Preparation method and application of novel mesoporous quantum photocatalytic formaldehyde removal material
By combining modified titanium dioxide with graphene to form rGO/nTiO2 material, the problem of poor formaldehyde removal efficiency of traditional adsorption methods is solved, achieving efficient and low-cost formaldehyde decomposition and possessing visible light response capability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 海南朗研光电有限公司
- Filing Date
- 2024-12-02
- Publication Date
- 2026-06-02
AI Technical Summary
In existing technologies, traditional adsorption methods are ineffective and costly in removing formaldehyde, and they are difficult to decompose formaldehyde quickly, failing to meet the demand for efficient and low-cost formaldehyde removal.
A novel mesoporous quantum photocatalytic formaldehyde removal material is prepared by bombarding titanium dioxide with metal ions and then combining it with graphene to form rGO/nTiO2 material, which broadens the photoresponse range and utilizes the high conductivity and catalytic properties of graphene to decompose formaldehyde.
It achieves efficient and stable formaldehyde decomposition with a degradation rate of 98%, significantly outperforming commercially available competitors. It also features visible light response capability, fast degradation rate, and low cost.
Smart Images
Figure CN122124768A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of air purification technology, specifically to a method for preparing and applying a novel mesoporous quantum photocatalytic formaldehyde removal material. Background Technology
[0002] In today's technologically advanced world, with the improvement of living standards, "healthy living" has become a research hotspot, and addressing formaldehyde pollution is an indispensable part of this topic. Formaldehyde, an organic pollutant primarily entering the human body through respiration, is widely found in paints, wood, leather, textiles, clothing, furniture, cosmetics, and other fields, accumulating indoors during renovations. As a known Group 1 carcinogen, formaldehyde is a toxic industrial chemical characterized by its rapid onset, low volatility, and mutagenic properties. Long-term exposure to formaldehyde can have toxic effects on the skin, mucous membranes, respiratory tract, nervous system, reproductive system, and kidneys, causing significant harm to the human body. Therefore, finding an effective method to remove formaldehyde is urgent. Currently, the main methods for formaldehyde removal include adsorption, plant purification, ventilation, and photocatalytic decomposition. Traditional formaldehyde removal primarily relies on adsorption, but this method is time-consuming, ineffective, costly, and does not decompose formaldehyde. To achieve faster and more efficient formaldehyde decomposition, developing novel photocatalytic materials capable of efficiently decomposing formaldehyde has become a key research focus. Summary of the Invention
[0003] The present invention aims to provide a method for preparing and applying a novel mesoporous quantum photocatalytic formaldehyde removal material, so as to improve the degradation rate and stability of formaldehyde.
[0004] To achieve the above objectives, the present invention adopts the following technical solution: a method for preparing a novel mesoporous quantum photocatalytic formaldehyde removal material, comprising the following steps:
[0005] S1. Preparation of titanium dioxide powder;
[0006] S2. Preparation of rGO / nTiO2 materials;
[0007] S3. The rGO / nTiO2 material prepared in S2 is mixed with other substances in a certain proportion to obtain a novel mesoporous quantum photocatalytic formaldehyde removal material.
[0008] Preferably, the preparation of titanium dioxide powder in S1 includes the following steps:
[0009] S1.1. Using the metal ion implantation method, high-energy metal ions are used to bombard TiO2 to obtain modified titanium dioxide that promotes absorption of visible light across the entire wavelength range.
[0010] S1.2 The modified TiO2 with full-band visible light absorption is annealed in oxygen.
[0011] Preferably, the preparation of rGO / nTiO2 material in S2 includes the following steps:
[0012] S2.1 The titanium dioxide powder and graphene prepared in S1 are constructed in layers, and the titanium dioxide layers and graphene are stacked on a nickel mesh.
[0013] S2.2 Under the protection of nitrogen, the stacked graphene and titanium dioxide are placed in a furnace. The graphene deforms at high temperature and then coats the titanium dioxide to obtain mixture A.
[0014] S2.3 Dissolve mixture A in deionized water and ethanol, ultrasonically disperse it for a certain time under pH 6-7 conditions, transfer it to an oven, dry it, and take it out to obtain rGO / nTiO2 material.
