Preparation method of metal phosphide, bactericidal composite material, preparation method and application thereof

Abstract

The present invention belongs to the technical field of bactericidal materials, and provides a preparation method of metal phosphide, a bactericidal composite material, a preparation method thereof and an application. The preparation method provided by the present invention includes: performing phosphating treatment on a metal oxide under the condition of a reaction gas to obtain the metal phosphide; the reaction gas contains phosphine. The preparation method provided by the present invention only needs to perform phosphating treatment on the metal oxide in a reaction gas containing phosphine gas to obtain the metal phosphide, with simple operation, short time consumption and easy industrialization. Further, the reaction gas is waste gas containing phosphine, realizing the resource recycling of phosphine gas in the waste gas. The bactericidal composite material provided by the present invention fully disperses the metal phosphide on a biochar carrier, combines the high specific surface area and adsorption effect of the biochar carrier, and the antibacterial property of the metal phosphide, improving the bactericidal property of the bactericidal composite material.

Description

Technical Field

[0001] The present invention relates to the technical field of bactericidal materials, and in particular to a preparation method of metal phosphide, a bactericidal composite material, a preparation method thereof and an application thereof. Background Art

[0002] The pollution of drinking water has always been a major problem troubling human health, and the pollution of drinking water is mainly caused by microbial infection. Killing microorganisms in water bodies is a key step in the purification of drinking water and a necessary means to protect human survival and health. However, traditional disinfection methods (chlorination, ozone and ultraviolet irradiation) all have some drawbacks, such as large energy consumption and secondary pollution. Among them, chlorination and ozonation use chemical substances as disinfectants, so the residual chemicals or disinfection by-products generated during the disinfection process will still pose a serious threat to biological health.

[0003] In recent years, some researchers have proposed that cuprous phosphide can be used as a modified material to enhance the electrode function to assist electric field sterilization. More recently, it has been reported that metal phosphides can generate reactive oxygen species due to their own enzyme-like properties, thus making themselves have bactericidal properties, so they can be used alone as bactericidal materials. However, the synthesis conditions of metal phosphides are harsh and time-consuming, which is not conducive to popularization and use. Specifically, for example, Chinese Patent with Publication No. CN104803364A discloses a preparation method of cuprous phosphide nanotubes, including the following steps: 1) Add 30-45 mL of N,N-dimethylformamide solution to a conical flask; 2) Add 0.10 g of cetyltrimethylammonium bromide CTAB to the conical flask, stir and ultrasonically dissolve until completely dissolved, and the concentration of CTAB is 2.22 g / L-3.33 g / L; 3) Add copper salt to the conical flask, stir and ultrasonically dissolve until completely dissolved, and the concentration of copper salt is 5.00 g / L-8.00 g / L; 4) Transfer the transparent solution obtained in step 3) into a polytetrafluoroethylene inner liner, and then add 0.08-0.20 g of yellow phosphorus to the transparent solution to make its concentration 1.50-7.00 g / L, and then seal the polytetrafluoroethylene inner liner into a stainless steel mold, and start heating from room temperature and heat react at 140-160 °C for 12-20 h under closed conditions; 5) After the reaction is completed, cool to room temperature with the furnace, and then filter with a fast quantitative filter paper to obtain the crude product; 6) Wash the crude product with deionized water, benzene and absolute ethanol in turn; 7) Place the washed product in a vacuum drying oven and vacuum dry at 50-60 °C for 4 h to obtain cuprous phosphide nanotubes. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a preparation method of metal phosphide, a bactericidal composite material, a preparation method thereof and an application thereof. The preparation method of the metal phosphide provided by the present invention is simple in operation, short in time-consuming, and easy to industrialize.

[0005] To achieve the above-mentioned invention objectives, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a metal phosphide, comprising the following steps:

[0007] The metal oxide is subjected to phosphating treatment under the condition of a reaction gas to obtain the metal phosphide;

[0008] The reaction gas contains phosphine.

