A sulfidized porous activated carbon composite material, a preparation method and application thereof

Abstract

The application discloses a sulfidized porous activated carbon composite material and a preparation method and application thereof, and belongs to the technical field of inorganic functional materials. The sulfidized porous activated carbon composite material is obtained by adopting a biological mineralization strategy to synthesize copper sulfide / chitosan quaternary ammonium salt composite particles and depositing the copper sulfide / chitosan quaternary ammonium salt composite particles on biomass porous activated carbon material. The biomass porous activated carbon material is used as a carrier to uniformly load the copper sulfide / chitosan quaternary ammonium salt composite particles. The sulfidized porous activated carbon composite material exhibits excellent photo-thermal conversion performance, generates high temperature after light treatment, and combines the structures of the biomass porous activated carbon material and the chitosan quaternary ammonium salt. Therefore, the sulfidized porous activated carbon composite material not only exhibits strong adsorption capacity for organic pollutants in sewage, but also can effectively inhibit and kill bacteria attached to the surface of the sulfidized porous activated carbon composite material.

Description

Technical Field

[0001] This invention belongs to the field of inorganic functional materials technology, specifically relating to a sulfurized porous activated carbon composite material, its preparation method, and its application. Background Technology

[0002] Organic wastewater treatment is a crucial aspect of environmental protection. In recent years, with the rapid development of industry, water pollution has become increasingly serious, with organic pollutants emerging as a major source. These pollutants not only affect the health of aquatic ecosystems but may also pose a threat to human health.

[0003] Chitosan is chemically modified and quaternized to obtain chitosan quaternary ammonium salt. This modification gives it a stronger positive charge density. The positively charged quaternary ammonium salt groups can effectively interact with negatively charged organic pollutants, promoting the adsorption and flocculation of pollutants.

[0004] Activated carbon is widely used in wastewater treatment due to its high surface area and excellent adsorption performance. However, activated carbon adsorption technology also has certain limitations. For example, its large specific surface area can become a breeding ground for bacteria and other microorganisms, leading to secondary pollution. To solve this problem, it is possible to load substances with antibacterial activity onto activated carbon. This not only maintains its original adsorption efficiency but also effectively inhibits the growth of bacteria and other microorganisms.

[0005] Patent CN107312204B discloses a chitosan-iron-titanium polymer material for removing organic matter from wastewater. This invention combines the advantages of chitosan quaternary ammonium salt, TiO2, and Fe2O3. Organic matter in wastewater is adsorbed onto the surface of the chitosan-iron-titanium polymer material and then oxidized and decomposed by a nano-Fe2O3-TiO2 composite catalyst. Simultaneously, the chitosan quaternary ammonium salt flocculant in the polymer material acts as a flocculation agent to remove other fine impurities, achieving thorough adsorption and degradation of organic matter in livestock and poultry wastewater. Patent CN112607832B discloses a nano-zero-valent iron-carbon material. In this material, zero-valent iron and carbon synergistically accelerate electron transfer, exhibiting highly efficient degradation of organic pollutants.