[0015] Preferably, in S1.1, the metal ion is any one of V, Mg, and Fe.
[0016] Preferably, in S1.1, the high-energy ion accelerator has an energy of 150 keV; the ion implantation rate is 10 × 10⁻⁶. -7 -20×10 -7 mol / gcat.
[0017] Preferably, in step S2.1, the weight ratio of graphene to titanium dioxide is 1:(0.1-1.5).
[0018] Preferably, in step S3, the rGO / nTiO2 material prepared in step S2 is mixed with other substances in a certain proportion to obtain a novel mesoporous quantum photocatalytic formaldehyde removal material, specifically including the following steps:
[0019] S3.1. Polyethylene glycol and the rGO / nTiO2 material prepared in S2 are dispersed in deionized water and ultrasonically milled for a certain time to obtain mixed solution A;
[0020] S3.2 Add the additive to deionized water and ultrasonically stir for a certain period of time to obtain mixed solution B;
[0021] S3.3. Mix the prepared mixed solution A with mixed solution B to obtain mixed solution C. Mix mixed solution C with adsorbent g and solvent D, and then ultrasonically mill to obtain a milky white transparent liquid, which is the novel mesoporous quantum photocatalytic formaldehyde removal material.
[0022] Preferably, in step S3.1, the mass ratio of polyethylene glycol, the rGO / nTiO2 material prepared in step S2, and deionized water is 1:(0.8-1.5):(10-20).
[0023] Preferably, in S3.2, the mass ratio of the additive to deionized water is 1:(10-20).
[0024] The present invention also provides another technical solution: the application of a novel mesoporous quantum photocatalytic formaldehyde removal material for indoor formaldehyde treatment.
[0025] The beneficial effects of this solution are as follows: This invention encapsulates nano-titanium dioxide atoms within graphene, utilizing the high conductivity and high catalytic activity of graphene to broaden the light response range of nano-titanium dioxide, absorbing light energy to generate highly oxidizing free negative ions, decomposing adsorbed formaldehyde to obtain water and carbon dioxide, thus obtaining a novel mesoporous quantum material with high-speed formaldehyde degradation, high stability, and excellent visible light response. Attached Figure Description
[0026] Figure 1 SEM image of the rGO / nTiO2 material prepared in Example 1 of this invention;
[0027] Figure 2 This is a comparison graph showing the rate of rhodamine degradation by titanium dioxide powder prepared in Example 1 and Comparative Example 1 of the present invention.
[0028] Figure 3 This is a comparison chart of the degradation rates of rGO-TiO2 composite material, expanded graphene, and TiO2 of rhodamine prepared in Example 1 and Comparative Examples 2-3 of the present invention.
[0029] Figure 4 This is a comparison chart showing the formaldehyde decomposition rate of the novel mesoporous quantum photocatalytic formaldehyde removal material prepared in Example 1 of the present invention with that of commercially available competing products 1, 2, 3, and 4 in Comparative Example 4.
[0030] Figure 5 The graph shows the decomposition rate of the novel mesoporous quantum photocatalytic formaldehyde removal material prepared in Example 1 of this invention after five repeated degradation cycles in a rhodamine solution.
[0031] Figure 6 This is a diagram illustrating the mechanism of action of the rGO / nTiO2 composite material prepared in Example 1 of this invention. Detailed Implementation
[0032] The following detailed description illustrates the specific implementation method:
[0033] Example 1
[0034] A novel mesoporous quantum photocatalytic formaldehyde removal material has the general chemical formula: rGO / nTiO2-g, where rGO represents graphene oxide, nTiO2 represents nano-titanium dioxide, and g represents an adsorbent containing at least one non-metallic element from Group IIIA, Group IVA, Group VA, Group VIA, or Group VIIA. The adsorbent g contains at least one of the elements B, C, Si, N, P, As, O, or S. In this embodiment, the adsorbent g is SiO2.