[0009] Preferably, the metal in the metal oxide includes one or more of copper, iron, magnesium, sodium, zinc, nickel, manganese, and cobalt.

[0010] Preferably, in the reaction gas, the concentration of phosphine is 600 - 1200 ppm, the volume concentration of oxygen is 0.5 - 1.5%, and the balance is nitrogen.

[0011] Preferably, the reaction gas is waste gas containing phosphine; the waste gas containing phosphine includes yellow phosphorus tail gas, biogas, landfill gas, semiconductor optoelectronic industry tail gas, or sealed calcium carbide furnace tail gas.

[0012] Preferably, the flow rate of the reaction gas is 100 - 200 mL / min.

[0013] Preferably, the temperature of the phosphating treatment is 60 - 120 °C.

[0014] The present invention also provides a method for preparing a bactericidal composite material, comprising the following steps:

[0015] Prepare a precursor loaded with a metal oxide;

[0016] The precursor is subjected to phosphating treatment according to the preparation method described in the above technical solution to obtain the bactericidal composite material.

[0017] Preferably, the method for preparing the precursor loaded with a metal oxide includes the following steps:

[0018] The biomass raw material is subjected to a first calcination to obtain a biochar carrier;

[0019] The biochar carrier, metal salt solution, and concentrated nitric acid are mixed, and hydrothermal reaction and a second calcination are carried out in sequence to obtain a precursor loaded with a metal oxide.

[0020] The present invention also provides a bactericidal composite material prepared by the preparation method described in the above technical solution.

[0021] The present invention also provides the application of the bactericidal composite material described in the above technical solution in the field of water body sterilization.

[0022] The present invention provides a method for preparing metal phosphide, comprising the following steps: subjecting a metal oxide to phosphating treatment under the condition of a reaction gas to obtain the metal phosphide; the reaction gas contains phosphine. The preparation method provided by the present invention only needs to subject the metal oxide to phosphating treatment in a reaction gas containing phosphine gas to obtain the metal phosphide, with simple operation, short time consumption, and easy industrialization.

[0023] Further, the metal in the metal oxide includes one or more of copper, iron, magnesium, sodium, zinc, nickel, manganese, and cobalt. Especially when it is copper, cuprous phosphide is prepared, making the preparation process of cuprous phosphide simple and easy for industrialization.

[0024] Further, the reaction gas is waste gas containing phosphine; the waste gas containing phosphine includes yellow phosphorus tail gas, biogas, landfill gas, semiconductor optoelectronic industry tail gas, or sealed calcium carbide furnace tail gas, realizing the removal of phosphine in the waste gas containing phosphine and the resource recycling of phosphine gas in the waste gas.

[0025] The present invention also provides a bactericidal composite material prepared by the preparation method described in the above technical solution. The bactericidal composite material of the present invention fully disperses the metal phosphide on the biochar carrier, combines the high specific surface area and adsorption effect of the biochar carrier, and the antibacterial property of the metal phosphide, improving the bactericidal property of the bactericidal composite material. Description of the Drawings

[0026] Figure 1 XRD spectrum of cuprous phosphide obtained in Example 1;

[0027] Figure 2 XRD pattern of the bactericidal composite material obtained in Example 3. Detailed Description of the Invention

[0028] The present invention provides a method for preparing metal phosphide, comprising the following steps:

[0029] Subjecting a metal oxide to phosphating treatment under the condition of a reaction gas to obtain the metal phosphide;

[0030] The reaction gas contains phosphine.

[0031] In the present invention, unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

[0032] In the present invention, the metal in the metal oxide preferably includes one or more of copper, iron, magnesium, sodium, zinc, nickel, manganese, and cobalt, and is further preferably copper. In the present invention, the particle size of the metal oxide is preferably 40 - 60 mesh.

