: the temperature is 80℃, the pressure is increased to 0.4MPa, maintained for 10 minutes, and the pressure is released instantly. The material completes the compressed air micro-explosion process under the action of the internal and external pressure difference.

[0026] Preparation of bamboo powder carbon powder: The bamboo powder was first washed and then dried in an oven at 60°C until all moisture was removed. Subsequently, the bamboo powder was heated to 600°C in a tube furnace at a heating rate of 5°C / min and held for 1 hour, and then heated to 800°C at a heating rate of 5°C / min and held for 2 hours. The entire process was carried out under nitrogen atmosphere.

[0027] (4) Prepare an agar-free liquid culture medium according to step (1) and store it in an Erlenmeyer flask; weigh 1.5 g of bamboo powder charcoal powder and add it to the Erlenmeyer flask, then complete the sterilization process. Cut the white-rot fungus on the PDA culture medium with a sterilized inoculation spatula in a laminar flow hood and add it to the Erlenmeyer flask. Then, incubate the Erlenmeyer flask in a constant temperature shaker at 28℃ and 150 rpm for 5 days to obtain white-rot fungus bamboo powder spheres; Preparation of liquid culture medium: Add 200g of fresh potato chunks to deionized water, boil and stir continuously for 30min, filter the solid, and make up the volume of the solution to 1L; add 20g of glucose, 3g of KH2PO4, 1.5g of MgSO4·7H2O and 5mg of thiamine to the solution, stir until completely dissolved, autoclave, and let the culture medium cool naturally to obtain the liquid culture medium.

[0028] (5) The white-rot fungal bamboo powder spheres obtained in step (4) are first dried at 60°C, and then mixed with sodium thiosulfate at a mass ratio of 1:1 for impregnation reaction. The mixture is kept at 45°C and 1200 rpm for 2 hours. After the reaction is completed, the solid material is collected and dried at 60°C. Finally, it is heated to 800°C at 5°C / min and kept for 2 hours under a nitrogen atmosphere to obtain the sulfur-doped mycelium bamboo-based composite material SBC1-1. Figure 1 The image shown is a scanning electron microscope (SEM) image of the sulfur-doped mycelium bamboo-based composite material.

[0029] Example 2 This embodiment provides another method for preparing sulfur-doped mycelium bamboo-based composite material. The only difference from embodiment 1 is that in step (5), the obtained white-rot fungal bamboo powder spheres are first dried at 40°C, and the white-rot fungal bamboo powder spheres are mixed with sodium thiosulfate at a mass ratio of 1:2 for impregnation reaction. The impregnation reaction conditions are: reaction at 40°C and 1500 rpm for 1.5 hours. All other steps and operations are the same as in Example 1. In this example, sulfur-doped mycelium bamboo-based composite material SBC1-2 was prepared.

[0030] Example 3 This embodiment provides another method for preparing sulfur-doped mycelium bamboo-based composite material. The only difference from embodiment 1 is that in step (5), the obtained white-rot fungal bamboo powder spheres are first dried at 50°C, and the white-rot fungal bamboo powder spheres are mixed with sodium thiosulfate at a mass ratio of 1:3 for impregnation reaction. The impregnation reaction conditions are: reaction at 50°C and 1000 rpm for 2 hours. All other steps and operations are the same as in Example 1. In this example, sulfur-doped mycelium bamboo-based composite material SBC1-3 was prepared.

[0031] Example 4 This embodiment provides another method for preparing sulfur-doped mycelium bamboo-based composite material. The only difference from embodiment 1 is that in step (5), the obtained white-rot fungal bamboo powder spheres are first dried at 50°C, and the white-rot fungal bamboo powder spheres are mixed with sodium thiosulfate at a mass ratio of 2:1 for impregnation reaction. The impregnation reaction conditions are: reaction at 50°C and 1000 rpm for 2 hours. All other steps and operations are the same as in Example 1. In this example, sulfur-doped mycelium bamboo-based composite material SBC2-1 was prepared.

