An antibacterial gas adsorbent and a method for preparing the same

Abstract

The application provides an antibacterial gas adsorbent and a preparation method thereof. The adsorbent comprises a carrier, an antibacterial agent, an adsorption auxiliary agent and a catalytic auxiliary agent. The carrier is a composite carrier of MOFs material and carbon material. The antibacterial agent comprises at least one of copper oxide, copper chloride, copper nitrate, silver salt and zinc salt. The adsorption auxiliary agent comprises at least one of lanthanum oxide, cerium oxide, magnesium oxide and cobalt oxide and at least one of sodium citrate, potassium pyrophosphate, sodium thiosulfate and sodium hydroxyl carboxylate. The catalytic auxiliary agent is prepared by sintering melamine, ferrocene and nano copper oxide. The antibacterial gas adsorbent of the application overcomes the problem of agglomeration, has excellent antibacterial and adsorption treatment performance on organic gas, and improves the repeated application performance and recovery performance of the antibacterial gas adsorbent by matching the adsorption auxiliary agent and the catalytic auxiliary agent. The performance of the used, failed or degraded antibacterial gas adsorbent can be restored after heat treatment.

Description

Technical Field

[0001] This invention relates to the field of materials for gas environment treatment, and specifically to an antibacterial gas adsorbent and its preparation method. Background Technology

[0002] Environmental pollutants not only damage the environment but also harm human health. Typical environmental pollutants include hydrogen sulfide, sulfur dioxide, methanethiol, ammonia, and methylamine, which have unpleasant odors and a low olfactory threshold, easily causing strong olfactory stimulation. High concentrations of these odorous gases can stimulate the central nervous system, leading to respiratory paralysis and potentially death. Therefore, the control of these environmental pollutants is of great significance to people's living environment and health.

[0003] Invention patent 202310759709.9 discloses a copper-zinc composite antibacterial agent for water and air purification and its preparation method. The copper-zinc composite antibacterial agent uses diatomaceous earth, mesoporous silica, vermiculite, zeolite, titanium dioxide, talc, and activated alumina as carriers to support a copper-zinc composite material. This material has antibacterial effects, but its gas purification function needs improvement. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the existing technology and provide an antibacterial gas adsorbent and its preparation method.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: an antibacterial gas adsorbent, wherein the adsorbent comprises a carrier, an antibacterial agent, an adsorption auxiliary agent, and a catalytic auxiliary agent;

[0006] The support is a composite support of MOFs material and carbon material, the antibacterial agent is loaded on the support, the adsorption aid is loaded on the support, and the catalytic aid is loaded on the support; the weight ratio of MOFs material to carbon material is (0.5~1.5):1.

[0007] The antibacterial agent includes at least one of copper oxide, copper chloride, copper nitrate, silver salt, and zinc salt;

[0008] The adsorption aid includes at least one of lanthanum oxide, cerium oxide, magnesium oxide, and cobalt oxide, and at least one of sodium citrate, potassium pyrophosphate, sodium thiosulfate, and sodium hydroxycarboxylate.

[0009] The catalytic aid is prepared by sintering melamine, ferrocene and nano-copper oxide.

[0010] The aforementioned antibacterial gas adsorbent uses a composite carrier of MOFs (Metal-Oxide-Factory) and carbon materials. MOFs possess large specific surface area, adjustable porosity and pore size, strong surface modification capabilities, and good chemical and thermal stability. Loading antibacterial agents onto MOFs enhances the antibacterial and organic gas adsorption performance of the adsorbent. However, MOFs are prone to aggregation after loading with antibacterial agents, affecting the antibacterial and organic gas adsorption performance. Through research, the inventors have overcome this aggregation problem with the aforementioned antibacterial gas adsorbent, which uses a composite carrier of MOFs and carbon materials. This results in excellent antibacterial and organic gas adsorption performance. Furthermore, the addition of adsorption aids and catalytic aids improves the reusability and recyclability of the adsorbent. Used, ineffective, or degraded antibacterial gas adsorbents can be restored to their original performance through heat treatment.

[0011] Preferably, the weight ratio of the support to the catalytic auxiliary is 1:(0.05-0.2).

[0012] Preferably, the mass ratio of the carrier to the antibacterial agent and the adsorption aid is 1:(0.1-0.25):(0.05-0.2).

