A rare earth composite photocatalyst disinfection material and its preparation process

Abstract

The present invention relates to the technical field of disinfection materials, and particularly relates to a rare earth composite photocatalyst disinfection material and its preparation process. The preparation process includes the following steps: preparing rare earth dopants; preparing biological rare earth dopants; preparing protonated cellulose composite graphite phase carbon nitride powder; preparing rare earth composite photocatalyst disinfection material. In the present invention, zinc acetate, rare earth ion solution and titanium sulfate are made into a gel, and the gel is calcined to obtain rare earth dopants. The rare earth ions in the rare earth dopants can serve as a transfer medium to promote the separation and transmission of photo-generated carriers. In the structure of the rare earth dopants, the rare earth ions penetrate through it, enabling photo-generated electrons to move directionally in the rare earth dopants, thereby improving the photocatalytic efficiency and enhancing the disinfection ability of the rare earth composite photocatalyst disinfection material by improving the photocatalytic efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of disinfection materials, and particularly relates to a rare earth composite photocatalyst disinfection material and a preparation process thereof. Background Art

[0002] Photocatalyst disinfectants are a technology that uses photocatalytic reactions for sterilization and disinfection. This technology has shown great potential in multiple fields such as environmental protection, public health, and personal care. A photocatalyst is a material that can generate reactive oxygen species under the action of light. These reactive oxygen species have strong oxidizing properties and can destroy the cell walls and cell membranes of microorganisms, thereby achieving the effect of sterilization and disinfection.

[0003] Common photocatalysts include titanium dioxide, graphitic carbon nitride, and zinc sulfide. These photocatalyst materials are common and the preparation methods are relatively simple, but their response to visible light is weak. For example, titanium dioxide requires ultraviolet irradiation, although graphitic carbon nitride does not require ultraviolet irradiation, it requires a certain irradiation duration, and the stability of zinc sulfide is poor. Rare earth elements have shown unique advantages in the field of photocatalysis. Rare earth elements have rich electronic energy levels. Introducing rare earth elements into photocatalysts can broaden the light absorption range of the photocatalysts, thereby improving the photocatalytic activity and efficiency. However, although rare earth elements are not considered heavy metal elements, they still possess some characteristics of heavy metal elements, including environmental toxicity. The disinfection materials prepared by introducing rare earth elements into photocatalysts may have an impact on the environment. Especially, photocatalyst-based disinfection materials are commonly used in environmental purification such as air purification, water disinfection, and soil remediation. It can be seen that such disinfection materials require both excellent disinfection performance and high environmental compatibility. Therefore, the present invention provides a rare earth composite photocatalyst disinfection material and a preparation process thereof to solve the above existing problems. Summary of the Invention

[0004] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a rare earth composite photocatalyst disinfection material and a preparation process thereof.

[0005] A preparation process of a rare earth composite photocatalyst disinfection material includes the following steps:

[0006] S1: Prepare rare earth dopants

[0007] Add zinc acetate solution into a reaction flask, then add rare earth ion solution and titanium sulfate thereto. The rare earth ion solution is a 0.1 - 0.5 M cerium ion solution or lanthanum ion solution to obtain a mixed solution. Add acrylamide monomer and N,N'-methylenebisacrylamide, and then ammonium persulfate as an initiator. Form a translucent gel in a water bath kettle, take out the translucent gel, cool it, dry it, grind the dried gel into powder and calcine it to finally obtain rare earth dopants;

[0008] S2: Preparation of biological rare earth dopants

[0009] Add the rare earth dopants into ultrapure water to obtain a suspension. Then, weigh gelatin, β-cyclodextrin, and glucose respectively and add them into the suspension. Stir magnetically and conduct hydrothermal reaction. After the reaction, wait for the hydrothermal kettle to cool down, pour out the supernatant, and centrifuge and wash the precipitate with ultrapure water and absolute ethanol respectively, then dry it. Grind the dried product evenly with a mortar to obtain the biological rare earth dopants;

[0010] S3: Preparation of protonated cellulose composite graphite phase carbon nitride powder

[0011] Weigh melamine and sodium carboxymethylcellulose and calcine them in a tubular furnace to obtain a yellow block. After cooling, grind and crush it to obtain a yellow powder. Add the yellow powder into an HCl solution, stir, filter to remove the filtrate, wash the filter residue with ultrapure water until it is neutral, and then dry it to obtain the protonated cellulose composite graphite phase carbon nitride powder;

[0012] S4: Preparation of rare earth composite photocatalyst disinfection material

[0013] Add the biological rare earth dopants into ultrapure water, disperse them by ultrasonic wave, and stir to form suspension A. Then, dissolve the protonated cellulose composite graphite phase carbon nitride powder in ultrapure water to obtain suspension B. Mix suspension A and suspension B and stir magnetically to obtain a composite suspension. Dry the composite suspension to obtain the rare earth composite photocatalyst disinfection material.