[0035] A method for preparing a novel mesoporous quantum photocatalytic formaldehyde removal material includes the following steps:
[0036] S1. Preparation of titanium dioxide powder;
[0037] S1.1. Titanium dioxide was bombarded using metal ion implantation at 150 keV with V ions, resulting in an ion content of 10 × 10⁻⁶. -7 -20×10 -7 Modified titanium dioxide was obtained by applying mol / gcat. In this example, the ion content was 10 × 10⁻⁶ mol / gcat. -7 mol / gcat;
[0038] S1.2 The modified TiO2 is annealed in an oxygen atmosphere at 400-600℃ for 4-6 hours to obtain titanium dioxide powder; in this embodiment, the annealing temperature is 400℃ and the annealing time is 4 hours.
[0039] S2. Preparation of rGO / nTiO2 materials;
[0040] S2.1 The titanium dioxide powder and graphene prepared in S1 are stacked layer by layer on a nickel grid, wherein the weight ratio of graphene to titanium dioxide is 1:(0.1-1.5), and the number of layers is 4-6. In this embodiment, the mass of titanium dioxide powder is 1g, the mass of graphene is 1g, and the number of layers is 4.
[0041] S2.2 Under the protection of nitrogen, the stacked graphene and titanium dioxide are placed in a furnace, and the graphene is deformed at 800-3000℃. The deformed graphene coats the titanium dioxide to obtain mixture A. In this embodiment, the graphene is deformed at 1200℃.
[0042] S2.3. Dissolve mixture A in deionized water and ethanol, and ultrasonically disperse it for a certain time under pH 6-7 conditions. Then transfer it to an oven and dry it at 60-100℃ for 6-12 hours to obtain rGO / nTiO2 material. In this example, the mass of deionized water is 5g, the mass of ethanol is 0.5g, the ultrasonic dispersion time is 20min, the ultrasonic dispersion power is 1000w, the pH is 6, the drying temperature is 80℃, and the drying time is 8h.
[0043] S3. The rGO / nTiO2 material prepared in S2 is mixed with other substances in a certain proportion to obtain a novel mesoporous quantum photocatalytic formaldehyde removal material;
[0044] S3.1 The polyethylene glycol and the rGO / nTiO2 material prepared in S2 are compositely dispersed in deionized water to obtain mixed solution A; wherein the mass ratio of polyethylene glycol, the rGO / nTiO2 material prepared in S2, and deionized water is 1:(0.8-1.5):(10-20), and ultrasonically milled for 30-60 min at an ultrasonic milling power of 500-1000 W to obtain mixed solution A; in this embodiment, the mass of polyethylene glycol is 1 g, the mass of the rGO / nTiO2 material prepared in S2 is 1 g, and the mass of deionized water is 15 g; ultrasonically milled for 40 min at an ultrasonic milling power of 600 W;
[0045] S3.2 Add the auxiliary agent to deionized water and ultrasonically stir for 10-30 min to obtain mixed solution B. The mass ratio of the auxiliary agent to deionized water is 1:(10-20), and the ultrasonic dispersion power is 1000-2000 W. The auxiliary agent is any one or a combination of polyacrylamide, N,N-dimethyl-p-toluenediamine, cyclohexylamine, sodium dodecyl diphenyl ether disulfonate, KBE-903, OFS-6040, OFS-6032, OFD-6011, Z-6121, Z-6030, Z-6020, dispersant DK-006, and dispersant DK-045. In this embodiment, the mass of deionized water is 15 g, the mass of the auxiliary agent is 1 g, the mixing and dispersion power of the auxiliary agent and deionized water is 1000 W, the stirring time is 20 min, and the auxiliary agent is polyacrylamide.