[0013] Through research, the inventors discovered that when the mass ratio of carrier, antibacterial agent, and catalytic auxiliary agent is 1:(0.1~0.25):(0.05~0.2), the antibacterial gas adsorbent exhibits better antibacterial performance, adsorption and treatment performance for organic gases, and reusability.

[0014] Preferably, the weight ratio of melamine, ferrocene and nano-copper oxide in the catalyst auxiliary agent is 10:(0.8-1.5):(1-2).

[0015] Through research, the inventors discovered that when the weight ratio of melamine, ferrocene, and nano-copper oxide in the catalytic auxiliary agent is 10:(0.8-1.5):(1-2), the antibacterial gas adsorbent exhibits better antibacterial properties, adsorption and treatment performance for organic gases, and reusability.

[0016] Preferably, the MOF material is MIL-100, MIL-101, MOF-74, or ZIF-8.

[0017] Preferably, the silver salt is silver nitrate.

[0018] Preferably, the antibacterial agent is a zinc salt, wherein the zinc salt is at least one selected from zinc nitrate, zinc sulfate, zinc chloride, zinc carbonate, zinc acetate, zinc phosphate, zinc pyrophosphate, and zinc citrate, and the adsorption aid includes at least one selected from lanthanum oxide and cerium oxide, and at least one selected from potassium pyrophosphate and sodium hydroxycarboxylate.

[0019] Preferably, the preparation method of the antibacterial gas adsorbent includes the following steps:

[0020] (1) MOFs materials are deposited on the surface of powdered wood or bamboo materials at 20-30℃ using in-situ deposition method to obtain a composite carrier of MOFs materials and carbon materials.

[0021] (2) The MOF material and carbon material composite carrier are immersed in an adsorption aid solution A with a mass concentration of 1% to 10% and ultrasonically treated at 20 to 30°C for 10 to 50 minutes. The solvent in the adsorption aid solution A is acidic water. Solid particles A are obtained by solid-liquid separation and the liquid on the surface of solid particles A is removed. Then, solid particles A are immersed in solution A with a mass concentration of 1% to 20% and stirred at 20 to 30°C for 1 to 5 hours.

[0022] (3) Separate solid particles from the system after step (2), dry them at 60-100°C for 1-5 hours, and treat them at 300-500°C for 1-5 hours in an inert gas atmosphere, and then cool them in an inert gas atmosphere to obtain sintered material A;

[0023] (4) Immerse the sintered material A in an antibacterial agent solution B with a mass concentration of 2% to 10% and sonicate it at 20 to 30°C for 10 to 50 minutes. The solvent of the antibacterial agent solution B is acidic water. Solid particles B are obtained by solid-liquid separation and the liquid on the surface of the solid particles B is removed. Then, the solid particles B are immersed in an antibacterial agent solution B with a mass concentration of 2% to 25% and stirred at 20 to 30°C for 1 to 5 hours.

[0024] (5) Separate solid particles from the system after step (4), dry them at 40-70°C for 1-5 hours, and treat them at 200-500°C for 1-5 hours in a reducing gas atmosphere, and then cool them to obtain sintered material B.

[0025] (6) After grinding the sintered material B with melamine, ferrocene and nano copper oxide in a certain proportion, it is subjected to high temperature treatment at 600-900°C for 1-2 hours in an inert gas atmosphere and then cooled to obtain the antibacterial gas adsorbent.

[0026] Preferably, in step (2), the material-to-liquid ratio is 1:(2-5); in step (4), the material-to-liquid ratio is 1:(2-5).

[0027] This invention also provides a method for preparing any of the above-described antibacterial gas adsorbents, the method comprising the following steps:

[0028] (1) MOFs materials are deposited on the surface of powdered wood or bamboo materials at 20-30℃ using in-situ deposition method to obtain a composite carrier of MOFs materials and carbon materials.

[0029] (2) The MOF material and carbon material composite carrier are immersed in an adsorption aid solution A with a mass concentration of 1% to 10% and ultrasonically treated at 20 to 30°C for 10 to 50 minutes. The solvent in the adsorption aid solution A is acidic water. Solid particles A are obtained by solid-liquid separation and the liquid on the surface of solid particles A is removed. Then, solid particles A are immersed in solution A with a mass concentration of 1% to 20% and stirred at 20 to 30°C for 1 to 5 hours.