[0014] Further, the preparation of the rare earth dopants in step S1 includes the following steps:

[0015] S1.1: Add 2-5 parts by mass of 0.3-0.4 mol / L zinc acetate solution into a reaction flask, and then add 2-7 parts by mass of rare earth ion solution and 5-8 parts by mass of titanium sulfate. The rare earth ion solution is 0.1-0.5 M cerium ion solution or lanthanum ion solution to obtain a mixed solution;

[0016] S1.2: Adjust the pH of the mixed solution to 5.5-6 with 65-70% nitric acid, then add 5-6 parts by mass of acrylamide monomer and 1-1.5 parts by mass of N,N'-methylenebisacrylamide, and then add 2-4 parts by mass of initiator ammonium persulfate. Place it on a magnetic stirrer and stir evenly, and then put it into a water bath kettle at 70-80 °C for 1.5-2 h to form a translucent gel;

[0017] S1.3: Take out the translucent gel, cool it for 4-6 h, wash it with absolute ethanol for 2-3 times, then put it into a constant temperature drying oven and dry it at 100-110 °C for 12-15 h. Grind the dried gel into powder and place it in a muffle furnace for calcination at 550-600 °C to finally obtain the rare earth dopants.

[0018] Further, the preparation of the biological rare earth dopant in step S2 includes the following steps:

[0019] S2.1: Add the rare earth dopant to ultrapure water at a liquid ratio of 1:(8 - 10) g / L, and stir magnetically until completely dissolved to obtain a suspension. Then, weigh 1 - 2 parts by mass of gelatin, 1 - 2 parts by mass of β-cyclodextrin, and 1 - 2 parts by mass of glucose and add them to the suspension. Stir magnetically for 0.5 - 1 h, then add 10 - 15 parts by volume of anhydrous ethylenediamine and stir for 1 - 2 h, and then transfer to a hydrothermal autoclave for hydrothermal reaction, and keep the temperature at 180 - 190 °C for 24 - 26 h;

[0020] S2.2: After the reaction, wait for the hydrothermal autoclave to cool to room temperature (24 - 26 °C) before opening the autoclave. Pour out the supernatant, and wash the precipitate with ultrapure water and anhydrous ethanol by centrifugation until the color of the centrifugate is clear. Then dry at 60 - 80 °C for 20 - 24 h, and grind the dried product evenly with a mortar to obtain the biological rare earth dopant.

[0021] Further, the preparation of the protonated cellulose composite graphite phase carbon nitride powder in step S3 includes the following steps:

[0022] S3.1: Weigh 20 - 25 parts by mass of melamine and 10 - 12 parts by mass of sodium carboxymethylcellulose, heat them in a tube furnace to 550 - 580 °C, calcine for 4 - 4.5 h, and the heating rate is 2 - 5 °C to obtain a yellow block. After cooling, grind and crush it through a 200-mesh sieve to obtain a yellow powder;

[0023] S3.2: Add the yellow powder to an HCl solution with a concentration of 1.5 - 1.8 mo / L. The liquid ratio of the yellow powder to the HCl solution is 1:(0.4 - 0.5) g / L, stir at a speed of 6000 - 8000 r / min for 4 - 5 h, filter to remove the filtrate, wash the filter residue with ultrapure water until neutral, and dry for 3 - 4 h to obtain the protonated cellulose composite graphite phase carbon nitride powder.

[0024] Further, the preparation of the rare earth composite photocatalyst disinfection material in step S4 includes the following steps:

[0025] S4.1: Add the biological rare earth dopant to ultrapure water, disperse it by ultrasonic wave, and stir to form suspension A. Then dissolve the protonated cellulose composite graphite phase carbon nitride powder in ultrapure water, and the mass fraction of the protonated cellulose composite graphite phase carbon nitride powder is 20 - 25% to obtain suspension B. Mix suspension A and suspension B at a volume ratio of 1:(0.5 - 1), ultrasonicate for 1 - 1.5 h, and then stir magnetically for 4 - 4.5 h to obtain a composite suspension;

[0026] S4.2: Dry the composite suspension in an oven at 60 - 70 °C for 12 - 14 h to obtain the rare earth composite photocatalyst disinfection material.

[0027] Further, in step S1.1, the rare earth ion is a cerium ion solution or a lanthanum ion solution with a concentration of 0.1 - 0.5 M.

[0028] Further, in step S4.1, the material ratio of the biological rare earth dopant to ultrapure water is 1:(0.4 - 0.5) g / L.

[0029] A rare earth composite photocatalyst disinfection material is prepared by the preparation process of the above rare earth composite photocatalyst disinfection material.

[0030] Compared with the prior art, the present invention has at least the following beneficial effects:

[0031] 1. In the present invention, zinc acetate, a rare earth ion solution, and titanium sulfate are made into a gel, and the gel is calcined to obtain a rare earth dopant. Zinc acetate and titanium sulfate can interact with each other during the gelation process to form a uniform precursor solution. Zinc acetate and titanium sulfate first undergo hydrolysis, and then co-precipitation occurs. During the co-precipitation, rare earth ions are incorporated, and then polycondensation occurs, thereby forming a composite oxide gel. By forming a gel, the molding tendency of the three components is controlled to be a three-dimensional structure, and finally a gel is formed. Subsequently, the gel is calcined at a high temperature to remove organic components and moisture, forming a stable oxide material with a three-dimensional structure, that is, a rare earth dopant. The rare earth ions in the rare earth dopant can act as a transfer medium to promote the separation and transmission of photo-generated carriers. In the structure of the rare earth dopant, the rare earth ions penetrate through it, enabling photo-generated electrons to move directionally in the rare earth dopant, thereby improving the photocatalytic efficiency, and improving the disinfection ability of the rare earth composite photocatalyst disinfection material by improving the photocatalytic efficiency.

