Wool powder material and preparation method thereof
By loading precious metal catalysts, especially platinum nanoparticles, on wool powder and combining it with thiol and amine oxime group modifications, the problem of insufficient purification capacity of existing adsorption materials is solved, efficient adsorption and catalytic conversion of formaldehyde is achieved, and the air purification effect is improved.
Patent Information
- Application Number
- CN202510923438.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-04
- Publication Date
- 2025-09-12
AI Technical Summary
Existing adsorption materials have poor purification capabilities in air purification, and pollutants are easily released after long-term use, and cannot effectively remove formaldehyde.
Wool powder is used to load precious metal catalysts, and platinum nanoparticles are loaded to catalyze the oxidation of formaldehyde at room temperature. The adsorption performance is improved by combining thiol and amine oxime group modifications.
It achieves efficient adsorption and catalytic conversion of formaldehyde, reduces indoor formaldehyde concentration, improves air purification effect, and reduces the use of chemical products.
Smart Images
Figure CN120618441A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of air treatment, in particular to a wool powder material and a preparation method thereof. Background Art
[0002] Formaldehyde is an extremely common indoor pollutant. While colorless, it has a pungent odor, but at low concentrations, this odor is not easily noticeable. Furthermore, its release cycle is very long, lasting from three to 15 years. Long-term exposure to low concentrations of formaldehyde can cause respiratory inflammation, resulting in symptoms such as coughing and wheezing, as well as skin irritation and allergies. More seriously, formaldehyde has been designated a Class 1 carcinogen by the World Health Organization. Long-term exposure to high concentrations of formaldehyde significantly increases the risk of serious illnesses such as leukemia and nasopharyngeal cancer.
[0003] In existing technologies, indoor polluted air is often treated by using materials with adsorption capacity to absorb harmful components in the air to achieve air purification. However, the purification capacity is limited and becomes ineffective after a certain adsorption period. Furthermore, when left for a long time, the adsorbed and fixed pollutants will slowly be released into the air, resulting in poor air purification performance. In summary, the air purification performance of adsorption materials in existing technologies is poor. Summary of the Invention
[0004] The main purpose of the present invention is to provide a wool powder material and a preparation method thereof, aiming to solve the problem of poor air purification ability of adsorption materials in the prior art.
[0005] To achieve the above object, the present invention provides a wool powder material for absorbing and catalyzing formaldehyde, comprising:
[0006] Wool powder, including micronized wool;
[0007] The noble metal catalyst is loaded on the surface of the wool powder and is used for catalyzing formaldehyde.
[0008] In one embodiment, the noble metal catalyst includes platinum.
[0009] In one embodiment, the wool powder is thiol-modified wool powder.
[0010] In one embodiment, the mercapto-modified wool powder is an amidoxime-modified wool powder.
[0011] The present invention also provides a method for preparing a wool powder material, which is used to prepare any of the wool powder materials described above, comprising the following steps:
[0012] Adjust the pH value of the aqueous solution to less than 4.2;
[0013] Add wool powder and chloroplatinic acid solution into water to allow chloroplatinate ions to adsorb onto the wool surface;
[0014] Sodium borohydride is added to water to reduce the platinum ligands into platinum nanoparticles, thereby obtaining platinum-loaded wool powder.
[0015] In one embodiment, before the step of adding wool and chloroplatinic acid solution to water, the method further comprises:
[0016] crushing wool fibers into wool powder;
[0017] Adding the wool powder to the L-cysteine solution and stirring;
[0018] The wool powder is centrifuged and washed to obtain thiol-modified wool powder.
[0019] In one embodiment, after the step of centrifugally washing the wool powder to obtain the thiol-modified wool powder, the method further comprises:
[0020] Adding tris(2-carbonylethyl)phosphine hydrochloride to the first prepared solution of ethanol and water;
[0021] adding the thiol-modified wool powder to the first configuration solution;
[0022] Prepare a sodium carbonate and sodium bicarbonate buffer solution, add the buffer solution to the mixed solution, and adjust the pH value to 7;
[0023] Add acrylonitrile and treat the reaction under nitrogen;
[0024] The wool powder after the reaction was washed by centrifugation with ethanol and water;
[0025] Dissolve hydroxylamine hydrochloride and sodium hydroxide in a second solution of methanol and water;
[0026] Add the washed wool powder to the second solution and heat and stir;
[0027] After the reaction is completed, the wool powder is washed with a third solution of methanol and water to obtain wool powder modified with amidoxime groups.