[0030] (3) Separate solid particles from the system after step (2), dry them at 60-100°C for 1-5 hours, and treat them at 300-500°C for 1-5 hours in an inert gas atmosphere, and then cool them in an inert gas atmosphere to obtain sintered material A;

[0031] (4) Immerse the sintered material A in an antibacterial agent solution B with a mass concentration of 2% to 10% and sonicate it at 20 to 30°C for 10 to 50 minutes. The solvent of the antibacterial agent solution B is acidic water. Solid particles B are obtained by solid-liquid separation and the liquid on the surface of the solid particles B is removed. Then, the solid particles B are immersed in an antibacterial agent solution B with a mass concentration of 2% to 25% and stirred at 20 to 30°C for 1 to 5 hours.

[0032] (5) Separate solid particles from the system after step (4), dry them at 40-70°C for 1-5 hours, and treat them at 200-500°C for 1-5 hours in a reducing gas atmosphere, and then cool them to obtain sintered material B;

[0033] (6) After grinding the sintered material B with melamine, ferrocene and nano copper oxide in a certain proportion, it is subjected to high temperature treatment at 600-900°C for 1-2 hours in an inert gas atmosphere and then cooled to obtain the antibacterial gas adsorbent.

[0034] Preferably, in step (2), the material-to-liquid ratio is 1:(2-5).

[0035] Preferably, in step (4), the material-to-liquid ratio is 1:(2-5).

[0036] The beneficial effects of this invention are as follows: This invention provides an antibacterial gas adsorbent. The antibacterial gas adsorbent of this invention uses a composite carrier of MOFs (Metal-Oxide-Factory Materials) and carbon materials. MOFs materials have a large specific surface area, adjustable porosity and pore size, strong surface modification function, and good chemical and thermal stability. Loading antibacterial agents onto MOFs materials is beneficial to improving the antibacterial and organic gas adsorption performance of the antibacterial gas adsorbent. However, after loading antibacterial agents, MOFs materials are prone to aggregation, affecting the antibacterial and organic gas adsorption performance of the antibacterial gas adsorbent. Through research, the inventors have overcome the aggregation problem of antibacterial gas adsorbents by using MOFs and carbon materials as a composite carrier, exhibiting excellent antibacterial and organic gas adsorption performance. Furthermore, the combination of adsorption aids and catalytic aids improves the reusability and recovery performance of the antibacterial gas adsorbent. Used, ineffective, or degraded antibacterial gas adsorbents can have their performance restored after heat treatment. Attached Figure Description

[0037] Figure 1 A schematic diagram of a simplified apparatus for testing the formaldehyde removal effect of the chitosan-modified adhesive of the present invention.

[0038] 1. Reaction chamber; 2. Pressure balance bag; 3. Formaldehyde solution bottle; 4. Formaldehyde inlet; 5 and 6. Rubber hose; 7. Airtight membrane; 8. Vent. Detailed Implementation

[0039] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0040] Example 1

[0041] As an antibacterial gas adsorbent according to an embodiment of the present invention, the adsorbent includes a carrier, an antibacterial agent, an adsorption aid, and a catalytic aid;

[0042] The support is a composite support of MOFs material and carbon material, the antibacterial agent is loaded on the support, the adsorption aid is loaded on the support, and the catalytic aid is loaded on the support; the weight ratio of MOFs material to carbon material is 0.8:1.

[0043] The antibacterial agent is a zinc salt, and the zinc salt is zinc chloride;

[0044] The adsorption aid is lanthanum oxide and potassium pyrophosphate, and the mass ratio of lanthanum oxide to potassium pyrophosphate is 1:1.

[0045] The catalytic aid is prepared by sintering melamine, ferrocene and nano-copper oxide.

[0046] The weight ratio of the support to the catalytic auxiliary is 1:0.1;

[0047] The weight ratio of melamine, ferrocene, and nano-copper oxide in the catalyst auxiliary agent is 10:1:1.5; the MOF material is MIL-100.

[0048] The preparation method of the antibacterial gas adsorbent in this embodiment includes the following steps:

[0049] (1) MOFs material was deposited on the surface of powdered bamboo material by in-situ deposition at 25℃ to obtain a composite carrier of MOFs material and carbon material.