[0032] 2. After the rare earth dopant of the present invention is mixed with cyclodextrin and glucose, heat treatment is carried out to make glucose form a stable carbon skeleton with the rare earth dopant as the core, and then cyclodextrin is included outside the carbon skeleton to form a cavity structure. The presence of the carbon skeleton can effectively separate the photo-generated electrons and holes moving in the rare earth dopant after binding to the rare earth dopant, reduce electron-hole recombination, improve the photocatalytic efficiency, and at the same time change the surface morphology of the rare earth dopant, increase the specific surface area and active sites, and further improve the photocatalytic activity. The photocatalyst absorbs light energy to generate reactive oxygen species, effectively destroying the cell walls and cell membranes of microorganisms, thereby achieving the effect of disinfection and sterilization. Moreover, the glucose carbon skeleton wrapped by cyclodextrin does not completely enclose the rare earth dopant into a sphere, but forms a three-dimensional structure. In such a structure, the biological materials on the outside, namely cyclodextrin and gelatin, have good biocompatibility with organisms, and the prepared rare earth composite photocatalyst disinfection material has lower toxicity compared with other disinfection materials, thus achieving the effect of being environmentally friendly while having excellent disinfection ability.

[0033] 3. In the present invention, melamine and sodium carboxymethyl cellulose are compounded by high-temperature heating to form cellulose composite graphite carbon nitride powder, and protonated by hydrochloric acid. Graphite carbon nitride is a two-dimensional layered material. After introducing sodium carboxymethyl cellulose, the polymerization of graphite carbon nitride can be prevented, and the structure of graphite carbon nitride can be laterally elongated, so that the composite graphite carbon nitride powder has a slender layered structure microscopically. When subsequently compounded with biological rare earth dopants, it can wrap around the surface of the biological rare earth dopants to form a highly transparent structure, thereby preventing the aggregation of rare earth composite photocatalyst disinfection materials with each other, increasing the contact area between the disinfection materials and external substances. At the same time, graphite carbon nitride is also an environmentally friendly material, and this material has good toughness and is not easy to fall apart, which can reduce the pollution of the disinfection materials to the natural environment and organisms and improve the disinfection performance of the disinfection materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings incorporated herein and constituting a part of the specification illustrate embodiments of the present disclosure and, together with the specification, are further used to explain the principles of the present disclosure and enable those skilled in the relevant art to implement and use the present disclosure.

[0035] Figure 1 It is a process flow chart of the preparation of the rare earth composite photocatalyst disinfection material adopted in the embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] The following describes in detail a rare earth composite photocatalyst disinfection material and its preparation process provided by the present invention with reference to the accompanying drawings and specific embodiments. At the same time, it should be noted here that in order to make the embodiments more detailed, the following embodiments are the best and preferred embodiments. For some well-known technologies, those skilled in the art can also adopt other alternative methods for implementation; moreover, the drawings are only for more specific description of the embodiments and are not intended to specifically limit the present invention.

[0037] Example 1:

[0038] A preparation process of a rare earth composite photocatalyst disinfection material, as Figure 1 shown, includes the following steps:

[0039] S1: Prepare rare earth dopants

[0040] S1.1: Add 2 parts by mass of 0.3 mol / L zinc acetate solution to a reaction flask, and then add 2 parts by mass of rare earth ion solution and 5 parts by mass of titanium sulfate thereto. The rare earth ion solution is 0.5 M cerium ion solution to obtain a mixed solution;

[0041] S1.2: After adjusting the pH of the mixed solution to 5.5 with 65% nitric acid, add 5 parts by mass of acrylamide monomer and 1 part by mass of N,N'-methylenebisacrylamide, then add 2 parts by mass of initiator ammonium persulfate, stir evenly on a magnetic stirrer, and then place it in a water bath at 70 °C for about 1.5 h to form a translucent gel;

[0042] S1.3: Take out the translucent gel, cool it for 4 h, wash it twice with absolute ethanol, then put it into a constant temperature drying oven and dry it at 100 °C for 12 h. Grind the dried gel into powder and place it in a muffle furnace for calcination at 550 °C to finally obtain the rare earth dopant.