[0033] In the present invention, in the reaction gas, the concentration of phosphine is preferably 600 - 1200 ppm, more preferably 800 - 1000 ppm; the volume concentration of oxygen is preferably 0.5 - 1.5%, more preferably 1.0%; the balance is nitrogen.

[0034] In the present invention, the reaction gas is preferably phosphine-containing waste gas; the phosphine-containing waste gas preferably includes yellow phosphorus tail gas, biogas, landfill gas, semiconductor optoelectronic industry tail gas or closed calcium carbide furnace tail gas.

[0035] In the present invention, the flow rate of the reaction gas is preferably 100 - 200 mL / min, more preferably 120 - 180 mL / min, and even more preferably 140 - 160 mL / min.

[0036] In the present invention, the temperature of the phosphating treatment is preferably 60 - 120 °C, more preferably 80 - 100 °C; the time of the phosphating treatment is preferably: when the concentration of phosphine in the reaction gas at the outlet is the same as that in the reaction gas at the inlet, it is considered that the phosphating treatment can be terminated.

[0037] In the present invention, the phosphating treatment is preferably carried out in a fixed-bed reactor.

[0038] The present invention also provides a preparation method of a bactericidal composite material, comprising the following steps:

[0039] Prepare a precursor loaded with metal oxide;

[0040] Phosphate-treat the precursor according to the preparation method described in the above technical solution to obtain the bactericidal composite material.

[0041] The present invention prepares a precursor loaded with metal oxide.

[0042] In the present invention, the preparation method of the precursor loaded with metal oxide preferably includes the following steps:

[0043] Perform a first calcination on the biomass raw material to obtain a biochar carrier;

[0044] Mix the biochar carrier, metal salt solution and concentrated nitric acid, and successively carry out a hydrothermal reaction and a second calcination to obtain a precursor loaded with metal oxide.

[0045] The present invention performs a first calcination on a biomass raw material to obtain a biochar carrier. In the present invention, the biomass raw material preferably includes one or more of peanut shells, rice husks, coconut shells, and straws. In the present invention, the particle size of the biomass raw material is preferably 40-60 mesh. In the present invention, the temperature of the first calcination is preferably 500-800 °C, more preferably 600-700 °C; the rate of heating up to the temperature of the first calcination is preferably 5 °C / min; the calcination time is preferably 2-6 h, more preferably 3-5 h. In the present invention, the first calcination is preferably carried out in a nitrogen atmosphere. After the first calcination, the present invention preferably further includes grinding; the particle size of the product obtained by grinding is preferably 40-60 mesh.

[0046] After obtaining the biochar carrier, the present invention mixes the biochar carrier, a metal salt solution, and concentrated nitric acid, and sequentially performs a hydrothermal reaction and a second calcination to obtain a precursor loaded with metal oxides. In the present invention, the concentration of the metal salt solution is preferably 0.1-3 mol / L. In the present invention, the metal in the metal salt solution preferably includes one or more of copper, iron, magnesium, sodium, zinc, nickel, manganese, and cobalt, more preferably copper. In the present invention, the type of metal salt in the metal salt solution preferably includes nitrates. In the present invention, the mass fraction of the concentrated nitric acid is preferably 65%-68%. In the present invention, the dosage ratio of the biochar carrier, the metal salt solution, and the concentrated nitric acid is preferably 2 g: 20-60 mL: 0.1-1 mL. In the present invention, the temperature of the hydrothermal reaction is preferably 140-200 °C, more preferably 160-180 °C; the time is preferably 5-12 h. In the present invention, the hydrothermal reaction is preferably carried out in a hydrothermal reaction kettle. After the hydrothermal reaction, the present invention preferably further includes naturally cooling to room temperature, taking out the hydrothermal reaction product, and sequentially performing washing and drying. In the present invention, the washing reagent is preferably water, and the water is preferably ultrapure water; the present invention does not make specific limitations on the number of washing times and the dosage of the washing reagent, as long as the pH value of the washing solution obtained by washing reaches 7. In the present invention, the drying temperature is preferably 80-100 °C, and the time is preferably 10-15 h; the drying is preferably carried out in an oven. In the present invention, the temperature of the second calcination is preferably 300-600 °C, more preferably 400-500 °C; the rate of heating up to the second calcination is preferably 5 °C / min; the second calcination time is preferably 1-5 h, more preferably 2-3 h. In the present invention, the second calcination is preferably carried out in a nitrogen atmosphere.

