Antibacterial formaldehyde-removing wear-resistant ceramic tile and preparation method thereof

Abstract

The invention discloses an antibacterial formaldehyde-removing wear-resistant ceramic tile and a preparation method thereof, and belongs to the technical field of ceramic products. The ceramic tile is prepared from the following raw materials in parts by weight: 40-60 parts of kaolin, 20-30 parts of quartz sand, 10-15 parts of potassium feldspar, 15-20 parts of albite, 1-5 parts of calcium carbonate, 3-6 parts of a composite antibacterial agent, 1-2 parts of a formaldehyde removal agent and 0.5-1.5 parts of silicon carbide micro powder. The composite antibacterial agent is modified zinc oxide nanoparticles; the formaldehyde removal agent is a Bi2MoO6 / g-C3N4 composite material. Through material compounding and structural design, triple functions of antibiosis, formaldehyde removal and wear resistance are coordinated, and the prepared product is good in antibiosis effect, capable of efficiently removing formaldehyde, good in wear resistance, suitable for scenes with high requirements for safety, sanitation and durability, such as medical treatment, home furnishing and public buildings, and remarkable in market competitiveness.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic tiles, and in particular to a ceramic tile having antibacterial, formaldehyde-removing and good wear resistance and a preparation method thereof, which is suitable for places with high requirements on environmental health, such as hospitals, schools, and residences. Background Art

[0002] Ceramic tiles are a building material made from inorganic, non-metallic materials such as clay and quartz sand, sintered at high temperatures. Due to their durability, aesthetics, and functionality, they are widely used in a variety of fields, including architectural decoration, industrial applications, public facilities, art, and culture. With the acceleration of urbanization and improvements in living standards, ceramic tiles used in building decoration must not only possess basic decorative properties but also meet higher performance requirements, such as antibacterial properties, formaldehyde removal, wear resistance, easy cleaning, and environmental adaptability. Consequently, the single-function nature of traditional ceramic tiles no longer meets market demand.

[0003] Existing antimicrobial ceramic tiles mostly use a single antimicrobial agent, such as silver ions and nano-ZnO. These commonly suffer from issues such as silver ions being easily oxidized and ineffective, and insufficient inhibitory effects against some drug-resistant bacteria (such as methicillin-resistant Staphylococcus aureus). Formaldehyde-removing ceramic tiles also suffer from low formaldehyde removal efficiency and dependence on light exposure. Existing photocatalytic ceramic tiles rely on photocatalysts such as TiO2, but their catalytic efficiency is insufficient under indoor visible light conditions, and the 24-hour formaldehyde degradation rate of ordinary TiO2 ceramic tiles is less than 60%. Furthermore, it is difficult to balance wear resistance and functionality. Therefore, there is an urgent need for multifunctional ceramic tiles with a broad antimicrobial spectrum, stable antimicrobial efficacy, efficient formaldehyde removal under visible light, and strong wear resistance. Summary of the Invention

[0004] The purpose of the present invention is to provide an antibacterial, formaldehyde-removing and wear-resistant ceramic tile. Through material compounding and structural design, the triple functions of "antibacterial-formaldehyde-removing-wear-resistant" are realized. The product has good antibacterial effect, can efficiently remove formaldehyde and has good wear resistance. It is suitable for scenarios with high requirements on safety, hygiene and durability, such as medical, home, public buildings and other scenarios, and has significant market competitiveness.

[0005] In order to achieve the above technical objectives, the technical solution adopted by the present invention is: An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 40-60 parts of kaolin, 20-30 parts of quartz sand, 10-15 parts of potassium feldspar, 15-20 parts of sodium feldspar, 1-5 parts of calcium carbonate, 3-6 parts of a composite antibacterial agent, 1-2 parts of a formaldehyde-removing agent, and 0.5-1.5 parts of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 / g-C3N4 composite material.

[0006] Preferably, the composite antibacterial agent is prepared by the following method: S1. Dissolve 0.1 mol Zn(NO₃)₂·6H₂O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add La(NO₃)₃·6H₂O and Ce(NO₃)₃·6H₂O and stir until completely dissolved. Then, add sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain La / Ce-ZnO nanoparticles. S4. The La / Ce-ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension with a concentration of 0.1 g / mL, and 1% PVP by volume was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in appropriate proportions, add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours, collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

[0007] Preferably, in step S1, the molar ratio of La(NO3)3·6H2O, Ce(NO3)3·6H2O and sodium citrate is 1.5:1:2.5; and the molar ratio of La(NO3)3·6H2O to Zn(NO3)2·6H2O is 3:200.