[0043] S2: Prepare the biological rare earth dopant

[0044] S2.1: Add the rare earth dopant to ultrapure water at a solid-liquid ratio of 1:8 g / L, stir magnetically until completely dissolved to obtain a suspension, then weigh 1 part by mass of gelatin, 1 part by mass of β-cyclodextrin and 1 part by mass of glucose and add them to the suspension, stir magnetically for 0.5 h, then add 10 parts by volume of anhydrous ethylenediamine and stir for 1 h, and then transfer it to a hydrothermal autoclave for hydrothermal reaction at 180 °C for 24 h;

[0045] S2.2: After the reaction, wait for the hydrothermal autoclave to cool to room temperature (24 °C) before opening the autoclave for treatment. Pour out the supernatant and wash the precipitate with ultrapure water and absolute ethanol by centrifugation until the color of the centrifugate is clear, then dry it at 60 °C for 20 h, and grind the dried product evenly with a mortar to obtain the biological rare earth dopant.

[0046] S3: Prepare protonated cellulose composite graphite phase carbon nitride powder

[0047] S3.1: Weigh 20 parts by mass of melamine and 10 parts by mass of sodium carboxymethylcellulose, heat them to 550 °C in a tubular furnace, calcine for 4 h at a heating rate of 2 °C to obtain a yellow block, cool it and grind it into powder, and pass it through a 200-mesh sieve to obtain a yellow powder;

[0048] S3.2: Add the yellow powder to a HCl solution with a concentration of 1.5 mo / L, and the solid-liquid ratio of the yellow powder to the HCl solution is 1:0.4 g / L. Stir at a speed of 6000 r / min for 4 h, filter to remove the filtrate, wash the filter residue with ultrapure water until neutral, and dry for 3 h to obtain the protonated cellulose composite graphite phase carbon nitride powder.

[0049] S4: Prepare the rare earth composite photocatalyst disinfection material

[0050] S4.1: Add the biological rare earth dopant into ultrapure water. The material ratio of the biological rare earth dopant to ultrapure water is 1:0.4 g / L. Through ultrasonic dispersion and stirring, a suspension A is formed. Then, dissolve the protonated cellulose composite graphite carbon nitride powder in ultrapure water with a mass fraction of the protonated cellulose composite graphite carbon nitride powder being 20% to obtain a suspension B. Mix suspension A and suspension B in a volume ratio of 1:0.5, then ultrasonic for 1 h and magnetically stir for 4 h to obtain a composite suspension;

[0051] S4.2: Dry the composite suspension in an oven at 60 °C for 12 h to obtain the rare earth composite photocatalyst disinfection material.

[0052] Example 2:

[0053] A preparation process of a rare earth composite photocatalyst disinfection material, as Figure 1 shown, includes the following steps:

[0054] S1: Prepare the rare earth dopant

[0055] S1.1: Add 5 parts by mass of 0.3 mol / L zinc acetate solution into a reaction flask, then add 7 parts by mass of the rare earth ion solution and 8 parts by mass of titanium sulfate. The rare earth ion solution is a 0.5 M cerium ion solution to obtain a mixed solution;

[0056] S1.2: After adjusting the pH of the mixed solution to 5.5 with 65% nitric acid, add 6 parts by mass of acrylamide monomer and 1.5 parts by mass of N,N'-methylenebisacrylamide, then add 4 parts by mass of initiator ammonium persulfate, stir evenly on a magnetic stirrer, and then place it in a water bath at 70 °C for about 1.5 h to form a semi-transparent gel;

[0057] S1.3: Take out the semi-transparent gel, cool it for 4 h, wash it twice with absolute ethanol, then put it into a constant temperature drying oven, dry it at 100 °C for 12 h, grind the dried gel into powder and place it in a muffle furnace, calcine it at 550 °C, and finally obtain the rare earth dopant.

[0058] S2: Prepare the biological rare earth dopant

[0059] S2.1: Add the rare earth dopant into ultrapure water at a material ratio of 1:10 g / L, magnetically stir until completely dissolved to obtain a suspension. Then, weigh 2 parts by mass of gelatin, 2 parts by mass of β-cyclodextrin, and 2 parts by mass of glucose and add them into the suspension, magnetically stir for 0.5 h, then add 15 parts by volume of anhydrous ethylenediamine and stir for 1 h, and then transfer it to a hydrothermal autoclave for hydrothermal reaction at 180 °C for 24 h;

[0060] S2.2: After the reaction, the hydrothermal reactor was cooled to room temperature (24 °C) before opening. The supernatant was poured out, and the precipitate was centrifuged and washed with ultrapure water and absolute ethanol until the color of the centrifugate was clear. Then it was dried at 60 °C for 20 h, and the dried product was ground evenly with a mortar to obtain the biological rare earth dopant.

[0061] S3: Preparation of protonated cellulose composite graphite phase carbon nitride powder

[0062] S3.1: Weigh 25 parts by mass of melamine and 12 parts by mass of sodium carboxymethylcellulose, heat them to 550 °C in a tubular furnace, calcine for 4 h, with a heating rate of 2 °C, to obtain a yellow block. After cooling, it was ground and crushed, and passed through a 200-mesh sieve to obtain a yellow powder.

[0063] S3.2: Add the yellow powder to a HCl solution with a concentration of 1.5 mo / L. The material-liquid ratio of the yellow powder to the HCl solution is 1:0.5 g / L. Stir at a speed of 6000 r / min for 4 h, filter to remove the filtrate, wash the filter residue with ultrapure water until neutral, and dry for 3 h to obtain the protonated cellulose composite graphite phase carbon nitride powder.