[0028] The present invention provides a wool powder material, comprising wool powder and a noble metal catalyst loaded on the surface of the wool micropowder. The wool powder has good gas removal performance, a large specific surface area and more active sites, a better adsorption effect on formaldehyde, can provide a larger gas contact area, and is more conducive to the occurrence of the reaction. The wool textile preparation can make waste textiles into green and ecological high-value-added products. At the same time, micropowders are prepared by wool fibers, and noble metals are loaded on the wool micropowders to prepare a formaldehyde catalyst with catalytic oxidation performance at room temperature. Chemical attraction is formed by the opposite charges carried by the wool surface and the platinum precursor itself, and a strong bond can be formed, thereby reducing the use of chemical products. After the wool fibers are prepared into powder, more active sites are exposed, which can have a better adsorption and fixation effect on formaldehyde. The formaldehyde can be directly converted into a non-toxic product at room temperature through the catalysis of the noble metal platinum, thereby achieving adsorption and catalytic conversion of formaldehyde and facilitating the purification of indoor air. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 This is an elemental analysis diagram of the surface of the wool powder material catalyst provided by the embodiment of the present invention;
[0030] Figure 2 is the XRD pattern of the wool powder material;
[0031] Figure 3 This is an infrared image of a wool-modified sample of the wool powder material;
[0032] Figure 4 This is a graph showing changes in formaldehyde concentration when the wool powder material is applied;
[0033] Figure 5 This is a graph showing changes in carbon dioxide concentration when the wool powder material acts.
[0034] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION
[0035] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.
[0036] It should be noted that if the embodiments of the present invention involve directional indications (such as up, down, left, right, front, back, etc.), the directional indications are only used to explain the relative position relationship, movement status, etc. between the various components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indications will also change accordingly.
[0037] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of such features. In addition, the meaning of "and / or" appearing throughout the text includes three parallel schemes. Taking "A and / or B" as an example, it includes scheme A, or scheme B, or a scheme in which A and B are satisfied at the same time. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.
[0038] The present invention provides a wool powder material for absorbing and catalyzing formaldehyde, comprising wool powder and a noble metal catalyst; the wool powder comprises wool micropowder; the noble metal catalyst is loaded on the surface of the wool micropowder to catalyze formaldehyde.
[0039] The present invention provides a wool powder material, comprising wool powder and a noble metal catalyst loaded on the surface of the wool micropowder. The wool powder has good gas removal performance, a large specific surface area and more active sites, has a better adsorption effect on formaldehyde, can provide a larger gas contact area, and is more conducive to the occurrence of the reaction. The wool textile preparation method can make waste textiles into green and ecological high-value-added products. At the same time, micropowders are prepared by wool fibers, and noble metals are loaded on the wool micropowders to prepare a formaldehyde catalyst with catalytic oxidation performance at room temperature. Chemical attraction is formed by the opposite charges carried by the wool surface and the platinum precursor itself, and a strong bond can be formed, thereby reducing the use of chemical products. After the wool fibers are prepared into powder, more active sites are exposed, which can have a better adsorption and fixation effect on formaldehyde. The formaldehyde can be directly converted into a non-toxic product at room temperature through the catalysis of the noble metal platinum, thereby achieving adsorption and catalytic conversion of formaldehyde and facilitating purification of indoor air.
[0040] See also Figure 1 The surface of the catalyst contains basic elements that make up proteins, such as C, H, O, N, S, as well as the precious metal Pt with catalytic properties.
[0041] It should be noted that common formaldehyde catalysts are precious metals, such as platinum and palladium, and non-precious metal oxides, such as manganese dioxide and cobalt oxide. Precious metals have high catalytic activity and high cost. Non-precious metal catalysts have problems such as insufficient activity or easy poisoning. For example, they are easily affected by other gas impurities, resulting in a decrease in catalytic effect. At room temperature, due to the slow gas movement speed and slow reaction kinetics, the required activation energy is high, so a highly active catalyst is required to proceed at low temperatures. The oxide activity of non-precious metal catalysts is low, so it is necessary to optimize the non-metallic catalyst structure or dope other elements to increase the activity and reduce the catalyst energy barrier. However, precious metal catalysts can solve this problem very well.
[0042] In this embodiment, the noble metal catalyst includes platinum.
[0043] Furthermore, the wool powder includes mercapto-modified wool powder. Mercapto groups have a good adsorption effect on precious metals.