[0032] The microstructure of sodium thiosulfate-modified biochar (sulfur-doped mycelium bamboo-based composite material) was observed by SEM. For example... Figure 1 As shown in (a), the SEM image of the original bamboo powder carbon (BC) reveals an overall blocky structure with a few pores on the surface. Figure 1 As shown in (b), the SEM image of the biochar composite material SBC2-1 obtained in Example 4 shows a large blocky structure with some fragmented edges, exhibiting relatively obvious erosion grooves overall. Increasing the doping ratio of sodium thiosulfate enhances the fragmentation of the biochar composite material SBC1-1 obtained in Example 1. This is because the high-temperature pyrolysis of biomass and sulfur-containing salts produces substances such as hydrogen and sulfur dioxide. Sulfur dioxide can act as a pore-forming agent, undergoing an etching reaction on the carbon structure to form mesopores or micropores. After activation with sodium thiosulfate, the surface morphology and pore structure of the biochar are improved.

[0033] Furthermore, the surface morphology of the sulfur-doped mycelium bamboo-based composite material SBC1-1(H) after adsorption was analyzed, along with the elemental mapping of the material surface (e.g., ...). Figure 2 As shown in the figure, Hg is uniformly distributed on the surface of biochar, which proves the adsorption effect of biochar on Hg.

[0034] Table 1 shows the specific surface area and average pore size of different biochar composite materials. It can be seen that the specific surface area of ​​the biochar composite material increases with the increase of the sodium thiosulfate ratio, and the average pore size is around 3 nm, confirming that the modified biochar is a mesoporous material. Sodium thiosulfate, as a pore-forming agent, causes the biochar to form more micropores and mesoporous structures during pyrolysis, thus increasing the specific surface area.

[0035] Table 1 - Specific surface area, average pore size, and pore volume of biochar Figure 3 The FTIR spectra of different biochar composites are shown. 3431 cm⁻¹ -1 The broad peak at 1591 cm⁻¹ is attributed to the combined effect of the OH bond and the stretching vibration of the OH group. -1 The peak at 1034 cm⁻¹ represents the result of the asymmetric stretching vibration of C=C / C=S. After modification, the peak intensity increased significantly, indicating that sulfur modification increased the intensity of the functional groups. -1 The peak enhancement at this point may belong to the symmetrical stretching vibration of -SO3-. 617 cm -1 The peak at 2723-2800 cm⁻¹ represents the asymmetric stretching vibration of the SC group in aromatic compounds. -1 The peak at that position belongs to the stretching vibration of methyl or methylene CH. The CO functional group is located at 1110 cm⁻¹. -1 The peak at that location is 772 cm. -1 The absorption peak is attributed to the CH bending and out-of-plane bending vibrations of the aromatic structure. (1353 cm⁻¹) -1 The peak is attributed to the stretching vibration of CN.

[0036] The surface chemistry and elemental composition of biochar were analyzed by XPS testing. Figure 4 (a) and Figure 4 (b) XPS spectra of modified biochar (SBC2-1 and SBC1-1) are shown. Compared with the full XPS spectrum of BC, a new S2p peak appears in the full spectrum of modified biochar at 150-165 eV. The peak at 1071 eV belongs to the Na1s peak, while the peak at 497 eV belongs to the Auger peak of Na. This indicates that sulfur doping was successfully achieved after the mycelial composite material was modified with sodium thiosulfate. To further analyze the surface properties of biochar, high-resolution spectra of C1s, O1s, and S2p of SBC2-1 and SBC1-1 were fitted and plotted. Figure 4(c)-4(e)). The C1s spectrum of SBC2-1 shows two peaks: the CC / C=C peak at 284.7 eV and the C=O / C=S peak at 286.1 eV. The C1s peaks of SBC1-1 can be fitted as CC / C=C at 284.7 eV, C=O / C=S at 286.1 eV, and OC=O at 289.7 eV, respectively. The O1s spectra of the two also differ; a CO peak is present at 531 eV, and the OC=O peak at 535.1 eV has shifted to OC=O / OH at 535.6 eV. In the fine spectrum of S2p, sulfur mainly forms CSC at 163.8 eV, C=S at 165.1 eV, and SO4 at 169.1 eV. After increasing the doping ratio, a new sulfur oxide peak appears at 170.5 eV (details omitted). Figure 4 (f)-4(h)).