[0064] S4: Preparation of rare earth composite photocatalyst disinfection material

[0065] S4.1: Add the biological rare earth dopant to ultrapure water. The material-liquid ratio of the biological rare earth dopant to ultrapure water is 1:0.5 g / L. Through ultrasonic dispersion and stirring, a suspension A is formed. Then dissolve the protonated cellulose composite graphite phase carbon nitride powder in ultrapure water, with a mass fraction of 25%, to obtain a suspension B. Mix suspension A and suspension B in a volume ratio of 1:1, ultrasonic for 1 h, and then magnetic stir for 4 h to obtain a composite suspension.

[0066] S4.2: Dry the composite suspension in an oven at 60 °C for 12 h to obtain the rare earth composite photocatalyst disinfection material.

[0067] Example 3:

[0068] A preparation process of a rare earth composite photocatalyst disinfection material, as Figure 1 shown, includes the following steps:

[0069] S1: Preparation of rare earth dopant

[0070] S1.1: Add 2 parts by mass of a 0.3 mol / L zinc acetate solution to a reaction flask, and then add 2 parts by mass of the rare earth ion solution and 5 parts by mass of titanium sulfate to it. The rare earth ion solution is a 0.5 M cerium ion solution to obtain a mixed solution.

[0071] S1.2: After adjusting the pH of the mixed solution to 6 with 65% nitric acid, add 5 parts by mass of acrylamide monomer and 1 part by mass of N,N'-methylenebisacrylamide, then add 2 parts by mass of initiator ammonium persulfate, stir evenly on a magnetic stirrer, and then place it in a water bath at 80 °C for about 2 h to form a translucent gel.

[0072] S1.3: Take out the translucent gel, cool it for 6 h, wash it 3 times with absolute ethanol, then put it into a constant temperature drying oven and dry it at 110 °C for 15 h. Grind the dried gel into powder and place it in a muffle furnace for calcination at 600 °C to finally obtain the rare earth dopant.

[0073] S2: Prepare the biological rare earth dopant

[0074] S2.1: Add the rare earth dopant to ultrapure water at a material-liquid ratio of 1:8 g / L, stir magnetically until completely dissolved to obtain a suspension, then weigh 1 part by mass of gelatin, 1 part by mass of β-cyclodextrin, and 1 part by mass of glucose and add them to the suspension, stir magnetically for 0.5 h, then add 10 parts by volume of anhydrous ethylenediamine and stir for 2 h, and then transfer it to a hydrothermal reactor for hydrothermal reaction at 190 °C for 26 h.

[0075] S2.2: After the reaction, wait for the hydrothermal reactor to cool to room temperature (26 °C) before opening the reactor. Pour out the supernatant and wash the precipitate with ultrapure water and absolute ethanol by centrifugation until the color of the centrifugate is clear, then dry it at 80 °C for 24 h, and grind the dried product evenly with a mortar to obtain the biological rare earth dopant.

[0076] S3: Prepare protonated cellulose composite graphite phase carbon nitride powder

[0077] S3.1: Weigh 20 parts by mass of melamine and 10 parts by mass of sodium carboxymethylcellulose, heat them to 600 °C in a tubular furnace, calcine for 4.5 h at a heating rate of 5 °C to obtain a yellow block, cool it and grind it into powder, and pass it through a 200-mesh sieve to obtain a yellow powder.

[0078] S3.2: Add the yellow powder to a HCl solution with a concentration of 1.5 mo / L, the material-liquid ratio of the yellow powder to the HCl solution is 1:0.4 g / L, stir at a speed of 8000 r / min for 5 h, filter to remove the filtrate, wash the filter residue with ultrapure water until neutral, and dry for 4 h to obtain the protonated cellulose composite graphite phase carbon nitride powder.

[0079] S4: Prepare the rare earth composite photocatalyst disinfection material

[0080] S4.1: Add the biological rare earth dopant into ultrapure water. The ratio of the biological rare earth dopant to the ultrapure water in the feed liquid is 1:0.4 g / L. Through ultrasonic dispersion and stirring, a suspension A is formed. Then, dissolve the protonated cellulose composite graphite carbon nitride powder in ultrapure water with the mass fraction of the protonated cellulose composite graphite carbon nitride powder being 20% to obtain a suspension B. Mix suspension A and suspension B at a volume ratio of 1:0.5 and then ultrasonicate for 1.5 h and magnetically stir for 4.5 h to obtain a composite suspension;

[0081] S4.2: Dry the composite suspension in an oven at 60 °C for 12 h to obtain the rare earth composite photocatalyst disinfection material.

[0082] Comparative Example 1:

[0083] Comparative Example 1 is a medical - specific chemical disinfectant on the market.

[0084] Comparative Example 2:

[0085] Compared with Example 1, the difference in Comparative Example 2 is that zinc acetate is not added in step S1.1. Specifically: "S1.1: Add 2 parts by mass of the rare earth ion solution and 5 parts by mass of titanium sulfate into the reaction flask. The rare earth ion solution is a 0.5 M cerium ion solution" and the remaining steps remain unchanged. The prepared rare earth composite photocatalyst disinfection material is denoted as Comparative Example 3.