[0008] Preferably, in step S5, the volume ratio of the mixed solution B, TEOS, and deionized water is 20:1:5.

[0009] Preferably, the Bi2MoO6 / g-C3N4 composite material is prepared by the following method: a. Weigh urea and melamine in a molar ratio, mix them evenly, stir them, put them into a ceramic crucible, heat them to 550 ° C and calcine them at high temperature for 4h, cool them to room temperature and grind them to obtain powdered g-C3N4; b. 0.01 mol Bi(NO3)3·5H2O was dissolved in 50 mL of dilute nitric acid solution, and 10 mL of g-C3N4 dispersion was added thereto under magnetic stirring to obtain a mixed solution A; c. Dissolve 0.005 mol (NH4)2MoO4·2H2O in 50 ml of deionized water to obtain an ammonium molybdate solution; d. Mix the mixed solution A with the ammonium molybdate solution, adjust the pH to 7.5-8.0, transfer to a 200 mL polytetrafluoroethylene reactor, and hydrothermally react at 180°C for 12 hours. After the reaction, centrifuge and wash to neutrality, dry in a vacuum at 60°C, and grind to obtain the Bi2MoO6 / g-C3N4 composite material.

[0010] Preferably, in step a, the molar ratio of urea to melamine is 5:1; and the heating rate during calcination is 2°C / min.

[0011] Preferably, the concentration of the dilute nitric acid solution in step b is 1 mol / L; the concentration of the g-C3N4 dispersion is 5 g / L.

[0012] Preferably, the volume ratio of the mixed solution A to the ammonium molybdate solution in step c is 1:1-1.1.

[0013] Preferably, the silicon carbide powder has a particle size of 60,000 mesh.

[0014] A method for preparing the antibacterial and formaldehyde-removing wear-resistant ceramic tile comprises the following steps: (1) Preparation of composite antimicrobial agents; (2) Preparation of formaldehyde removal agent; (3) Weigh kaolin, quartz sand, potassium feldspar, sodium feldspar, and calcium carbonate by weight, add them into a ball mill, use water as the medium, and mill at a speed of 250 rpm for 4 h. Pass through a 200-mesh sieve to obtain a uniform matrix slurry. (4) Add the composite antibacterial agent, formaldehyde remover, and silicon carbide micropowder to the matrix slurry, adjust the speed to 150 rpm and continue ball milling for 2 hours to obtain a mixed slurry; (5) The mixed slurry is pumped into a spray drying tower for granulation, and the moisture content of the particles is controlled to be ≤6% to obtain a green body powder. The powder is then filled into a mold and pressed into shape to obtain a green body; (6) The green body is subjected to gradient sintering treatment, heating the temperature to 300°C at a heating rate of 3°C / min, keeping it warm for 30 minutes, then heating it to 800°C at a heating rate of 5°C / min, keeping it warm for 1 hour, and then heating it to 1150-1200°C at a heating rate of 4°C / min, keeping it warm for 2 hours, and then cooling it to room temperature to obtain the final product.

[0015] Compared with the prior art, the present invention has the following beneficial effects: (1) The composite antibacterial agent prepared by the present invention is La 3+ and Ce 3+ Doped modified ZnO and coated with nano-silicon dioxide to form a core-shell structure ( Figure 1), double rare earth doping adjusts the band structure of ZnO through different ionic radius and electronic properties, increases oxygen vacancy defects, and broadens the light response range of ZnO to the visible light region, thereby promoting the generation of reactive oxygen species (ROS), making the photocatalytic activity stronger, significantly improving the antibacterial activity and Zn 2+ with La 3+ / Ce 3+ It is released from the core layer and slowly released through the SiO2 shell layer, forming a "sustained antibacterial" effect, and the antibacterial effect is stable and long-lasting.