[0050] (2) The MOFs material and carbon material composite carrier were immersed in a 3% (w / w) adsorption aid solution A and ultrasonically treated at 25°C for 30 minutes. The solvent in the adsorption aid solution A was acidic water, i.e., the adsorption aid was dispersed in water and hydrochloric acid was added dropwise until the adsorption aid dissolved. Solid particles A were obtained by solid-liquid separation and the liquid on the surface of solid particles A was removed. Then, solid particles A were immersed in a 5% (w / w) solution A and stirred at 25°C for 2 hours. The material-to-liquid ratio was 1:3.

[0051] (3) The solid particles were separated from the system after step (2), dried at 70°C for 2 hours, and then treated at 400°C for 2 hours under a nitrogen atmosphere and cooled under an inert gas atmosphere to obtain sintered material A.

[0052] (4) Immerse the sintered material A in a 4% (w / w) antibacterial agent solution B and sonicate it at 20-30°C for 30 minutes. The solvent of the antibacterial agent solution B is acidic water, i.e., the antibacterial agent is dispersed in water and hydrochloric acid is added dropwise until the antibacterial agent dissolves. Solid particles B are obtained by solid-liquid separation and the liquid on the surface of solid particles B is removed. Then, the solid particles B are immersed in an 8% (w / w) antibacterial agent solution B and stirred at 25°C for 2 hours. The material-to-liquid ratio is 1:3.

[0053] (5) Separate solid particles from the system after step (4), dry them at 50°C for 2 hours, and treat them at 350°C for 2 hours in a reducing gas atmosphere. Cool them to obtain sintered material B.

[0054] (6) The sintered material B is ground with melamine, ferrocene and nano copper oxide in a certain proportion and then treated at 700°C for 1.5 hours in an inert gas atmosphere and cooled to obtain the antibacterial gas adsorbent.

[0055] The antibacterial gas adsorbent prepared in this embodiment was tested for zinc and lanthanum content by ICP. After mass conversion, the mass ratio of carrier to antibacterial agent and adsorption aid was 1:0.13:0.08.

[0056] Example 2

[0057] As an antibacterial gas adsorbent in this embodiment of the invention, the difference between this embodiment and Embodiment 1 is as follows:

[0058] The antibacterial agent is a zinc salt, and the zinc salt is zinc nitrate;

[0059] The adsorption aid is cerium oxide and sodium hydroxycarboxylate, with a weight ratio of cerium oxide to sodium hydroxycarboxylate of 1:1.

[0060] The catalytic aid is prepared by sintering melamine, ferrocene and nano-copper oxide.

[0061] The weight ratio of melamine, ferrocene, and nano-copper oxide in the catalyst auxiliary agent is 10:1:1.5; the MOF material is MIL-101.

[0062] The antibacterial gas adsorbent prepared in this embodiment was tested for zinc and cerium content by ICP. After mass conversion, the mass ratio of carrier to antibacterial agent and adsorption aid was 1:0.12:0.08.

[0063] Example 3

[0064] As an antibacterial gas adsorbent in this embodiment of the invention, the difference between this embodiment and Embodiment 1 is as follows:

[0065] The antibacterial agent is copper chloride;

[0066] The adsorption aid is cerium oxide and sodium hydroxycarboxylate, with a weight ratio of cerium oxide to sodium hydroxycarboxylate of 1:1.

[0067] The catalytic aid is prepared by sintering melamine, ferrocene and nano-copper oxide.

[0068] The weight ratio of melamine, ferrocene, and nano-copper oxide in the catalyst auxiliary agent is 10:1:1.5; the MOF material is MIL-101.

[0069] Example 4

[0070] As an antibacterial gas adsorbent in this embodiment of the invention, the difference between this embodiment and Embodiment 1 is as follows:

[0071] The antibacterial agent is a zinc salt, and the zinc salt is zinc chloride;

[0072] The adsorption aid is magnesium oxide and sodium hydroxycarboxylate, with a weight ratio of 1:1.

[0073] The catalytic aid is prepared by sintering melamine, ferrocene and nano-copper oxide.