[0006] The adsorbents described above will concentrate on the surface of the adsorbent material after adsorbing pollutants. Since the adsorbent material needs to be placed in the water for a relatively long time to achieve its function of removing pollutants, if the adsorbent material cannot be removed from the water in time, some harmful microorganisms in the water can use the adsorbed and accumulated pollutants to grow and reproduce, thus causing secondary pollution to the water. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a sulfurized porous activated carbon composite material, its preparation method, and its application. Plant fibers and an activator are pretreated and then activated under an inert gas atmosphere to obtain biomass porous activated carbon material. The biomass porous activated carbon material is reacted with a copper ammonia solution to obtain a first mixture. Chitosan quaternary ammonium salt is reacted with the first mixture to obtain a second mixture. A sulfurizing agent is reacted with the second mixture and then freeze-dried to obtain a sulfurized porous activated carbon composite material loaded with copper sulfide / chitosan quaternary ammonium salt composite particles. The prepared sulfurized porous activated carbon composite material has dual functions of adsorbing organic pollutants in wastewater and precise sterilization. On the one hand, the excellent gelling properties of chitosan quaternary ammonium salt improve the bonding stability between copper sulfide and biomass porous activated carbon material. Simultaneously, the gelling properties of chitosan quaternary ammonium salt enhance the adsorption capacity of the biomass porous activated carbon material, resulting in a sulfurized porous activated carbon composite material modified with copper sulfide / chitosan quaternary ammonium salt composite particles exhibiting stronger adsorption of organic pollutants compared to ordinary commercial activated carbon. On the other hand, through chemical deposition on the surface of biomass porous activated carbon, copper ions are deposited and bound to the surface of the biomass porous activated carbon in the solid form of copper sulfide. Copper sulfide has a strong photothermal conversion effect, which gives the prepared sulfide porous activated carbon composite material excellent photothermal conversion characteristics. After light treatment, it can produce high bactericidal performance. Through the synergistic effect of chitosan quaternary ammonium salt and copper sulfide, the adsorption and antibacterial effect of sulfide porous activated carbon composite material on pollutants is achieved, avoiding the secondary pollution problem caused by adsorbents during sewage treatment. Specifically, the technical solution of the present invention includes the following:

[0008] The preparation method of the sulfurized porous activated carbon composite material includes the following steps:

[0009] Step 1:

[0010] Preparation of biomass porous activated carbon material: 50-80 parts by weight of plant fiber and 15-30 parts by weight of activator are mixed in ultrapure water, homogenized and then freeze-dried to obtain precursor carbon material. The precursor carbon material is transferred to a sealed container and activated under inert gas to obtain biomass porous activated carbon material.

[0011] Step Two:

[0012] Preparation of sulfurized porous activated carbon composite material: Biomass porous activated carbon material is dispersed in a copper ammonia solution and shaken to obtain mixture one. Then, chitosan quaternary ammonium salt is added to mixture one and mixed to obtain mixture two. A sulfurizing agent is added to mixture two at 60~70℃ and stirred to react. After the stirring reaction is completed, freeze drying is performed to obtain sulfurized porous activated carbon composite material.

[0013] Furthermore, the plant fiber is soybean residue, and the activator is potassium hydroxide.

[0014] Furthermore, the homogenization conditions include an ultrasonic time of 30-60 min and an ultrasonic power of 100-400 W.

[0015] Furthermore, the freeze-drying conditions include a temperature of -60 to -45°C and a time of 12 to 24 hours.

[0016] Furthermore, the inert gas is argon or nitrogen.

[0017] Furthermore, the inert gas has a flow rate of 300 mL / min and a pressure of 0.5 MPa.

[0018] Furthermore, the activation conditions include a temperature of 600~900℃ and a time of 50~80min.

[0019] Furthermore, the method for preparing the copper ammonia solution includes the following steps:

[0020] Dissolve 100g of copper sulfate in 2500mL of ultrapure water, add 500mL of ammonia water, and stir thoroughly to form a copper ammonia solution.

[0021] Furthermore, the molar concentration of the ammonia solution is 7M.

[0022] Furthermore, the chitosan quaternary ammonium salt includes chitosan quaternary ammonium salt prepared by homogeneous synthesis or commercially available chitosan quaternary ammonium salt.

[0023] Furthermore, the mass ratio of the biomass porous activated carbon material, copper ammonia solution, and chitosan quaternary ammonium salt is 1:20~50:10~40.

[0024] Preferably, the mass ratio of the biomass porous activated carbon material, copper ammonia solution, and chitosan quaternary ammonium salt is 1:40:30.

[0025] Furthermore, the biomass porous activated carbon material reacts with the copper ammonia solution under the following conditions: temperature 20-30°C and time 3-6 hours.

[0026] Furthermore, the conditions for the reaction of the chitosan quaternary ammonium salt with the mixed solution include a temperature of 20-25°C and a time of 2-5 hours.