[0037] Figure 5 (a) shows the X-ray diffraction spectra of the original biochar and the sodium thiosulfate-modified biochar samples. The peak at 24.5° represents the (002) crystal plane of the biochar, and the peak at 44.3° represents the (100) crystal plane of the biochar. These represent the disordered arrangement of the crystalline layered structure and the ordered arrangement of graphene layers in the biochar, respectively. After doping with sodium thiosulfate, the peak intensity and relative intensity of the (002) crystal plane increased, while the (100) crystal plane showed a flattening trend. This indicates that the introduction of sulfur, to some extent, disrupted the original graphitic structure of the biochar, increased the number of defect sites, increased the amorphization of the biochar, and decreased the graphitization. This may generate more active sites and improve adsorption performance.

[0038] Raman spectra of raw biochar (BC) and sodium thiosulfate modified biochar samples are as follows: Figure 5 (b) shows the biochar spectral lines at 1320 and 1590 cm⁻¹. -1 There are two distinct characteristic peaks at 1320 cm⁻¹. -1 The D peak reflects the disorder of the graphite lattice structure in biochar. The 1590 cm⁻¹ peak... -1 The characteristic peak at this location is the G peak, which typically indicates graphitization (sp2 hybridization) of biochar. D / I G This can indicate the degree of graphitization and defects in carbon materials. Sodium thiosulfate modified biochar has an I... D / I GThe values ​​increase with increasing doping ratio and are all higher than BC. This means that sulfur-modified biochar has a higher degree of defect and a reduced graphitization structure. This indicates that sulfur doping introduces structural defects into the biochar structure because sulfur atoms replace carbon atoms, thus exacerbating the defects. The increased degree of biochar defect provides more adsorption sites and improves the adsorption effect.

[0039] Experimental Example The adsorption properties of the different composite materials obtained in Examples 1-3 were tested, and the results are shown in Table 2.

[0040] Table 2 - Removal rate of mercury ions from mercury-containing wastewater treated with different composite materials As can be seen from Table 1, Example 3 showed the best results. This is because in the preparation process of the mycelium bamboo-based composite material in Example 3, the mass ratio of sodium thiosulfate was higher, resulting in more sulfur doping and anchoring of more sulfur-based active functional groups, which in turn attracted mercury ions (Hg). 2+ It forms a strong specific mercury-sulfur bond (Hg-S), thus achieving the best adsorption effect.

[0041] In summary, the sulfur-doped mycelium-based bamboo composite material and its preparation method described in this invention first prepare a potato dextrose agar medium, then propagate white-rot fungi on this medium, and then culture white-rot fungi with bamboo powder and carbon powder prepared under specific conditions in a liquid culture medium to obtain white-rot fungi bamboo powder spheres; finally, the obtained white-rot fungi bamboo powder spheres are mixed with sodium thiosulfate for impregnation reaction, and after the reaction is completed, the solid material is collected and dried; finally, it is heated under a nitrogen atmosphere to obtain the sulfur-doped mycelium-based bamboo composite material, which has high adsorption capacity for heavy metal ions and can effectively remove heavy metal ions when used to treat mercury-containing wastewater.