[0074] The weight ratio of melamine, ferrocene, and nano-copper oxide in the catalyst auxiliary agent is 10:1:1.5; the MOF material is MIL-101.

[0075] The antibacterial gas adsorbent prepared in this embodiment was tested for zinc and magnesium content by ICP. After mass conversion, the mass ratio of carrier to antibacterial agent and adsorption aid was 1:0.13:0.07.

[0076] Comparative Example 1

[0077] As an antibacterial gas adsorbent for comparative examples of the present invention, the difference between this embodiment and Comparative Example 1 is that the carrier is a MOF material, and the MOF material is MIL-100.

[0078] Comparative Example 2

[0079] As an antibacterial gas adsorbent for comparative examples of the present invention, the difference between this embodiment and Comparative Example 1 is that the carrier is bamboo activated carbon.

[0080] Comparative Example 3

[0081] As an antibacterial gas adsorbent for comparative examples of the present invention, the difference between this embodiment and Comparative Example 1 is that the adsorption aid is cerium oxide.

[0082] Comparative Example 4

[0083] As an antibacterial gas adsorbent for comparative examples of the present invention, the difference between this embodiment and Comparative Example 1 is that the adsorption aid is lanthanum oxide.

[0084] Comparative Example 5

[0085] As an antibacterial gas adsorbent for comparative examples of the present invention, the difference between this embodiment and Comparative Example 1 is that the catalytic aid is prepared by sintering melamine, ferrocene and nano zinc oxide.

[0086] Comparative Example 6

[0087] As an antibacterial gas adsorbent for comparative examples of the present invention, the difference between this embodiment and Comparative Example 1 is that the catalytic aid is prepared by sintering melamine and nano zinc oxide.

[0088] Experimental methods

[0089] 1. The antibacterial performance of the antibacterial gas adsorbents in the examples and comparative examples was tested using the patch method.

[0090] The specific method is as follows: Prepare the required volumes of agar culture medium and nutrient broth. The agar culture medium formula is: 15 g / L peptone, 5 g / L yeast extract, 15 g / L agar powder, and 10 g / L sodium chloride. The nutrient broth formula is: 15 g / L peptone, 5 g / L yeast extract, and 10 g / L sodium chloride. Place 20 mL of the prepared nutrient broth, 20 mL of distilled water, and agar culture medium into a high-temperature sterilizer for sterilization. The sterilization temperature is 121℃, the pressure is 103 kPa, and the time is 25 min. Inoculate a colony of *E. coli* into 20 mL of nutrient broth using a circular needle, and incubate in a vertical constant temperature shaker at (37±1)℃, a rotation speed of 110 r / min, and a time of 18–24 h. Take 1 mL of the nutrient broth containing the bacterial culture and dilute it with 20 mL of sterilized distilled water until the bacterial concentration is 1×10⁻⁶. 8 ~5×10 8 CFU / mL, shake well. Use a pipette to transfer 100 μL of the diluted bacterial solution onto an agar medium, and spread it evenly on the surface of the medium until the nutrient broth is absorbed by the medium.

[0091] Take a sterile paper disc with a diameter of 1 cm, disperse 1 mg of the antibacterial gas adsorbent from the examples and comparative examples in 100 μL of sterile water, and coat it evenly on the sterile paper disc. Place the paper disc containing the antibacterial gas adsorbent on an agar plate inoculated with test bacteria, incubate at 37°C for 18 hours, and measure the size of the inhibition zone formed.

[0092] The bacterial strains used were Escherichia coli and Staphylococcus aureus, with blank sterilized paper discs used as controls.

[0093] The inhibition zone size of the antibacterial gas adsorbent is a1, and the inhibition zone size of the reference standard is a0.

[0094] Antibacterial rate (%) = (a1-a0) / a1×100%.

[0095] The experimental results are shown in Table 1.

[0096] Table 1. Antibacterial rate (%) of the antibacterial gas adsorbents in the examples and comparative examples.