[0027] Furthermore, the vulcanizing agent is a sodium sulfide solution, and the molar concentration of the sodium sulfide solution is 0.02M~0.06M.

[0028] Furthermore, the mass ratio of the copper ammonia solution to the sulfiding agent is 1:0.3~1.5.

[0029] Furthermore, the stirring reaction conditions for the vulcanizing agent and the second mixture include a temperature of 80~95℃ and a time of 1~3h.

[0030] Furthermore, the freeze-drying conditions include a temperature of -60 to -40°C and a time of 24 to 48 hours.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] (1) The sulfurized porous activated carbon composite material prepared by the present invention not only has excellent adsorption performance for organic pollutants in wastewater, but also has excellent photothermal conversion performance. After being treated with light, it achieves antibacterial performance through the conversion of light energy and heat energy. Combined with the strong adsorption force and photothermal conversion effect of biomass porous activated carbon material and chitosan quaternary ammonium salt, it not only achieves the adsorption and removal of pollutants in water, but also achieves good antibacterial effect, reducing the secondary pollution problem caused by the adsorption material being placed in wastewater for a long time.

[0033] (2) Traditional methods for preparing inorganic materials usually involve the use of toxic surfactants and organic solvents, which may cause environmental pollution and are contrary to the principles of green chemistry. This invention adopts a biomineralization synthesis strategy to prepare copper sulfide composite materials in a green manner, avoiding the use of traditional organic solvents and surfactants, and is more in line with the concept of green chemistry. Detailed Implementation

[0034] The technical solution of the present invention will be clearly and completely described below through embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be prepared by known methods.

[0036] Chitosan quaternary ammonium salt was purchased from Shanghai Yuanye Biotechnology Co., Ltd. Copper sulfide powder was purchased from Shanghai Koraman Reagent Co., Ltd.

[0037] Preparation example:

[0038] Preparation method of copper ammonia solution:

[0039] Dissolve 100g of copper sulfate in 2500mL of ultrapure water, add 500mL of ammonia (molar concentration of ammonia is 7M), and stir thoroughly to form a copper ammonia solution.

[0040] Example 1:

[0041] A method for preparing a sulfurized porous activated carbon composite material specifically includes the following steps:

[0042] Step 1:

[0043] Preparation of biomass porous activated carbon material: 50 parts by weight of soybean residue and 15 parts by weight of potassium hydroxide were weighed and mixed together in 100 parts by weight of ultrapure water to form a homogeneous mixture. The mixture was then treated in an ultrasonic environment with a power of 100W for 30 minutes. After ultrasonication, the mixture was freeze-dried at -45℃ for 12 hours to obtain the precursor carbon material. The precursor carbon material was transferred to a sealed container, and the air in the sealed container was completely replaced with argon gas. Under an argon atmosphere, the sealed container was heated to 600℃ and activated for 50 minutes. After activation, it was naturally cooled to room temperature to obtain the biomass porous activated carbon material.

[0044] Step Two:

[0045] Preparation of sulfurized porous activated carbon composite material: 50g of biomass porous activated carbon material was dispersed in 1000g of the copper ammonia solution obtained in the preparation example, and placed in a shaker. The mixture was shaken at 20℃ for 3 hours to obtain mixture one. After shaking, 500g of chitosan quaternary ammonium salt was added to mixture one and mixed, then reacted in a water bath at 20℃ for 2 hours to obtain mixture two. After the reaction, the temperature was further increased to 60℃, and 300g of sodium sulfide solution (molar concentration of sodium sulfide solution was 0.02M) was added to mixture two. The mixture was stirred at 80℃ for 1 hour. After the reaction, the mixture was naturally cooled to room temperature and then freeze-dried in a freeze dryer at -40℃ for 24 hours to obtain the sulfurized porous activated carbon composite material.