[0016] (2) The formaldehyde removal agent prepared by the present invention is a heterojunction structure formed by a Bi2MoO6 / g-C3N4 composite material ( Figure 2 ) optimizes the separation efficiency of photogenerated carriers. The narrow bandgap of Bi2MoO6 complements the wide bandgap of g-C3N4, suppressing electron-hole recombination. This significantly improves quantum efficiency and extends the absorption edge into the visible light region, significantly increasing the formaldehyde degradation rate under visible light. Furthermore, the formaldehyde remover exhibits good compatibility with the ceramic matrix material, and the functional components exhibit excellent activity after high-temperature sintering.

[0017] (3) The raw materials of the components of the present invention are reasonably proportioned, and the product is sintered and formed in one step. The composite antibacterial agent and the formaldehyde removal agent work synergistically, and combined with the SiC reinforced network, the efficient integration of the triple functions of antibacterial, formaldehyde removal and wear resistance is achieved. The prepared product has excellent antibacterial, formaldehyde removal and wear resistance, and the service life of the product is extended, and the market application prospect is good. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The SEM and TEM images of the composite antibacterial agent prepared by the present invention are shown in Figure 1, where a is the SEM image and b is the TEM image. Figure 2 This is the SEM image of the formaldehyde scavenger prepared by the present invention, where a is Bi2MoO6 nanosheets, b is g-C3N4, and c is the formaldehyde scavenger. DETAILED DESCRIPTION

[0019] The technical solution of the present invention will be further described below with reference to specific embodiments, but is not limited thereto.

[0020] Example 1 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 40 parts of kaolin, 20 parts of quartz sand, 10 parts of potassium feldspar, 15 parts of sodium feldspar, 1 part of calcium carbonate, 3 parts of a composite antibacterial agent, 1 part of a formaldehyde-removing agent, and 0.5 part of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 / g-C3N4 composite material.

[0021] The composite antibacterial agent is prepared by the following method: S1. Dissolve 0.1 mol Zn(NO₃)₂·6H₂O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add 1.5 mmol La(NO₃)₃·6H₂O and 1 mmol Ce(NO₃)₃·6H₂O and stir until completely dissolved. Then, add 6.45 g sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain La / Ce-ZnO nanoparticles. S4. The La / Ce-ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension at a concentration of 0.1 g / mL, and a volume ratio of 1% PVP was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in a volume ratio of 20:1:5. Add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours. Collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

[0022] The Bi2MoO6 / g-C3N4 composite material is prepared by the following method: a. Weigh urea and melamine in a molar ratio of 5:1, mix well, stir evenly, put into a ceramic crucible, heat to 550℃ at a rate of 2℃ / min, calcine at high temperature for 4h, cool to room temperature and grind to obtain powdered g-C3N4; b. 0.01 mol Bi(NO3)3·5H2O was dissolved in 50 mL of a 1 mol / L dilute nitric acid solution, and 10 mL of a 5 g / L g-C3N4 dispersion was added thereto under magnetic stirring to obtain a mixed solution A; c. Dissolve 0.005 mol (NH4)2MoO4·2H2O in 50 ml of deionized water to obtain an ammonium molybdate solution; d. Mixed solution A and ammonium molybdate solution in a volume ratio of 1:1, adjust the pH to 7.5, transfer to a 200 mL polytetrafluoroethylene reactor, and hydrothermally react at 180°C for 12 hours. After the reaction, centrifuge and wash to neutrality, dry in a vacuum at 60°C, and grind to obtain the Bi2MoO6 / g-C3N4 composite material.

[0023] The particle size of the silicon carbide micropowder is 60000 mesh.

[0024] A method for preparing the antibacterial and formaldehyde-removing wear-resistant ceramic tile comprises the following steps: (1) Preparation of composite antimicrobial agents; (2) Preparation of formaldehyde removal agent; (3) Weigh kaolin, quartz sand, potassium feldspar, sodium feldspar, and calcium carbonate by weight, add them into a ball mill, use water as the medium, and mill at a speed of 250 rpm for 4 h. Pass through a 200-mesh sieve to obtain a uniform matrix slurry. (4) Add the composite antibacterial agent, formaldehyde remover, and silicon carbide micropowder to the matrix slurry, adjust the speed to 150 rpm and continue ball milling for 2 hours to obtain a mixed slurry; (5) The mixed slurry is pumped into a spray drying tower for granulation, and the moisture content of the particles is controlled to be ≤6% to obtain a green body powder. The powder is then filled into a mold and pressed into shape to obtain a green body; (6) The green body was subjected to gradient sintering treatment, heating the temperature to 300°C at a heating rate of 3°C / min, keeping it warm for 30 minutes, then heating the temperature to 800°C at a heating rate of 5°C / min, keeping it warm for 1 hour, and then heating the temperature to 1150°C at a heating rate of 4°C / min, keeping it warm for 2 hours, and then cooling to room temperature to obtain the final product.