[0046] S3.3. Mix the prepared mixed solution A and mixed solution B for 30-60 min, with a mass ratio of mixed solution A to mixed solution B of 1:(1-1.3), to obtain mixed solution C. Mix mixed solution C with adsorbent g and solvent D, and ultrasonically mill for 10-30 min to obtain a milky white transparent liquid. The ultrasonic milling power is 1000-2000 W, thus obtaining a novel mesoporous quantum photocatalytic formaldehyde removal material. Solvent D is any one of acetonitrile, pyridine, cyclohexane, cyclohexanone, ethanol, isopropanol, styrene, perchloroethylene, trichloroethylene, and acetic acid. The mass ratio of mixed solution C, adsorbent g, and solvent D is 1:(500-1000):(0.5-1). In this embodiment, the mass of mixed solution A is 17 g, the mass of mixed solution B is 16 g, and solvent D is acetonitrile; the mass of adsorbent g is 500 g, the mass of solvent D is 1 g, the ultrasonic milling power is 1000 W, and the ultrasonic milling time is 20 min.
[0047] The rGO / nTiO2 material prepared in Example 1 was observed using a scanning electron microscope, and the results are as follows: Figure 1 As shown, the microstructure of rGO-coated TiO2 was obtained.
[0048] The novel mesoporous quantum photocatalytic formaldehyde removal material was subjected to repeated degradation experiments in 4 mL of rhodamine solution (1‰), repeated 5 times. The degradation stability was found to be approximately 98%, as shown in the results. Figure 5 As shown.
[0049] The application of a novel mesoporous quantum photocatalytic formaldehyde removal material for indoor formaldehyde treatment.
[0050] Example 2
[0051] Unlike Example 1, in the preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material, in S3.1, the amount of rGO / nTiO2 material prepared in S2 is 1.5g. Experiments have shown that increasing the content of rGO / nTiO2 can promote the efficiency of photocatalytic formaldehyde removal.
[0052] Example 3
[0053] Unlike Example 1, in the preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material, in step S3.1, the amount of polyethylene glycol used is 2g, and the change in the amount of ethanol has no effect on its photocatalytic performance.
[0054] Comparative Example 1
[0055] Unlike Example 1, in the preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material, in step S1, Mg and Fe elements are used to bombard titanium dioxide at 150 keV, resulting in an ion content of 10 × 10⁻⁶. -7 Modified titanium dioxide was obtained by calcining at mol / gcat, and then annealed at 400℃ for 4 h in an oxygen atmosphere to obtain titanium dioxide powder.
[0056] The rate of rhodamine degradation by titanium dioxide powder prepared in Example 1 and Comparative Example 1 was tested, wherein the volume of rhodamine was 4 mL and the concentration was 1‰. Figure 2 It can be seen that the degradation efficiency of modified titanium dioxide containing different elements is: V>Fe>Mg.
[0057] Comparative Example 2
[0058] Unlike Example 1, the preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material does not include steps S2 and S3. In S1, V-ion-expanded graphene is used to obtain expanded graphene powder.
[0059] Comparative Example 3
[0060] Unlike Example 1, the preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material does not include steps S2 and S3, but only includes S1.
[0061] The degradation rates of rhodamine by the rGO / nTiO2 material (1 g / L) prepared in Example 1, the expanded graphene powder (1 g / L) prepared in Comparative Example 2, and the titanium dioxide powder prepared in Comparative Example 3 were tested. The volume of rhodamine was 4 mL, and its concentration was 1‰. The degradation rates were as follows: Figure 3 As shown, comparing their degradation efficiencies, it was found that the rGO-TiO2 composite material was significantly better than expanded graphene and titanium dioxide.
[0062] Comparative Example 4
[0063] Unlike Example 1, commercially available 100mL versions of competitor product 1 (Shenzhen Bohua Kangsheng Technology Co., Ltd., Bohua Kangsheng Composite Photocatalytic Formaldehyde Remover), 100mL versions of competitor product 2 (Shanghai Youben Environmental Protection Technology Co., Ltd., Honeywell No. 1 All-Effect Formaldehyde Removal Liquid), 100mL versions of competitor product 3 (Hangzhou Shupai Environmental Protection Technology Co., Ltd., Shupai Photocatalytic Formaldehyde Removal Type I), and 100mL versions of competitor product 4 (Zhejiang Bingchong Environmental Protection Technology Co., Ltd., Zhejiang University Bingchong Photocatalytic Anatase Titanium Dioxide Composite Formaldehyde Removal Agent) were used for comparison with the novel mesoporous quantum photocatalytic formaldehyde removal material prepared in Example 1, decomposing the same amount of formaldehyde. The degradation rates of rhodamine (4mL, 1‰) were compared. Figure 4As shown, the novel mesoporous quantum photocatalytic formaldehyde removal material prepared in Example 1 is significantly better than competing products 1, 2, 3, and 4.