[0047] After obtaining the precursor loaded with metal oxides, the present invention performs a phosphating treatment on the precursor according to the preparation method described in the above technical solution to obtain the sterilizing composite material.

[0048] In the present invention, the operations and parameters of the phosphating treatment are the same as those of the above technical solution, and will not be elaborated here.

[0049] The present invention also provides a bactericidal composite material prepared by the preparation method described in the above technical solution. In the present invention, the bactericidal composite material includes a biochar carrier and metal phosphides dispersed on the biochar carrier.

[0050] The present invention also provides the application of the bactericidal composite material described in the above technical solution in the field of water body sterilization.

[0051] The present invention does not specifically limit the application of the bactericidal composite material in the field of water body sterilization, and operations well-known to those skilled in the art can be adopted.

[0052] The following will describe in detail the preparation method of the metal phosphide, the bactericidal composite material and its preparation method and application provided by the present invention with reference to embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0053] Example 1

[0054] The preparation of cuprous phosphide, the specific steps are as follows:

[0055] The nano-CuO material is ground and sieved to 40 - 60 mesh for standby.

[0056] A reaction gas with a PH3 concentration of 1000 ppm, an oxygen volume content of 1%, and the balance being nitrogen is configured. The flow rate of the reaction gas is controlled to be 100 mL / min. Weigh 1 g of the sieved nano-CuO adsorbent and put it into a quartz glass reaction tube. The loaded nano-CuO adsorbent is placed in a small tubular furnace and heated to 90°C, and then the prepared reaction gas is introduced. When the inlet concentration of phosphine in the reaction gas is the same as the outlet concentration, the reaction ends, and cuprous phosphide is obtained.

[0057] Example 2

[0058] (1) Weigh 30 g of peanut shells (particle size of 40 - 60 mesh), place them in a quartz boat and put them into a tubular furnace. Under a nitrogen atmosphere, heat them to 700°C at a heating rate of 5°C / min and keep for 4 h. After the temperature drops to room temperature, take out the calcined black substance, grind and sieve it to 40 - 60 mesh for standby.

[0059] (2) Prepare a 1 mol / L copper nitrate solution: Weigh 24.16 g of Cu(NO3)2·3H2O and make up the volume to 100 mL in a volumetric flask and shake well. Take 2 g of the sieved peanut shell activated carbon obtained in step (1) and put it into a 100 mL autoclave. Then add 20 mL of the prepared copper nitrate solution, and then add 0.5 mL of concentrated nitric acid (mass fraction 65% - 68%), stir and mix evenly. Transfer it to an oven and keep it at 160 °C for 9 h. After the temperature drops to room temperature, take out the solid-liquid mixture in the autoclave, wash it with ultrapure water until the supernatant is clear, and put it into an oven at 100 °C for drying for 12 h to obtain the precursor loaded with metal oxides for standby.

[0060] (3) Prepare a PH3 mixed gas with a concentration of 1000 ppm, a reaction gas with an oxygen volume content of 1% and the balance being nitrogen. Control the flow rate of the reaction gas at 100 mL / min. Weigh 1 g of the precursor loaded with metal oxides obtained in step (2) and put it into a quartz glass reaction tube. Place the loaded precursor in a small tube furnace and heat it to 90 °C, and then introduce the prepared reaction gas. When the inlet concentration of phosphine in the reaction gas is the same as the outlet concentration, the reaction ends to obtain the bactericidal composite material.