[0025] Example 2 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 60 parts of kaolin, 30 parts of quartz sand, 15 parts of potassium feldspar, 20 parts of sodium feldspar, 5 parts of calcium carbonate, 6 parts of a composite antibacterial agent, 2 parts of a formaldehyde-removing agent, and 1.5 parts of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 / g-C3N4 composite material.

[0026] The composite antibacterial agent is prepared by the following method: S1. Dissolve 0.1 mol Zn(NO₃)₂·6H₂O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add 1.5 mmol La(NO₃)₃·6H₂O and 1 mmol Ce(NO₃)₃·6H₂O and stir until completely dissolved. Then, add 6.45 g sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain La / Ce-ZnO nanoparticles. S4. The La / Ce-ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension at a concentration of 0.1 g / mL, and a volume ratio of 1% PVP was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in a volume ratio of 20:1:5. Add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours. Collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

[0027] The Bi2MoO6 / g-C3N4 composite material is prepared by the following method: a. Weigh urea and melamine in a molar ratio of 5:1, mix well, stir evenly, put into a ceramic crucible, heat to 550℃ at a rate of 2℃ / min, calcine at high temperature for 4h, cool to room temperature and grind to obtain powdered g-C3N4; b. 0.01 mol Bi(NO3)3·5H2O was dissolved in 50 mL of a 1 mol / L dilute nitric acid solution, and 10 mL of a 5 g / L g-C3N4 dispersion was added thereto under magnetic stirring to obtain a mixed solution A; c. Dissolve 0.005 mol (NH4)2MoO4·2H2O in 50 ml of deionized water to obtain an ammonium molybdate solution; d. Mixed solution A and ammonium molybdate solution in a volume ratio of 1:1.1, adjusted the pH to 8.0, transferred to a 200 mL polytetrafluoroethylene reactor, and subjected to hydrothermal reaction at 180°C for 12 h. After the reaction, centrifugation and washing were performed until neutral, vacuum dried at 60°C, and ground to obtain the Bi2MoO6 / g-C3N4 composite material.

[0028] The particle size of the silicon carbide micropowder is 60000 mesh.

[0029] A method for preparing the antibacterial and formaldehyde-removing wear-resistant ceramic tile comprises the following steps: (1) Preparation of composite antimicrobial agents; (2) Preparation of formaldehyde removal agent; (3) Weigh kaolin, quartz sand, potassium feldspar, sodium feldspar, and calcium carbonate by weight, add them into a ball mill, use water as the medium, and mill at a speed of 250 rpm for 4 h. Pass through a 200-mesh sieve to obtain a uniform matrix slurry. (4) Add the composite antibacterial agent, formaldehyde remover, and silicon carbide micropowder to the matrix slurry, adjust the speed to 150 rpm and continue ball milling for 2 hours to obtain a mixed slurry; (5) The mixed slurry is pumped into a spray drying tower for granulation, and the moisture content of the particles is controlled to be ≤6% to obtain a green body powder. The powder is then filled into a mold and pressed into shape to obtain a green body; (6) The green body was subjected to gradient sintering treatment, heating the temperature to 300°C at a heating rate of 3°C / min, keeping it warm for 30 minutes, then heating the temperature to 800°C at a heating rate of 5°C / min, keeping it warm for 1 hour, and then heating the temperature to 1180°C at a heating rate of 4°C / min, keeping it warm for 2 hours, and then cooling to room temperature to obtain the final product.

[0030] Example 3 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 50 parts of kaolin, 25 parts of quartz sand, 12 parts of potassium feldspar, 18 parts of sodium feldspar, 3 parts of calcium carbonate, 5 parts of a composite antibacterial agent, 1.5 parts of a formaldehyde-removing agent, and 1 part of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 / g-C3N4 composite material.