[0097] sample Escherichia coli inhibition rate (%) Staphylococcus aureus inhibition rate (%) Example 1 97.6 98.3 Example 2 97.3 98.6 Example 3 94.3 95.1 Example 4 93.9 94.6 Comparative Example 1 82.0 87.4 Comparative Example 2 76.8 72.9 Comparative Example 3 85.6 88.6 Comparative Example 4 88.1 84.7 Comparative Example 5 89.7 87.8 Comparative Example 6 89.3 86.0

[0098] 2. Odor Gas Adsorption Performance Test

[0099] (1) As Figure 1As shown, conical flask 3 serves as a gas generator. The conical flask containing the gas solution is placed in a water bath and the temperature is adjusted; slight heating accelerates gas evaporation. The gas is delivered to reaction chamber 1 via rubber hose 5. Reaction chamber 1 is a transparent glass cube with a side length of 0.3m. A 10cm × 10cm glass door is installed on the side wall, with a ring-shaped rubber sealing strip affixed to the edge of the door. On the other side of the reaction chamber, there are two vents 8. One vent is connected to the pressure balance bag 2 via rubber hose 6, and the other vent is sealed by an airtight membrane (either silicone or latex material) 7. After the gas concentration in the reaction chamber reaches the set initial concentration, the rubber hose between conical flask 3 and reaction chamber 1 is clamped, and the sample to be tested is quickly placed in the reaction chamber. The experiment begins at 25℃. After 30 minutes, a sample is taken through the vent sealed by the airtight membrane (either silicone or latex material) 7 to measure the concentration of the gas to be tested. Throughout the experiment, the initial gas concentration should be maintained at the set concentration. All interfaces should be sealed with Vaseline. After determining the initial concentration, the gas generator should be turned off, and the rubber tube between the conical flask 3 and the reaction chamber 1 should be clamped to prevent leakage. After the sample is placed in, the glass door should also be sealed with Vaseline. After sampling, the pinholes of the airtight membrane (either silicone or latex material) 7 should also be sealed with Vaseline.

[0100] (2) The test samples are 0.1g of the antibacterial gas adsorbent of the example and the comparative example. The test samples are spread as flat as possible in the petri dish and placed in the reaction chamber.

[0101] (3) The gases to be tested are hydrogen sulfide, sulfur dioxide, and ammonia. The initial concentration of the gases is 10 mg / m³. 3 The experimental results are shown in Table 2.

[0102] Table 2. Adsorption rates (%) of odor gases by the antibacterial gas adsorbents in the examples and comparative examples.

[0103] sample Hydrogen sulfide adsorption rate (%) Sulfur dioxide adsorption rate (%) Ammonia adsorption rate (%) Example 1 98.9 98.8 97.3 Example 2 97.1 98.6 95.4 Example 3 92.1 91.8 91.7 Example 4 93.4 92.8 92.6 Comparative Example 1 69.5 71.0 66.8 Comparative Example 2 65.5 67.2 73.8 Comparative Example 3 77.5 84.0 79.2 Comparative Example 4 80.9 79.2 78.0 Comparative Example 5 80.2 76.0 80.1 Comparative Example 6 80.6 81.4 83.8

[0104] 3. Reusability and recovery performance of antibacterial gas adsorbents

[0105] (1) As Figure 1 As shown, the conical flask 3 serves as a gas generator. The conical flask containing the gas solution is placed in a water bath and the temperature is adjusted. Slight heating accelerates gas evaporation. The gas is transported to the reaction chamber 1 via a rubber hose 5. The reaction chamber 1 is a transparent glass cube with a side length of 0.3m. A 10cm × 10cm glass door is provided on the side wall. The edge of the glass door is affixed with a ring-shaped rubber sealing strip. There are two vents 8 on the other side of the reaction chamber. One vent is connected to the pressure balance bag 2 by a rubber hose 6, and the other vent is sealed by an airtight membrane (either silicone or latex material) 7.

[0106] (2) Using ammonia as the test gas, the conical flask containing concentrated ammonia solution was heated to accelerate gas volatilization, so that the initial concentration of the gas in the reaction chamber was 10 mg / m³. 3 Then, clamp the rubber hose 5 with a clip.

[0107] (3) The test samples are 0.1g of the antibacterial gas adsorbent of the examples and comparative examples, respectively. The test samples are spread as flat as possible in the petri dish and placed in the reaction chamber.

[0108] (4) After 1 hour, samples were taken through the air holes sealed by the airtight membrane (both silicone and latex materials) 7 to measure the concentration of the gas to be tested.