[0061] Example 3

[0062] (1) Weigh 30 g of peanut shells (particle size 40 - 60 mesh), place them in a quartz boat and put them into a tube furnace. Under a nitrogen atmosphere, heat it to 700 °C at a heating rate of 5 °C / min and keep it for 4 h. After the temperature drops to room temperature, take out the calcined black substance, grind and sieve it to 40 - 60 mesh for standby.

[0063] (2) Prepare a 2 mol / L copper nitrate solution: Weigh 48.32 g of Cu(NO3)2·3H2O and make up the volume to 100 mL in a volumetric flask and shake well. Take 2 g of the sieved peanut shell activated carbon obtained in step (1) and put it into a 100 mL autoclave. Then add 20 mL of the prepared copper nitrate solution, and then add 0.5 mL of concentrated nitric acid (mass fraction 65% - 68%), stir and mix evenly. Transfer it to an oven and keep it at 160 °C for 9 h. After the temperature drops to room temperature, take out the solid-liquid mixture in the autoclave, wash it with ultrapure water until the supernatant is clear, and put it into an oven at 100 °C for drying for 12 h to obtain the precursor loaded with metal oxides for standby.

[0064] (3) Prepare a PH3 mixed gas with a concentration of 1000 ppm, where the volume content of oxygen is 1% and the balance is nitrogen as the reaction gas. Control the flow rate of the reaction gas at 100 mL / min. Weigh 1 g of the precursor loaded with metal oxide obtained in step (2) and place it in a quartz glass reaction tube. Place the loaded precursor in a small tube furnace and heat it to 90 °C, then introduce the prepared reaction gas. When the inlet concentration of phosphine in the reaction gas is the same as the outlet concentration, the reaction ends, and a bactericidal composite material is obtained.

[0065] Example 4

[0066] (1) Weigh 30 g of coconut shell (particle size 40 - 60 mesh) and place it in a quartz boat, then put it into a tube furnace. Under a nitrogen atmosphere, heat it to 700 °C at a heating rate of 5 °C / min and hold for 4 h. After the temperature drops to room temperature, take out the calcined black material, grind and sieve it to 40 - 60 mesh for standby.

[0067] (2) Prepare a 2 mol / L copper nitrate solution: Take 48.32 g of Cu(NO3)2·3H2O and make up the volume to 100 mL in a volumetric flask and shake well. Take 2 g of the sieved coconut shell activated carbon from step (1) and put it into a 100 mL reaction kettle, then add 20 mL of the prepared copper nitrate solution, and then add 0.5 mL of pure nitric acid, stir and mix evenly. Transfer it to an oven and keep it at 160 °C for 9 h. After the temperature drops to room temperature, take out the solid-liquid mixture in the reaction kettle, wash it with ultrapure water until the supernatant is clear, and put it into an oven at 100 °C to dry for 12 h to obtain a precursor loaded with metal oxide for standby.

[0068] (3) Prepare a PH3 mixed gas with a concentration of 1000 ppm, where the volume content of oxygen is 1% and the balance is nitrogen as the reaction gas. Control the flow rate of the reaction gas at 100 mL / min. Weigh 1 g of the precursor loaded with metal oxide obtained in step (2) and place it in a quartz glass reaction tube. Place the loaded precursor in a small tube furnace and heat it to 90 °C, then introduce the prepared reaction gas. When the inlet concentration of phosphine in the reaction gas is the same as the outlet concentration, the reaction ends, and a bactericidal material is obtained.

[0069] Material Characterization

[0070] Perform XRD characterization on the cuprous phosphide obtained in Example 1 and the bactericidal composite material obtained in Example 3. Determine the structure of the relevant crystalline substances through a D / MAX-2200 type X-ray diffractometer, with CuKa radiation (λ = 0.15406 nm), voltage 36 kV, current 30 mA, scanning range 0 - 90°, scanning speed 5° / min. The obtained results are as Figure 1 and Figure 2 shown.