[0031] The composite antibacterial agent is prepared by the following method: S1. Dissolve 0.1 mol Zn(NO₃)₂·6H₂O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add 1.5 mmol La(NO₃)₃·6H₂O and 1 mmol Ce(NO₃)₃·6H₂O and stir until completely dissolved. Then, add 6.45 g sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain La / Ce-ZnO nanoparticles. S4. The La / Ce-ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension at a concentration of 0.1 g / mL, and a volume ratio of 1% PVP was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in a volume ratio of 20:1:5. Add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours. Collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

[0032] The Bi2MoO6 / g-C3N4 composite material is prepared by the following method: a. Weigh urea and melamine in a molar ratio of 5:1, mix well, stir evenly, put into a ceramic crucible, heat to 550℃ at a rate of 2℃ / min, calcine at high temperature for 4h, cool to room temperature and grind to obtain powdered g-C3N4; b. 0.01 mol Bi(NO3)3·5H2O was dissolved in 50 mL of a 1 mol / L dilute nitric acid solution, and 10 mL of a 5 g / L g-C3N4 dispersion was added thereto under magnetic stirring to obtain a mixed solution A; c. Dissolve 0.005 mol (NH4)2MoO4·2H2O in 50 ml of deionized water to obtain an ammonium molybdate solution; d. Mixed solution A was mixed with ammonium molybdate solution in a volume ratio of 1:1.1, the pH was adjusted to 7.8, and the mixture was transferred to a 200 mL polytetrafluoroethylene reactor. The mixture was hydrothermally reacted at 180°C for 12 hours. After the reaction, the mixture was centrifuged and washed until neutral, dried in a vacuum at 60°C, and ground to obtain the Bi2MoO6 / g-C3N4 composite material.

[0033] The particle size of the silicon carbide micropowder is 60000 mesh.

[0034] A method for preparing the antibacterial and formaldehyde-removing wear-resistant ceramic tile comprises the following steps: (1) Preparation of composite antimicrobial agents; (2) Preparation of formaldehyde removal agent; (3) Weigh kaolin, quartz sand, potassium feldspar, sodium feldspar, and calcium carbonate by weight, add them into a ball mill, use water as the medium, and mill at a speed of 250 rpm for 4 h. Pass through a 200-mesh sieve to obtain a uniform matrix slurry. (4) Add the composite antibacterial agent, formaldehyde remover, and silicon carbide micropowder to the matrix slurry, adjust the speed to 150 rpm and continue ball milling for 2 hours to obtain a mixed slurry; (5) The mixed slurry is pumped into a spray drying tower for granulation, and the moisture content of the particles is controlled to be ≤6% to obtain a green body powder. The powder is then filled into a mold and pressed into shape to obtain a green body; (6) The green body was subjected to gradient sintering treatment, heating the temperature to 300°C at a heating rate of 3°C / min, keeping it warm for 30 minutes, then heating the temperature to 800°C at a heating rate of 5°C / min, keeping it warm for 1 hour, and then heating the temperature to 1200°C at a heating rate of 4°C / min, keeping it warm for 2 hours, and then cooling to room temperature to obtain the final product.

[0035] Comparative Example 1 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 50 parts of kaolin, 25 parts of quartz sand, 12 parts of potassium feldspar, 18 parts of sodium feldspar, 3 parts of calcium carbonate, 5 parts of a composite antibacterial agent, 1.5 parts of a formaldehyde-removing agent, and 1 part of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 / g-C3N4 composite material.

[0036] This comparative example is basically the same as Example 3, except that La(NO3)3·6H2O and Ce(NO3)3·6H2O are not added to the composite antibacterial agent. The specific preparation method of the composite antibacterial agent is as follows: S1. Dissolve 0.1 mol Zn(NO3)2·6H2O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add 6.45 g of sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain ZnO nanoparticles. S4. The ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension at a concentration of 0.1 g / mL, and a volume ratio of 1% PVP was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in a volume ratio of 20:1:5. Add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours. Collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

[0037] Comparative Example 2 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 50 parts of kaolin, 25 parts of quartz sand, 12 parts of potassium feldspar, 18 parts of sodium feldspar, 3 parts of calcium carbonate, 5 parts of a composite antibacterial agent, 1.5 parts of a formaldehyde-removing agent, and 1 part of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 / g-C3N4 composite material.