Claims

1. A method for preparing a sulfur-doped mycelium bamboo-based composite material, characterized in that, Includes the following steps: (1) Preparation of potato dextrose agar medium; (2) Propagate white rot fungi based on the potato dextrose agar medium described in step (1); (3) Take bamboo material and steam it first, then perform high temperature and high pressure micro-explosion to crush the bamboo material into bamboo powder, and then carbonize the bamboo powder to obtain bamboo powder carbon powder. The specific operation of the high temperature and high pressure micro-explosion is as follows: the temperature is 80℃, the pressure is increased to 0.4MPa, maintained for 10 minutes, and the pressure is released instantly. The material completes the compressed air micro-explosion process under the action of the internal and external pressure difference. The bamboo powder carbon powder is prepared by the following method: the bamboo powder is first washed, then dried in an oven at 60°C until the moisture is completely removed; the bamboo powder is heated to 600°C in a tube furnace at a heating rate of 5°C / min and held for 1 hour, then heated to 800°C at a heating rate of 5°C / min and held for 2 hours, with nitrogen atmosphere maintained throughout the process, thus obtaining the bamboo powder carbon powder. (4) After culturing bamboo powder and carbon powder with white-rot fungi in a liquid culture medium, the culture medium is removed to obtain white-rot fungi bamboo powder spheres; (5) The white-rot fungus bamboo powder spheres obtained in step (4) are first dried, and then mixed and impregnated with sodium thiosulfate. After the reaction is completed, the solid material is collected and dried. Finally, the mixture is heated under a nitrogen atmosphere to obtain the sulfur-doped mycelium bamboo-based composite material. The conditions for the impregnation reaction are: reaction at 40-50℃ and 1000-1500rpm for 1.5-2 hours; The heating treatment is as follows: heat to 800°C at 5°C / min and hold for 2 hours.

2. The method for preparing the sulfur-doped mycelium bamboo-based composite material according to claim 1, characterized in that, In step (1), the specific method for preparing the potato dextrose agar medium is as follows: Add 200g of fresh potato chunks to deionized water, boil and stir continuously for 30 min, filter the solids, and bring the solution to a final volume of 1 L; add 20 g of glucose, 20 g of agar powder, 3 g of KH2PO4, 1.5 g of MgSO4·7H2O and 5 mg of thiamine to the solution, stir until completely dissolved, autoclave, and allow the culture medium to cool naturally to prepare the potato glucose agar medium.

3. The method for preparing the sulfur-doped mycelium bamboo-based composite material according to claim 1, characterized in that, In step (2), the specific operation of the white rot fungus expansion culture is as follows: take a small piece of white rot fungus slant culture medium, put it into the potato dextrose agar medium, and then place it in a biochemical incubator at 28℃ for 5-7 days to complete the white rot fungus expansion culture.

4. The method for preparing the sulfur-doped mycelium bamboo-based composite material according to claim 1, characterized in that, In step (4), the liquid culture medium is prepared by the following method: 200g of fresh potato chunks are added to deionized water, boiled and stirred continuously for 30 min, the solid is filtered, and the solution is brought to a final volume of 1 L; 20g of glucose, 3g of KH2PO4, 1.5g of MgSO4·7H2O and 5mg of thiamine are added to the solution, stirred until completely dissolved, and after autoclaving, the culture medium is naturally cooled to prepare the liquid culture medium.

5. The method for preparing the sulfur-doped mycelium bamboo-based composite material according to claim 1, characterized in that, In step (4), bamboo powder and carbon powder are cultured with white rot fungi in a liquid culture medium for 5 days.

6. The method for preparing the sulfur-doped mycelium bamboo-based composite material according to claim 1, characterized in that, In step (5), the white-rot fungus bamboo powder spheres are dried at 40-60℃.

7. The method for preparing the sulfur-doped mycelium bamboo-based composite material according to claim 1, characterized in that, In step (5), the mass ratio of the white-rot fungus bamboo powder spheres to sodium thiosulfate is 1:1-1:

3.

8. The sulfur-doped mycelium bamboo-based composite material prepared by the method according to any one of claims 1-7.

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