[0086] Comparative Example 3:

[0087] Compared with Example 1, the difference in Comparative Example 3 is that titanium sulfate is not added in step S1.1. Specifically: "S1.1: Add 2 parts by mass of a 0.3 mol / L zinc acetate solution into the reaction flask, and then add 2 parts by mass of the rare earth ion solution. The rare earth ion solution is a 0.5 M cerium ion solution" to obtain a mixed solution, and the remaining steps remain unchanged. The prepared rare earth composite photocatalyst disinfection material is denoted as Comparative Example 3.

[0088] Comparative Example 4:

[0089] Compared with Example 1, the difference in Comparative Example 4 is that in step S1.1, the rare earth ion solution is not added, but a 0.5 M iron ion solution is added. Specifically: "S1.1: Add 2 parts by mass of a 0.3 mol / L zinc acetate solution into the reaction flask, and then add 2 parts by mass of a 0.5 M iron ion solution and 5 parts by mass of titanium sulfate" to obtain a mixed solution, and the remaining steps remain unchanged. The prepared rare earth composite photocatalyst disinfection material is denoted as Comparative Example 4.

[0090] Comparative Example 5:

[0091] Compared with Example 1, the difference in Comparative Example 5 is that β-cyclodextrin is not added in step S2.1. Specifically, it is as follows: "S2.1: Add the rare earth dopant to ultrapure water at a material-liquid ratio of 1:8 g / L, and magnetically stir until completely dissolved to obtain a suspension. Then, weigh 1 part by mass of gelatin and 1 part by mass of glucose and add them to the suspension, magnetically stir for 0.5 h, then add 10 parts by volume of anhydrous ethylenediamine and stir for 1 h, and then transfer to a hydrothermal reactor for hydrothermal reaction, and keep the temperature at 180 °C for 24 h", and the remaining steps remain unchanged. The rare earth composite photocatalyst disinfection material prepared is denoted as Comparative Example 5.

[0092] Comparative Example 6:

[0093] Compared with Example 1, the difference in Comparative Example 6 is that glucose is not added in step S2.1. Specifically, it is as follows: "S2.1: Add the rare earth dopant to ultrapure water at a material-liquid ratio of 1:8 g / L, and magnetically stir until completely dissolved to obtain a suspension. Then, weigh 1 part by mass of gelatin and 1 part by mass of β-cyclodextrin, magnetically stir for 0.5 h, then add 10 parts by volume of anhydrous ethylenediamine and stir for 1 h, and then transfer to a hydrothermal reactor for hydrothermal reaction, and keep the temperature at 180 °C for 24 h", and the remaining steps remain unchanged. The rare earth composite photocatalyst disinfection material prepared is denoted as Comparative Example 6.

[0094] Comparative Example 7:

[0095] Compared with Example 1, the difference in Comparative Example 7 is that step S2 for preparing the biological rare earth dopant is not carried out, and the rare earth dopant is used instead of the biological rare earth dopant in step S4. Specifically, it is as follows: "S4.1: Add the rare earth dopant to ultrapure water, and the material-liquid ratio of the rare earth dopant to ultrapure water is 1:0.4 g / L. Through ultrasonic dispersion, stir to form suspension A. Then, dissolve the protonated cellulose composite graphite carbon nitride powder in ultrapure water, and the mass fraction of the protonated cellulose composite graphite carbon nitride powder is 20%, to obtain suspension B. Mix suspension A and suspension B at a volume ratio of 1:0.5 and ultrasonicate for 1 h, and then magnetically stir for 4 h to obtain a composite suspension", and the remaining steps remain unchanged. The rare earth composite photocatalyst disinfection material prepared is denoted as Comparative Example 7.

[0096] Comparative Example 8:

[0097] Compared with Example 1, the difference in Comparative Example 8 is that melamine is not added in step S3.1. Specifically, it is as follows: "S3.1: Weigh 10 parts by mass of sodium carboxymethylcellulose, heat it to 550 °C in a tube furnace, calcine for 4 h, and the heating rate is 2 °C to obtain a block. After cooling, grind and crush it through a 200-mesh sieve to obtain a powder", and the remaining steps remain unchanged. The rare earth composite photocatalyst disinfection material prepared is denoted as Comparative Example 8.

[0098] Comparative Example 9:

[0099] Compared with Example 1, the difference in Comparative Example 9 is that sodium carboxymethylcellulose is not added in step S3.1. Specifically, it is as follows: "S3.1: Weigh 20 parts by mass of melamine, heat it to 550 °C in a tube furnace, calcine for 4 h, and the heating rate is 2 °C to obtain yellow lumps. After cooling, grind and crush it through a 200-mesh sieve to obtain yellow powder". The remaining steps remain unchanged, and the rare earth composite photocatalyst disinfection material prepared is denoted as Comparative Example 9.

[0100] Cultivate Gram-negative bacteria (E. coli) and Gram-positive bacteria (S. aureus) to 10 CFU / mL for standby.