[0038] This comparative example is basically the same as Example 3, except that Ce(NO3)3·6H2O is not added to the composite antibacterial agent. The specific preparation method of the composite antibacterial agent is as follows: S1. Dissolve 0.1 mol Zn(NO3)2·6H2O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add 1.5 mmol La(NO3)3·6H2O and stir until completely dissolved. Then, add 6.45 g sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain La / ZnO nanoparticles. S4. The La / ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension at a concentration of 0.1 g / mL, and a volume ratio of 1% PVP was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in a volume ratio of 20:1:5. Add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours. Collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

[0039] Comparative Example 3 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 50 parts of kaolin, 25 parts of quartz sand, 12 parts of potassium feldspar, 18 parts of sodium feldspar, 3 parts of calcium carbonate, 5 parts of a composite antibacterial agent, 1.5 parts of a formaldehyde-removing agent, and 1 part of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 / g-C3N4 composite material.

[0040] This comparative example is basically the same as Example 3, except that La(NO3)3·6H2O is not added to the composite antibacterial agent. The specific preparation method of the composite antibacterial agent is as follows: S1. Dissolve 0.1 mol Zn(NO3)2·6H2O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add 1 mmol Ce(NO3)3·6H2O and stir until completely dissolved. Then, add 6.45 g sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain Ce / ZnO nanoparticles. S4. The Ce / ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension at a concentration of 0.1 g / mL, and a volume ratio of 1% PVP was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in a volume ratio of 20:1:5. Add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours. Collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

[0041] Comparative Example 4 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 50 parts of kaolin, 25 parts of quartz sand, 12 parts of potassium feldspar, 18 parts of sodium feldspar, 3 parts of calcium carbonate, 5 parts of a composite antibacterial agent, 1.5 parts of a formaldehyde-removing agent, and 1 part of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is g-C3N4.

[0042] This comparative example is basically the same as Example 3, the only difference being that the formaldehyde removal agent is g-C3N4.

[0043] The preparation method of the g-C3N4 is as follows: urea and melamine are weighed and mixed in a molar ratio of 5:1, stirred evenly, placed in a ceramic crucible, heated to 550°C at a rate of 2°C / min, and then calcined at high temperature for 4 hours. After cooling to room temperature, the mixture is ground to obtain powdered g-C3N4.

[0044] Comparative Example 5 An antibacterial and formaldehyde-removing wear-resistant ceramic tile is made of the following raw materials in parts by weight: 50 parts of kaolin, 25 parts of quartz sand, 12 parts of potassium feldspar, 18 parts of sodium feldspar, 3 parts of calcium carbonate, 5 parts of a composite antibacterial agent, 1.5 parts of a formaldehyde-removing agent, and 1 part of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde-removing agent is a Bi2MoO6 nanomaterial.

[0045] This comparative example is basically the same as Example 3, the only difference being that the formaldehyde removal agent is Bi2MoO6 nanomaterial.

[0046] 1) The Bi2MoO6 nanomaterial is prepared by the following method: 0.01 mol Bi(NO3)3·5H2O is dissolved in 50 mL of 1 mol / L dilute nitric acid solution to obtain a mixed solution A; 2) Dissolve 0.005 mol (NH4)2MoO4·2H2O in 50 ml of deionized water to obtain an ammonium molybdate solution. 3) Mixed solution A and ammonium molybdate solution were mixed in a volume ratio of 1:1.1, the pH was adjusted to 7.8, and the mixture was transferred to a 200 mL polytetrafluoroethylene reactor. The mixture was hydrothermally reacted at 180°C for 12 hours. After the reaction, the mixture was centrifuged and washed until neutral, dried in a vacuum at 60°C, and ground to obtain Bi2MoO6 nanomaterials.

[0047] Performance Testing The morphology of the composite antibacterial agent prepared by the present invention was tested, and the SEM and TEM test results were as follows: Figure 1 As shown. Figure 1 It can be seen from Figure 1 that the composite antibacterial agent prepared by the present invention has a spherical structure as a whole, and the particle size is about 300-400 nm; Figure 1b It can be seen that the modified zinc oxide nanoparticles prepared by the present invention have an obvious core-shell structure, with La / Ce-ZnO nanoparticles as the core, covered with SiO2 shell, and Zn 2+ with La 3+ / Ce 3+ It is released from the core layer and slowly released through the SiO2 shell layer, forming a "sustained antibacterial" effect.