[0109] (5) Heat the conical flask containing concentrated ammonia to accelerate gas volatilization, and then control the gas concentration in the reaction chamber to 10 mg / m³ again. 3 Then, clamp the rubber hose 5 with a clamp, and after 1 hour of adsorption, take a sample through the air hole sealed by the airtight membrane (both silicone and latex materials) 7 to measure the concentration of the gas to be tested.

[0110] (6) Repeat step (5) until the gas concentration of the sampled gas reaches equilibrium at 10 mg / m³. 3 This indicates that the antibacterial gas adsorbent in the reaction chamber no longer has the activity to treat and adsorb odorous gases, that is, it is in a deactivated state.

[0111] (7) The antibacterial gas adsorbents of the examples and comparative examples that were deactivated in step (6) were dried at 70°C for 30 minutes.

[0112] The adsorption performance of the antibacterial gas obtained in step (7) above on ammonia was tested using the same method as in "2. Adsorption performance test of odor gas". The experimental results are shown in Table 3.

[0113] Table 3. Reusability and recovery performance of antibacterial gas adsorbents

[0114] sample Ammonia adsorption rate (%) Example 1 87.9 Example 2 86.7 Example 3 84.0 Example 4 86.6 Comparative Example 1 38.5 Comparative Example 2 45.2 Comparative Example 3 60.4 Comparative Example 4 58.0 Comparative Example 5 60.2 Comparative Example 6 61.9

[0115] The aforementioned antibacterial gas adsorbent was placed in a reaction chamber, and ammonia was continuously added until the adsorbent lost its ability to treat and adsorb ammonia. After a simple drying process, the antibacterial gas adsorbent in the examples could basically recover its ammonia adsorption performance, but the antibacterial gas adsorbent in the comparative examples showed an extremely low recovery rate in ammonia adsorption removal performance. Comparing the results of the examples and Comparative Example 1 in Tables 2 and 3 shows that the antibacterial gas adsorbent in Comparative Example 1, using MOFs as a carrier, suffered performance degradation due to agglomeration. This indicates that the antibacterial gas adsorbent using a composite carrier of MOFs and carbon materials overcomes the agglomeration problem, exhibiting excellent antibacterial and organic gas adsorption performance. Furthermore, the combination of adsorption aids and catalytic aids improves the reusability and recyclability of the antibacterial gas adsorbent. Used, ineffective, or degraded antibacterial gas adsorbents can have their performance restored through heat treatment.

[0116] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An antibacterial gas adsorbent, characterized in that, The adsorbent includes a carrier, an antibacterial agent, an adsorption aid, and a catalytic aid; The support is a composite support of MOFs material and carbon material, the antibacterial agent is loaded on the support, the adsorption aid is loaded on the support, and the catalytic aid is loaded on the support; the weight ratio of MOFs material to carbon material in the composite support of MOFs material and carbon material is (0.5~1.5):

1. The antibacterial agent includes at least one of copper oxide, copper chloride, copper nitrate, silver salt, and zinc salt; The adsorption aid includes at least one of lanthanum oxide, cerium oxide, magnesium oxide, and cobalt oxide, and at least one of sodium citrate, potassium pyrophosphate, sodium thiosulfate, and sodium hydroxycarboxylate. The catalytic aid is prepared by sintering melamine, ferrocene and nano-copper oxide. The preparation method of the antibacterial gas adsorbent includes the following steps: (1) MOFs materials are deposited on the surface of powdered wood or bamboo materials at 20~30℃ using in-situ deposition method to obtain MOFs material and carbon material composite carrier; (2) The MOFs material and carbon material composite carrier are immersed in an adsorption aid solution A with a mass concentration of 1%~10% and ultrasonically treated at 20~30℃ for 10~50 minutes. The solvent in the adsorption aid solution A is acidic water, that is, the adsorption aid is dispersed in water and hydrochloric acid is added dropwise until the adsorption aid dissolves. Solid-liquid separation is performed to obtain solid particles A and the liquid on the surface of solid particles A is removed. Then, solid particles A are immersed in solution A with a mass concentration of 1%~20% and stirred at 20~30℃ for 1~5 h. (3) Separate solid particles from the system after step (2), dry them at 60~100℃ for 1~5 h, and treat them at 300~500℃ for 1~5 h in an inert gas atmosphere, and then cool them in an inert gas atmosphere to obtain sintered material A; (4) Immerse the sintered material A in an antibacterial agent solution B with a mass concentration of 2%~10% and sonicate it at 20~30℃ for 10~50 minutes. The solvent of the antibacterial agent solution B is acidic water, that is, the antibacterial agent is dispersed in water and hydrochloric acid is added dropwise until the antibacterial agent dissolves. Solid-liquid separation is performed to obtain solid particles B and the liquid on the surface of solid particles B is removed. Then, immerse the solid particles B in an antibacterial agent solution B with a mass concentration of 2%~25% and stir it at 20~30℃ for 1~5 hours. (5) Separate solid particles from the system after step (4), dry them at 40~70℃ for 1~5 h, and treat them at 200~500℃ for 1~5 h in a reducing gas atmosphere, and then cool them to obtain sintered material B; (6) After grinding the sintered material B with melamine, ferrocene and nano copper oxide in a certain proportion, it is treated at high temperature of 600~900℃ for 1~2 hours in an inert gas atmosphere and then cooled to obtain the antibacterial gas adsorbent.