[0101] Divide 24 parts of the culture medium into two groups, with 12 parts in each group. Add 10 3 CFU / mL of Gram-negative bacteria to one group, and add 1 mg / mL of Examples 1-3 and Comparative Examples 1-9 to each part of the culture medium; add 10 3 CFU / mL of Gram-positive bacteria to the other group, and then add 1 mg / mL of Examples 1-3 and Comparative Examples 1-9 to each part of the culture medium.

[0102] React the two groups of culture media under light for 120 min, then take 100 μL of the solution and coat it on a plate. Place the plate in an incubator at 30 °C for 36 h, and use the filter paper method and the dilution plate colony counting method to test the antibacterial effect and measure the size of the microbial antibacterial zone (unit: mm), as shown in Table 1.

[0103] Table 1

[0104] E.coli S.aureus Example 1 17.3 16.4 Example 2 17.4 16.1 Example 3 17.1 16.2 Comparative Example 1 15.9 14.7 Comparative Example 2 14.2 13.6 Comparative Example 3 14.7 13.4 Comparative Example 4 8.5 6.7 Comparative Example 5 14.8 13.1 Comparative Example 6 15.1 12.8 Comparative Example 7 14.6 12.5 Comparative Example 8 10.8 9.7 Comparative Example 9 12.2 10.6

[0105] The diameters of the antibacterial zones of Gram-negative bacteria (E. coli) and Gram-positive bacteria (S. aureus) in Examples 1-3 are all larger than those in the comparative examples, indicating that the bactericidal and disinfection effects of the examples are better. Comparative Example 1 is a commercially available chemical disinfectant, so it can be seen that the disinfection effect of the present invention is better than that of the commercially available product.

[0106] The diameters of the antibacterial zones of Comparative Example 2 for the two strains are 14.2 mm and 13.6 mm respectively, those of Comparative Example 3 for the two strains are 14.7 mm and 13.4 mm respectively, and those of Comparative Example 4 for the two strains are 8.5 mm and 6.7 mm respectively. It can be seen that zinc acetate and titanium sulfate have a synergistic effect when preparing rare earth dopants with rare earth ion solutions. The effects of single use are not as good as those of the examples. Replacing the rare earth ion solution with other metal ion solutions cannot achieve the synergistic effect with zinc acetate and titanium sulfate, and the bactericidal and disinfection effects decrease significantly.

[0107] The differences in the diameters of the antibacterial zones of Comparative Examples 5-7 were small, but they were all worse than those of the Examples. This shows that the combination of cyclodextrin, glucose and rare earth dopants improved the antibacterial effect. Moreover, since the main component of the rare earth dopant is metal oxide and it is easy to precipitate heavy metal ions to pollute the environment, after adding cyclodextrin and glucose, the disinfection material prepared from the biological rare earth dopant not only reduces environmental pollution, but also has a better disinfection effect.

[0108] The diameters of the antibacterial zones of Comparative Example 8 for the two bacterial strains were 10.8 mm and 9.7 mm respectively, and the diameters of the antibacterial zones of Comparative Example 9 for the two bacterial strains were 12.2 mm and 10.6 mm respectively. The diameter of the antibacterial zone of Comparative Example 8 without adding melamine was smaller and the disinfection effect was worse. It can be seen that the graphitic carbon nitride prepared by calcination with melamine as the main substance and the calcined cellulose substance of sodium carboxymethylcellulose as the dopant. After the protonated cellulose composite graphitic carbon nitride powder prepared from the cellulose composite graphitic carbon nitride powder is compounded with the biological rare earth dopant, it has a better disinfection effect.

[0109] The above examples are only illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Any person familiar with this technology can modify or change the above examples without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A preparation process of a rare earth composite photocatalyst disinfection material, characterized in that: The steps include: S1: Preparation of rare earth dopants Add zinc acetate solution to a reaction flask, then add rare earth ion solution and titanium sulfate thereto, wherein the rare earth ion solution is a 0.1-0.5M cerium ion solution or lanthanum ion solution, to obtain a mixed solution, add acrylamide monomer and N,N'-methylenebisacrylamide, then add initiator ammonium persulfate, and form a translucent gel in a water bath, take out the translucent gel, cool it, dry it, grind the dried gel into powder and calcine it, and finally obtain a rare earth dopant; S2: Preparation of biological rare earth dopants The rare earth dopant is added into ultrapure water to obtain a suspension, and then gelatin, β-cyclodextrin and glucose are weighed and added into the suspension, magnetic stirring is performed, and a hydrothermal reaction is performed. After the reaction, the hydrothermal reactor is cooled, and the supernatant is poured out, and the precipitate is washed by centrifugation with ultrapure water and anhydrous ethanol respectively, and dried. The dried product is evenly ground with a mortar to obtain a biological rare earth dopant; S3: Preparation of protonated cellulose composite graphite phase carbon nitride powder Weigh melamine and sodium carboxymethyl cellulose, calcine in a tube furnace to obtain a yellow block, grind and crush after cooling to obtain a yellow powder, add the yellow powder to an HCl solution, stir, filter and remove the filtrate, wash the filter residue with ultrapure water until neutral, and dry to obtain a protonated cellulose composite graphite phase carbon nitride powder; S4: Preparation of rare earth composite photocatalyst disinfection materials The biological rare earth dopant is added into ultrapure water, dispersed and stirred by ultrasound to form suspension A, and then the protonated cellulose composite graphite phase carbon nitride powder is dissolved in ultrapure water to obtain suspension B, and the suspension A and suspension B are mixed and magnetically stirred to obtain a composite suspension, and the composite suspension is dried to obtain a rare earth composite photocatalyst disinfection material.