[0046] Example 2:

[0047] A method for preparing a sulfurized porous activated carbon composite material specifically includes the following steps:

[0048] Step 1:

[0049] Preparation of biomass porous activated carbon material: 60 parts by weight of soybean residue and 20 parts by weight of potassium hydroxide were weighed and mixed together in 180 parts by weight of ultrapure water to form a homogeneous mixture. The mixture was then treated in an ultrasonic environment with a power of 200W for 40 minutes. After ultrasonication, the mixture was freeze-dried at -50℃ for 18 hours to obtain the precursor carbon material. The precursor carbon material was transferred to a sealed container, and the air in the sealed container was completely replaced with argon gas. Under an argon atmosphere, the sealed container was heated to 700℃ and activated for 60 minutes. After activation, it was naturally cooled to room temperature to obtain the biomass porous activated carbon material.

[0050] Step Two:

[0051] Preparation of sulfurized porous activated carbon composite material: 50g of biomass porous activated carbon material was dispersed in 1500g of the copper ammonia solution obtained in the preparation example, and placed in a shaker. The mixture was shaken at 22℃ for 4 hours to obtain mixture one. After shaking, 1000g of chitosan quaternary ammonium salt was added to mixture one and mixed, then reacted in a water bath at 22℃ for 3 hours to obtain mixture two. After the reaction, the temperature was further increased to 65℃, and 600g of sodium sulfide solution (molar concentration of sodium sulfide solution was 0.04M) was added to mixture two. The mixture was stirred at 85℃ for 1.5 hours. After the reaction, the mixture was naturally cooled to room temperature and then freeze-dried in a freeze dryer at -45℃ for 30 hours to obtain the sulfurized porous activated carbon composite material.

[0052] Example 3:

[0053] Step 1:

[0054] Preparation of biomass porous activated carbon material: 70 parts by weight of soybean residue and 25 parts by weight of potassium hydroxide were weighed and mixed together in 200 parts by weight of ultrapure water to form a homogeneous mixture. The mixture was then treated in an ultrasonic environment with a power of 300W for 50 minutes. After ultrasonication, the mixture was freeze-dried at -55℃ for 24 hours to obtain the precursor carbon material. The precursor carbon material was transferred to a sealed container, and the air in the sealed container was completely replaced with argon gas. Under an argon atmosphere, the sealed container was heated to 800℃ and activated for 70 minutes. After activation, it was naturally cooled to room temperature to obtain the biomass porous activated carbon material.

[0055] Step Two:

[0056] Preparation of sulfurized porous activated carbon composite material: 50g of biomass porous activated carbon material was dispersed in 2000g of the copper ammonia solution obtained in the preparation example, and placed in a shaker. The mixture was shaken and reacted at 25℃ for 5h to obtain mixture one. After shaking, 1250g of chitosan quaternary ammonium salt was added to mixture one and mixed, and then reacted in a water bath at 23℃ for 4h to obtain mixture two. After the reaction, the temperature was further increased to 70℃, and 900g of sodium sulfide solution (molar concentration of sodium sulfide solution was 0.06M) was added to mixture two at this temperature. The mixture was stirred at 90℃ for 2h. After the reaction, the mixture was naturally cooled to room temperature, and then freeze-dried in a freeze dryer at -50℃ for 36h to obtain the sulfurized porous activated carbon composite material.

[0057] Example 4:

[0058] Step 1:

[0059] Preparation of biomass porous activated carbon material: 80 parts by weight of soybean residue and 30 parts by weight of potassium hydroxide were weighed and mixed together in 250 parts by weight of ultrapure water to form a homogeneous mixture. The mixture was then treated in an ultrasonic environment with a power of 400W for 60 minutes. After ultrasonication, the mixture was freeze-dried at -60℃ for 24 hours to obtain the precursor carbon material. The precursor carbon material was transferred to a sealed container, and the air in the sealed container was completely replaced with argon gas. Under an argon atmosphere, the sealed container was heated to 900℃ and activated for 80 minutes. After activation, it was naturally cooled to room temperature to obtain the biomass porous activated carbon material.