[0071] FromFigure 1 It can be seen that only the diffraction peak of Cu3P appears in the phosphated sample, indicating that it is feasible to prepare Cu3P by phosphating pure CuO in a reaction gas containing PH3.

[0072] From Figure 2 It can be seen that the XRD characteristic diffraction peaks of C and Cu3P appear in the sterilizing composite material after phosphating treatment, indicating that Cu3P has been obtained in the sterilizing composite material prepared by the present invention.

[0073] Sterilization performance test

[0074] Disperse the sterilizing composite materials prepared in Examples 2 to 4 in water, and the mass ratio of the sterilizing composite material to water is 1:1000 to obtain a sample solution (one-thousandth). At the same time, use the purchased nano-CuO material for the sterilization experiment comparison. Grind and screen the nano-CuO material to 40 - 60 mesh, and disperse it in water according to the mass ratio of 1:1000 as the sample solution for standby.

[0075] Take Escherichia coli, deionized water and nutrient agar to prepare an experimental bacteria-contaminated water sample. For the sterilization experiment comparison, take 4.5 mL of deionized water + 0.5 mL of bacterial solution (10 8 ) as the blank control sample. Take 4 mL of the sample solution (the sample solutions prepared from the sterilizing composite materials in Examples 2 to 4 and the sample solution prepared from the nano-copper oxide material), add 0.5 mL of deionized water and 0.5 mL of bacterial solution, shake well, then let it stand for reaction for 30 min, and then add a neutralizing agent and let it stand for reaction for 10 min, followed by gradient dilution and calculation of the sterilization rate. The results are shown in Table 1.

[0076] Table 1 Sterilization effects of the sterilizing composite materials obtained in Examples 1 to 4

[0077]

[0078] It can be seen from Table 1 that the sterilizing composite material prepared by hydrothermal calcination and then phosphating treatment of 2 ml / L copper nitrate solution with biochar as the carrier has the best sterilization effect on Escherichia coli, and the sterilization performance is related to the ratio of biomass to copper nitrate solution in the preparation process. It can be speculated that the sterilization performance may be related to the purity of cuprous phosphide produced after phosphating.

[0079] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can still be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a bactericidal composite material, characterized in that, It includes the following steps: Prepare a precursor loaded with metal oxide; Perform phosphating treatment on the precursor under the condition of reaction gas to obtain the sterilizing composite material; The reaction gas contains phosphine; The preparation method of the precursor loaded with metal oxide includes the following steps: Perform first calcination on the biomass raw material to obtain a biochar carrier; Mix the biochar carrier, metal salt solution and concentrated nitric acid, and perform hydrothermal reaction and second calcination in sequence to obtain a precursor loaded with metal oxide; The biomass raw material is peanut shell; The dosage ratio of the biochar carrier, metal salt solution and concentrated nitric acid is 2g:20:0.5mL; The metal salt solution is a copper nitrate solution with a concentration of 2mol / L.

2. The preparation method according to claim 1, characterized in that, In the reaction gas, the concentration of phosphine is 600 - 1200ppm, the volume concentration of oxygen is 0.5 - 1.5%, and the balance is nitrogen.

3. The preparation method according to claim 1 or 2, characterized in that, The reaction gas is phosphine-containing waste gas; the phosphine-containing waste gas includes yellow phosphorus tail gas, biogas, landfill gas, semiconductor optoelectronic industry tail gas or closed calcium carbide furnace tail gas.

4. The preparation method according to claim 1 or 2, characterized in that, The flow rate of the reaction gas is 100 - 200mL / min.

5. The preparation method according to claim 1, characterized in that, The temperature of the phosphating treatment is 60 - 120°C.

6. The sterilizing composite material prepared by the preparation method according to any one of claims 1 - 5.

7. The application of the sterilizing composite material according to claim 6 in the field of water body sterilization.

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