2. The preparation process of a rare earth composite photocatalyst disinfection material according to claim 1, characterized in that: Step S1: preparing rare earth dopants, including the following steps: S1.1: Add 2-5 parts by weight of 0.3-0.4 mol / L zinc acetate solution into a reaction flask, and then add 2-7 parts by weight of rare earth ion solution and 5-8 parts by weight of titanium sulfate, wherein the rare earth ion solution is a 0.1-0.5 M cerium ion solution or lanthanum ion solution, to obtain a mixed solution; S1.2: After adjusting the pH of the mixed solution to 5.5-6 with 65-70% nitric acid, add 5-6 parts by mass of acrylamide monomer and 1-1.5 parts by mass of N,N'-methylenebisacrylamide, and then add 2-4 parts by mass of initiator ammonium persulfate, place on a magnetic stirrer and stir evenly, then place in a 70-80°C water bath for 1.5-2 hours to form a translucent gel; S1.3: Take out the translucent gel, cool it for 4-6 hours, wash it with anhydrous ethanol 2-3 times, and then put it into a constant temperature drying oven, dry it at 100-110℃ for 12-15 hours, grind the dried gel into powder and place it in a muffle furnace, calcine it at 550-600℃, and finally obtain rare earth dopants.

3. The preparation process of a rare earth composite photocatalyst disinfection material according to claim 2, characterized in that: Step S2 is to prepare biological rare earth dopants, comprising the following steps: S2.1: Add the rare earth dopant into ultrapure water at a solid-liquid ratio of 1:(8-10) g / L, stir magnetically until completely dissolved to obtain a suspension, then weigh 1-2 parts by mass of gelatin, 1-2 parts by mass of β-cyclodextrin and 1-2 parts by mass of glucose and add them to the suspension, stir magnetically for 0.5-1h, then add 10-15 parts by volume of anhydrous ethylenediamine and stir for 1-2h, then transfer to a hydrothermal reactor for hydrothermal reaction, and keep warm at 180-190°C for 24-26h; S2.2: After the reaction, wait for the hydrothermal autoclave to cool to room temperature (24-26°C) before opening the autoclave. Pour away the supernatant and wash the precipitate by centrifugation with ultrapure water and anhydrous ethanol respectively until the centrifuge liquid is clear. Dry the precipitate at 60-80°C for 20-24h and grind the dried product evenly with a mortar to obtain a biological rare earth dopant.

4. The preparation process of a rare earth composite photocatalyst disinfection material according to claim 1, characterized in that: Step S3 prepares protonated cellulose composite graphite phase carbon nitride powder, comprising the following steps: S3.1: Weigh 20-25 parts by weight of melamine and 10-12 parts by weight of sodium carboxymethyl cellulose, heat to 550-580°C in a tube furnace, and calcine for 4-4.5 hours at a heating rate of 2-5°C to obtain a yellow mass, which is then ground and sieved through a 200-mesh sieve to obtain a yellow powder; S3.2: Add the yellow powder into a 1.5-1.8 mol / L HCl solution, the solid-liquid ratio of the yellow powder to the HCl solution is 1:(0.4-0.5) g / L, stir at a speed of 6000-8000 r / min for 4-5 hours, remove the filtrate by suction, wash the filter residue with ultrapure water until it is neutral, and dry for 3-4 hours to obtain protonated cellulose composite graphite phase carbon nitride powder.

5. The preparation process of a rare earth composite photocatalyst disinfection material according to claim 4, characterized in that: Step S4 prepares a rare earth composite photocatalyst disinfection material, comprising the following steps: S4.1: Add the biological rare earth dopant to ultrapure water, disperse it by ultrasound, and stir to form a suspension A, then dissolve the protonated cellulose composite graphite phase carbon nitride powder in ultrapure water, the mass fraction of the protonated cellulose composite graphite phase carbon nitride powder is 20-25%, and obtain a suspension B, and mix the suspension A and the suspension B in a volume ratio of 1: (0.5-1), ultrasonicate for 1-1.5h, and then magnetically stir for 4-4.5h to obtain a composite suspension; S4.2: Dry the composite suspension in an oven at 60-70°C for 12-14 hours to obtain a rare earth composite photocatalyst disinfection material.

6. The preparation process of a rare earth composite photocatalyst disinfection material according to claim 5, characterized in that: In step S4.1, the material-liquid ratio of the biological rare earth dopant and ultrapure water is 1: (0.4-0.5) g / L.

7. A rare earth composite photocatalyst disinfection material, characterized in that: The material is prepared by the preparation process of the rare earth composite photocatalyst disinfection material described in any one of claims 1 to 6.

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