2. The antibacterial gas adsorbent according to claim 1, characterized in that, The weight ratio of the support to the catalytic auxiliary is 1:(0.05~0.2).

3. The antibacterial gas adsorbent according to claim 1, characterized in that, The mass ratio of the carrier to the antibacterial agent and the adsorption aid is 1:(0.1~0.25):(0.05~0.2).

4. The antibacterial gas adsorbent according to claim 1, characterized in that, The weight ratio of melamine, ferrocene and nano-copper oxide in the catalyst is 10:(0.8~1.5):(1~2).

5. The antibacterial gas adsorbent according to claim 1, characterized in that, The MOFs material is MIL-100, MIL-101, MOF-74, or ZIF-8.

6. The antibacterial gas adsorbent according to claim 1, characterized in that, The zinc salt is at least one of zinc nitrate, zinc sulfate, zinc chloride, zinc carbonate, zinc acetate, zinc phosphate, zinc pyrophosphate, and zinc citrate, and the silver salt is silver nitrate.

7. The method for preparing the antibacterial gas adsorbent according to any one of claims 1-6, characterized in that, The preparation method includes the following steps: (1) MOFs materials are deposited on the surface of powdered wood or bamboo materials at 20~30℃ using in-situ deposition method to obtain MOFs material and carbon material composite carrier; (2) The MOFs material and carbon material composite carrier are immersed in an adsorption aid solution A with a mass concentration of 1%~10% and ultrasonically treated at 20~30℃ for 10~50 minutes. The solvent in the adsorption aid solution A is acidic water, that is, the adsorption aid is dispersed in water and hydrochloric acid is added dropwise until the adsorption aid dissolves. Solid-liquid separation is performed to obtain solid particles A and the liquid on the surface of solid particles A is removed. Then, solid particles A are immersed in solution A with a mass concentration of 1%~20% and stirred at 20~30℃ for 1~5 h. (3) Separate solid particles from the system after step (2), dry them at 60~100℃ for 1~5 h, and treat them at 300~500℃ for 1~5 h in an inert gas atmosphere, and then cool them in an inert gas atmosphere to obtain sintered material A; (4) Immerse the sintered material A in an antibacterial agent solution B with a mass concentration of 2%~10% and sonicate it at 20~30℃ for 10~50 minutes. The solvent of the antibacterial agent solution B is acidic water, that is, the antibacterial agent is dispersed in water and hydrochloric acid is added dropwise until the antibacterial agent dissolves. Solid-liquid separation is performed to obtain solid particles B and the liquid on the surface of solid particles B is removed. Then, immerse the solid particles B in an antibacterial agent solution B with a mass concentration of 2%~25% and stir it at 20~30℃ for 1~5 hours. (5) Separate solid particles from the system after step (4), dry them at 40~70℃ for 1~5 h, and treat them at 200~500℃ for 1~5 h in a reducing gas atmosphere, and then cool them to obtain sintered material B; (6) After grinding the sintered material B with melamine, ferrocene and nano copper oxide in a certain proportion, it is treated at high temperature of 600~900℃ for 1~2 hours in an inert gas atmosphere and then cooled to obtain the antibacterial gas adsorbent.

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