[0060] Step Two:

[0061] Preparation of sulfurized porous activated carbon composite material: 50g of biomass porous activated carbon material was dispersed in 2000g of the copper ammonia solution obtained in the preparation example, and placed in a shaker. The mixture was shaken at 30℃ for 6 hours to obtain mixture one. After shaking, 1500g of chitosan quaternary ammonium salt was added to mixture one and mixed, then reacted in a water bath at 25℃ for 6 hours to obtain mixture two. After the reaction, the temperature was further increased to 70℃, and 1200g of sodium sulfide solution (molar concentration of sodium sulfide solution was 0.06M) was added to mixture two. The mixture was stirred at 95℃ for 3 hours. After the reaction, the mixture was naturally cooled to room temperature and then freeze-dried in a freeze dryer at -60℃ for 48 hours to obtain the sulfurized porous activated carbon composite material.

[0062] Example 5:

[0063] Step 1:

[0064] Preparation of biomass porous activated carbon material: 80 parts by weight of soybean residue and 30 parts by weight of potassium hydroxide were weighed and mixed together in 250 parts by weight of ultrapure water to form a homogeneous mixture. The mixture was then treated in an ultrasonic environment with a power of 400W for 60 minutes. After ultrasonication, the mixture was freeze-dried at -60℃ for 24 hours to obtain the precursor carbon material. The precursor carbon material was transferred to a sealed container, and the air in the sealed container was completely replaced with argon gas. Under an argon atmosphere, the sealed container was heated to 900℃ and activated for 80 minutes. After activation, it was naturally cooled to room temperature to obtain the biomass porous activated carbon material.

[0065] Step Two:

[0066] Preparation of sulfurized porous activated carbon composite material: 50g of biomass porous activated carbon material was dispersed in 2500g of the copper ammonia solution obtained in the preparation example, and placed in a shaker. The mixture was shaken at 30℃ for 6 hours to obtain mixture one. After shaking, 2000g of chitosan quaternary ammonium salt was added to mixture one and mixed, then reacted in a water bath at 25℃ for 6 hours to obtain mixture two. After the reaction, the temperature was further increased to 70℃, and 1500g of sodium sulfide solution (molar concentration of sodium sulfide solution was 0.06M) was added to mixture two. The mixture was stirred at 95℃ for 3 hours. After the reaction, the mixture was naturally cooled to room temperature and then freeze-dried in a freeze dryer at -60℃ for 48 hours to obtain the sulfurized porous activated carbon composite material.

[0067] Comparative Example 1:

[0068] A method for preparing a sulfurized porous activated carbon composite material specifically includes the following steps.

[0069] The biomass porous activated carbon material in Example 4 was replaced with ordinary commercial activated carbon, and all other conditions remained the same as in Example 4.

[0070] Comparative Example 2:

[0071] A method for preparing a sulfurized porous activated carbon composite material specifically includes the following steps:

[0072] The copper ammonia solution in Example 4 was replaced with an acidic solution containing zinc oxide, while the other conditions remained the same as in Example 4.

[0073] Comparative Example 3:

[0074] A method for preparing a sulfurized porous activated carbon composite material specifically includes the following steps:

[0075] The chitosan quaternary ammonium salt in Example 4 was removed, and the remaining conditions were the same as in Example 4.

[0076] Comparative Example 4:

[0077] A method for preparing a sulfurized porous activated carbon composite material specifically includes the following steps:

[0078] Step 1: Same as Example 4.

[0079] Step Two:

[0080] 50g of biomass porous activated carbon material and 200g of copper sulfide powder were mixed in ultrapure water at 30℃ and reacted with shaking for 6h to obtain mixture one. After shaking, 1500g of chitosan quaternary ammonium salt was added to mixture one and mixed, and then reacted in a water bath at 25℃ for 6h to obtain mixture two. After the reaction was completed, the mixture was freeze-dried in a freeze dryer at -60℃ for 48h to obtain the copper sulfide porous activated carbon composite material.