[0064] The above descriptions are merely embodiments of the present invention, and common knowledge such as specific technical solutions and / or characteristics are not described in detail here. It should be noted that those skilled in the art can make various modifications and improvements without departing from the technical solutions of the present invention, and these should also be considered within the scope of protection of the present invention. These modifications and improvements will not affect the effectiveness of the implementation of the present invention or the practicality of the patent. The scope of protection claimed in this application should be determined by the content of its claims, and the specific embodiments described in the specification can be used to interpret the content of the claims.
Claims
1. A method for preparing a novel mesoporous quantum photocatalytic formaldehyde removal material, characterized in that: Includes the following steps: S1. Preparation of titanium dioxide powder; S2. Preparation of rGO / nTiO2 materials; S3. The rGO / nTiO2 material prepared in S2 is mixed with polyethylene glycol, additives, adsorbent g and solvent D in a certain proportion to obtain a novel mesoporous quantum photocatalytic formaldehyde removal material.
2. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 1, characterized in that: The preparation of titanium dioxide powder in S1 includes the following steps: S1.
1. Using the metal ion implantation method, high-energy metal ions are used to bombard TiO2 to obtain modified titanium dioxide that promotes absorption of visible light across the entire wavelength range. S1.2 The modified TiO2 with full-band visible light absorption is annealed in oxygen.
3. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 2, characterized in that: The preparation of rGO / nTiO2 materials in S2 includes the following steps: S2.1 The titanium dioxide powder and graphene prepared in S1 are constructed in layers, and the titanium dioxide layers and graphene are stacked on a nickel mesh. S2.2 Under the protection of nitrogen, the stacked graphene and titanium dioxide are placed in a furnace. The graphene deforms at high temperature and then coats the titanium dioxide to obtain mixture A. S2.3 Dissolve mixture A in deionized water and ethanol, ultrasonically disperse it for a certain time under pH 6-7 conditions, transfer it to an oven, dry it, and take it out to obtain rGO / nTiO2 material.
4. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 3, characterized in that: In S1.1, the metal ion is any one of V, Mg, or Fe.
5. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 4, characterized in that: In S1.1, the high-energy ion accelerator has an energy of 150 keV; the ion implantation rate is 10 × 10⁻⁶. -7 -20×10 -7 mol / gcat.
6. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 5, characterized in that: In S2.1, the weight ratio of graphene to titanium dioxide is 1:(0.1-1.5).
7. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 6, characterized in that: In step S3, the rGO / nTiO2 material prepared in step S2 is mixed with other substances in a certain proportion to obtain a novel mesoporous quantum photocatalytic formaldehyde removal material, which specifically includes the following steps: S3.
1. Polyethylene glycol and the rGO / nTiO2 material prepared in S2 are dispersed in deionized water and ultrasonically milled for a certain time to obtain mixed solution A; S3.2 Add the additive to deionized water and ultrasonically stir for a certain period of time to obtain mixed solution B; S3.
3. Mix the prepared mixed solution A with mixed solution B to obtain mixed solution C. Mix mixed solution C with adsorbent g and solvent D, and then ultrasonically mill to obtain a milky white transparent liquid, which is the novel mesoporous quantum photocatalytic formaldehyde removal material.
8. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 7, characterized in that: In S3.1, the mass ratio of polyethylene glycol, the rGO / nTiO2 material prepared in S2, and deionized water is 1:(0.8-1.5):(10-20).
9. The preparation method of a novel mesoporous quantum photocatalytic formaldehyde removal material according to claim 8, characterized in that: In S3.2, the mass ratio of the additive to deionized water is 1:(10-20).
10. The application of a novel mesoporous quantum photocatalytic formaldehyde removal material, characterized in that: It is used for the treatment of indoor formaldehyde.