[0048] like Figure 2 As shown, Figure 2 a is a smooth Bi2MoO6 nanosheet structure, Figure 2 b is the porous stacked sheet structure g-C3N4, Figure 2 c is a doped sheet structure. Bi2MoO6 nanosheets are uniformly loaded on the surface of the g-C3N4 porous layered skeleton, resulting in close interface contact, increased specific surface area, and more formaldehyde adsorption sites.

[0049] According to JC / T897-2014, "Antibacterial Properties of Antibacterial Ceramic Products," the antibacterial and formaldehyde-removing wear-resistant ceramic tiles prepared in Examples 1-3 and Comparative Examples 1-5 were tested for their antibacterial properties and durability. The surfaces of the samples were repeatedly scrubbed 1000 times with a 5% sodium hypochlorite disinfectant, and the antibacterial properties of the samples after scrubbing were measured. The results are shown in Table 1 below.

[0050] Table 1 Antibacterial performance test results The above results demonstrate that, when using La / Ce dual-doped modified zinc oxide nanomaterials as composite antimicrobial agents in Examples 1-3, the synergistic effect of the two rare earth elements significantly enhances antimicrobial performance. The SiO2 coating effectively releases antimicrobial ions, resulting in a durable antimicrobial rate attenuation of less than 1.1%. Comparative Example 1, which relies solely on the antimicrobial activity of SiO2-coated ZnO, exhibits poor antimicrobial efficacy and significant attenuation after washing. The data from Comparative Examples 2-3 demonstrate that the synergistic effect of La and Ce is essential for the composite antimicrobial materials of the present invention.

[0051] The ceramic tiles prepared in Examples 1-3 and Comparative Examples 4-5 were placed in a test chamber and tested for formaldehyde removal effectiveness for 24 hours according to QB / T2761-2006, "Method for Determining the Purification Effectiveness of Indoor Air Purification Products." Simultaneously, the surfaces of the samples were repeatedly scrubbed 1000 times with a 5% sodium hypochlorite disinfectant. The formaldehyde removal effectiveness of the washed samples was tested, and the results are shown in Table 2.

[0052] Table 2 Formaldehyde removal effect The above data show that the Bi2MoO6 / g-C3N4 composite material heterojunction used in the present invention significantly improves the photocatalytic efficiency, the formaldehyde degradation rate under visible light is greater than 90%, the attenuation after washing is less than 2.5%, and the formaldehyde removal effect is excellent in durability.

[0053] The antibacterial and formaldehyde-removing wear-resistant ceramic tiles prepared by the present invention have excellent wear resistance. According to the GB / T 3810.6-2016 standard, the wear resistance revolution number is ≥2100 revolutions, and the wear resistance is excellent.

[0054] It should be noted that the above embodiments are only some of the preferred embodiments of the present invention, and not all of them. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present invention.

Claims

1. An antibacterial and formaldehyde-removing wear-resistant ceramic tile, characterized in that: The invention is prepared from the following raw materials in parts by weight: 40-60 parts of kaolin, 20-30 parts of quartz sand, 10-15 parts of potassium feldspar, 15-20 parts of sodium feldspar, 1-5 parts of calcium carbonate, 3-6 parts of a composite antibacterial agent, 1-2 parts of a formaldehyde scavenger, and 0.5-1.5 parts of silicon carbide micropowder; the composite antibacterial agent is modified zinc oxide nanoparticles; and the formaldehyde scavenger is a Bi2MoO6 / g-C3N4 composite material.

2. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 1, characterized in that: The composite antibacterial agent is prepared by the following method: S1. Dissolve 0.1 mol Zn(NO₃)₂·6H₂O in 200 ml of deionized water and stir magnetically until completely dissolved. Then, add La(NO₃)₃·6H₂O and Ce(NO₃)₃·6H₂O and stir until completely dissolved. Then, add sodium citrate to the mixture and stir until completely dissolved to obtain a mixture A. S2. Ammonia was slowly added dropwise to the mixture A to adjust the pH to 9-10 to form a white sol. After continuous stirring for 2 hours, the sol was transferred to a 60°C water bath and allowed to stand for 12 hours to form a gel; S3. The gel was centrifuged and washed three times with deionized water and ethanol, respectively. After drying, the gel was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min for 3 hours to obtain La / Ce-ZnO nanoparticles. S4. The La / Ce-ZnO nanoparticles were ultrasonically dispersed in anhydrous ethanol solution to form a suspension with a concentration of 0.1 g / mL, and 1% PVP by volume was added to the suspension to obtain a mixed solution B; S5. Evenly mix mixed solution B, TEOS, and deionized water in appropriate proportions, add ammonia dropwise and adjust the pH to 10-11. React at 40°C for 4-6 hours, collect the product by centrifugation, wash three times with anhydrous ethanol, and vacuum dry to obtain a composite antimicrobial agent.

3. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 2, characterized in that: In step S1, the molar ratio of La(NO3)3·6H2O, Ce(NO3)3·6H2O, and sodium citrate is 1.5:1:2.5; the molar ratio of La(NO3)3·6H2O to Zn(NO3)2·6H2O is 3:

200.

4. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 2, characterized in that: In step S5, the volume ratio of the mixed solution B, TEOS, and deionized water is 20:1:

5.

5. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 1, characterized in that: The Bi2MoO6 / g-C3N4 composite material is prepared by the following method: a. Weigh urea and melamine in a molar ratio, mix them evenly, stir them, put them into a ceramic crucible, heat them to 550 ° C and calcine them at high temperature for 4h, cool them to room temperature and grind them to obtain powdered g-C3N4; b. 0.01 mol Bi(NO3)3·5H2O was dissolved in 50 mL of dilute nitric acid solution, and 10 ml of g-C3N4 dispersion was added thereto under magnetic stirring to obtain a mixed solution A; c. Dissolve 0.005 mol (NH4)2MoO4·2H2O in 50 ml of deionized water to obtain an ammonium molybdate solution; d. Mix solution A with ammonium molybdate solution, adjust the pH to 7.5-8.0, transfer to a 200 mL polytetrafluoroethylene reactor, and hydrothermally react at 180°C for 12 hours. After completion of the reaction, centrifuge and wash to neutrality, dry in a vacuum at 60°C, and grind to obtain the Bi2MoO6 / g-C3N4 composite material.

6. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 5, characterized in that: In step a, the molar ratio of urea to melamine is 5:1; and the heating rate during calcination is 2°C / min.

7. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 5, characterized in that: The concentration of the dilute nitric acid solution in step b is 1 mol / L; the concentration of the g-C3N4 dispersion is 5 g / L.

8. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 5, characterized in that: In step c, the volume ratio of the mixed solution A to the ammonium molybdate solution is 1:1-1.

1.

9. The antibacterial and formaldehyde-removing wear-resistant ceramic tile according to claim 1, characterized in that: The particle size of the silicon carbide micropowder is 60000 mesh.

10. A method for preparing the antibacterial and formaldehyde-removing wear-resistant ceramic tile according to any one of claims 1 to 9, characterized in that: It includes the following steps: (1) Preparation of composite antimicrobial agents; (2) Preparation of formaldehyde removal agent; (3) Weigh kaolin, quartz sand, potassium feldspar, sodium feldspar, and calcium carbonate by weight, add them into a ball mill, use water as the medium, and mill at a speed of 250 rpm for 4 h. Pass through a 200-mesh sieve to obtain a uniform matrix slurry. (4) Add the composite antibacterial agent, formaldehyde remover, and silicon carbide micropowder to the matrix slurry, adjust the speed to 150 rpm and continue ball milling for 2 hours to obtain a mixed slurry; (5) The mixed slurry is pumped into a spray drying tower for granulation, and the moisture content of the particles is controlled to be ≤6% to obtain a green body powder. The powder is then filled into a mold and pressed into shape to obtain a green body; (6) The green body is subjected to gradient sintering treatment, heating the temperature to 300°C at a heating rate of 3°C / min, keeping it warm for 30 minutes, then heating it to 800°C at a heating rate of 5°C / min, keeping it warm for 1 hour, and then heating it to 1150-1200°C at a heating rate of 4°C / min, keeping it warm for 2 hours, and then cooling it to room temperature to obtain the final product.

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