[0081] To more clearly illustrate the present invention, the sulfurized porous activated carbon composite materials prepared in Examples 1-5 and Comparative Examples 1-4 of the present invention were subjected to wastewater treatment tests, photothermal performance tests, and antibacterial tests. The specific tests and results are as follows:

[0082] Experiment 1: Wastewater Treatment Experiment

[0083] Take 1L of untreated wastewater (pH 7.0~8.0) into each beaker, add ordinary commercial activated carbon, sulfurized porous activated carbon materials prepared in Examples 1~5 and Comparative Examples 1~4 of this invention, and shake in a constant temperature shaker at 25℃ for 24h. Test the COD content in the supernatant and calculate the COD removal rate. The results are shown in Tables 1 and 2 below.

[0084] Table 1: COD removal rate test results (all input amounts were 250 mg)

[0085]

[0086] Table 2: COD removal rate test results for different input amounts in Example 4

[0087]

[0088] As can be seen from Tables 1 and 2, the sulfurized porous activated carbon composite material prepared by the preparation method of the present invention has a good COD removal effect.

[0089] (1) The COD removal rate of the sulfurized porous activated carbon composite material prepared by Comparative Example 4 was only 69.8%, indicating that the COD removal effect of the sulfurized porous activated carbon composite material prepared by directly mixing copper sulfide powder, chitosan quaternary ammonium salt and biomass porous activated carbon material was lower than that of the sulfurized porous activated carbon composite material prepared in Example 4.

[0090] (2) The COD removal rate of the sulfurized porous activated carbon composite material prepared in Example 5 was compared with that in Example 4, indicating that when the amount of chitosan quaternary ammonium salt is too large, its gelling property may cause the sulfurized porous activated carbon composite material to agglomerate, thereby reducing the adsorption capacity of the sulfurized porous activated carbon composite material.

[0091] (3) The COD removal rate of the sulfurized porous activated carbon composite material prepared by Example 4 can reach 85.9%, indicating that after the ratio of chitosan quaternary ammonium salt to biomass porous activated carbon material is preferably controlled, the sulfurized porous activated carbon composite material prepared by the present invention can effectively adsorb organic pollutants in wastewater through the combined action of chitosan quaternary ammonium salt and biomass porous activated carbon material.

[0092] (4) By verifying the COD removal rate of the sulfurized porous activated carbon composite material obtained in Example 4 with different input amounts during sewage treatment through Table 2, it can be found that when the input amount of sulfurized porous activated carbon composite material is 250 mg, the COD removal rate reaches the best, reaching 85.9%. When the input amount of sulfurized porous activated carbon composite material is 500 mg, the COD removal rate drops to 79.2%. This indicates that the input amount of sulfurized porous activated carbon composite material needs to be controlled during sewage treatment. If the input amount of sulfurized porous activated carbon composite material is too high, it will also cause an increase in the chitosan quaternary ammonium salt content. Excessive chitosan quaternary ammonium salt will promote the aggregation and agglomeration of sulfurized porous activated carbon composite material due to its gelling properties, ultimately leading to a decrease in the COD removal rate of sulfurized porous activated carbon composite material.

[0093] Experiment 2: Photothermal Performance Test

[0094] Take 1L of untreated wastewater (pH 7.0~8.0, temperature 23℃) into a beaker, add the sulfurized porous activated carbon composite materials prepared in Examples 1~5 and Comparative Examples 1~4 of this invention (250mg each), and treat them under natural light and 808nm laser for 30min respectively. Record the temperature with an infrared thermal imager and calculate the heating effect.

[0095] Table 3. Results of Photothermal Heating

[0096]

[0097] As can be seen from Table 3, the sulfurized porous activated carbon composite material prepared by the preparation method of the present invention has a good photothermal heating effect. Compared with comparative examples 1 to 4, the sulfurized porous activated carbon composite materials prepared in examples 1 to 5 can achieve a good photothermal conversion effect after being treated with natural light and 808nm laser. This indicates that the preparation method of the present invention successfully imparts the photothermal properties of copper sulfide to the sulfurized porous activated carbon composite material, so that the temperature of the sulfurized porous activated carbon composite material increases after light treatment, so as to better exert the antibacterial effect.

[0098] Experiment 3: Antibacterial Test

[0099] Add agar medium to a sterile culture dish, and transfer 2 mL of bacterial suspension using a pipette to a concentration of 5 × 10⁻⁶. 6After mixing CFU / mL, 0.5g of the sulfurized porous activated carbon composite material from Examples 1-5 and Comparative Examples 1-4 was added, and the mixture was dispersed evenly. Each petri dish was then placed in a constant temperature incubator and incubated for 30 min under natural light followed by 6 h, and for 30 min under 808nm laser light followed by 6 h, respectively. The antibacterial performance was tested using the inhibition zone method. The bacterial solutions used in the experiment were *Escherichia coli*, *Staphylococcus aureus*, and *Candida albicans*. The test results are shown in Table 4.

[0100] Table 4. Antibacterial test results after natural light treatment

[0101]

[0102] Table 5. Antibacterial test results after 808nm laser treatment

[0103]

[0104] As can be seen from Tables 4 and 5, the sulfurized porous activated carbon composite material prepared by the method of this invention has obvious antibacterial effects against different bacteria. Compared with Comparative Examples 1-4, the inhibition zone of Example 4 against different bacteria reached more than 10 mm, indicating that the synergistic antibacterial effect of chitosan quaternary ammonium salt and copper sulfide with photothermal conversion effect on the sulfurized porous activated carbon composite material can exert a good antibacterial effect. Moreover, the sulfurized porous activated carbon composite material after 808 nm laser treatment showed an even better antibacterial effect, indicating that the sulfurized porous activated carbon composite material constructed by the present invention through chemical deposition and the gelation effect of chitosan quaternary ammonium salt is an excellent antibacterial material.

[0105] The embodiments described above provide a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. A method for preparing a sulfurized porous activated carbon composite material, characterized in that, The preparation method includes the following steps: Step 1: Preparation of biomass porous activated carbon material: 50-80 parts by weight of plant fiber and 15-30 parts by weight of activator are mixed in ultrapure water, homogenized and then freeze-dried to obtain precursor carbon material. The precursor carbon material is transferred to a sealed container and activated under inert gas to obtain biomass porous activated carbon material. Step Two: Preparation of sulfurized porous activated carbon composite material: Biomass porous activated carbon material is dispersed in a copper ammonia solution and shaken to obtain mixture one. Then, chitosan quaternary ammonium salt is added to mixture one and mixed to obtain mixture two. A sulfurizing agent is added to mixture two at 60~70℃ and stirred to react. After the stirring reaction is completed, freeze drying is performed to obtain sulfurized porous activated carbon composite material.

2. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The plant fiber is soybean residue, and the activator is potassium hydroxide.

3. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The homogenization conditions include an ultrasonic time of 30-60 min and an ultrasonic power of 100-400 W.

4. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The freeze-drying conditions include a temperature of -60 to -45°C and a time of 12 to 24 hours.

5. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The inert gas is argon or nitrogen.

6. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The activation conditions include a temperature of 600-900℃ and a time of 50-80 minutes.

7. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The mass ratio of the biomass porous activated carbon material, copper ammonia solution, and chitosan quaternary ammonium salt is 1:20~50:10~40.

8. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The vulcanizing agent is a sodium sulfide solution, and the molar concentration of the sodium sulfide solution is 0.02M~0.06M.

9. The method for preparing a sulfurized porous activated carbon composite material as described in claim 1, characterized in that, The volume ratio of the copper ammonia solution to the sulfiding agent is 1:0.3~1.

5.

10. The application of a sulfurized porous activated carbon composite material prepared by the preparation method of any one of claims 1 to 9 in the field of inorganic functional materials technology.

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