[0044] Furthermore, the thiol-modified wool powder includes wool powder modified with amidoxime groups. Using a catalyst prepared by direct adsorption of platinum ions onto wool and subsequent reduction, the formaldehyde concentration in the sample chamber was reduced by approximately 20%. Adding thiol groups reduced the formaldehyde concentration by 42%. Grafting amidoxime groups further reduced the formaldehyde concentration compared to the catalyst with thiol groups.
[0045] See also Figure 2 The diffraction peaks at 9° and 19° correspond to the wool β-pleated structure. The diffraction peak at 19° is significantly enhanced after the disulfide bond is cleaved to generate thiol groups and the amidoxime groups are grafted. Furthermore, the peaks observed at 38.5° and 42.1° correspond to the 111 and 200 facets of the face-centered cubic structure, respectively, demonstrating successful platinum loading.
[0046] Based on the above-mentioned wool powder material, the present invention provides a method for preparing the wool powder material, comprising the following steps:
[0047] S10, adjusting the pH value of the aqueous solution to 4;
[0048] S20, adding wool powder and chloroplatinic acid solution to water to allow chloroplatinic acid ions to adsorb onto the wool surface;
[0049] S30. Sodium borohydride is added to water to reduce the platinum ligand into platinum nanoparticles to obtain platinum-loaded wool powder.
[0050] At pH 4.2-4.8, wool's amino groups carry a positive charge, while its carboxyl groups carry a negative charge. When the pH is below 4.2, the amino groups carry a positive charge, making the wool positively charged. At pH above 4.8, the carboxyl groups carry a negative charge, making the wool negatively charged. First, the pH is adjusted to 4. Then, wool and a chloroplatinic acid solution are added to water. Electrostatic attraction creates an attraction between the wool and the chloroplatinic acid ions, causing them to adsorb to the wool surface. Subsequently, the platinum ligands are further reduced to platinum nanoparticles using sodium borohydride to produce a platinum-loaded powder catalyst that catalyzes the oxidation of formaldehyde at room temperature.
[0051] Furthermore, before step S20, the following steps are also included:
[0052] S01, crushing wool fibers into wool powder;
[0053] S02, adding the wool powder to the L-cysteine solution and stirring;
[0054] S03. Centrifugally washing the wool powder to obtain thiol-modified wool powder.
[0055] See also Figure 3 After wool fibers are crushed into powder, the surface scale layer has long been destroyed, exposing more functional groups such as carboxyl and amine groups within the wool. Because thiol groups have a good adsorption effect on precious metals, thiol functional groups can be prepared through disulfide bonds between wool molecules. To release free thiol groups on wool, 0.5g of wool powder was added to 25mL of 24g / L L-cysteine solution. After stirring at 70°C for 2h, the wool powder was centrifuged and washed to obtain thiol-modified wool powder.
[0056] Furthermore, after step S03, the following steps are further included:
[0057] S04, adding tris(2-carbonylethyl)phosphine hydrochloride to the first solution prepared by ethanol and water;
[0058] S05, adding the thiol-modified wool powder to the first prepared solution;
[0059] S06, preparing a sodium carbonate and sodium bicarbonate buffer solution, adding the buffer solution to the mixed solution, and adjusting the pH value to 7;
[0060] S07, adding acrylonitrile and treating the reaction under nitrogen;
[0061] S08, washing the wool powder after the reaction by centrifugation with ethanol and water;
[0062] S09, dissolving hydroxylamine hydrochloride and sodium hydroxide in a second solution of methanol and water;
[0063] S010, adding the washed wool powder to the second prepared solution and heating with stirring;
[0064] S011. After the reaction is completed, the wool powder is washed with a third solution of methanol and water to obtain wool powder modified with amidoxime groups.
[0065] Preparation of amidoxime-modified wool powder: 0.1 g of tris(2-carbonylethyl)phosphine hydrochloride was added to 25 mL of a 1:1 solution of ethanol and water. 0.5 g of the thiol-modified wool powder prepared by the above method was added to the solution. A 0.1 mol / L sodium carbonate and sodium bicarbonate buffer solution was prepared, pH = 10.8, and added to the mixture to adjust the pH to 7. 0.12 mL of acrylonitrile was added and the mixture was treated at 40°C under nitrogen for 24 hours. The reacted wool powder was washed by centrifugation with a 1:1 solution of ethanol and water. 0.7 g of hydroxylamine hydrochloride and 0.35 g of sodium hydroxide were dissolved in 25 mL of a 1:1 solution of methanol and water. After adding the wool powder, the solution was heated to 70°C and stirred for 2 hours. After the reaction, the amidoxime-grafted wool sample was thoroughly washed with a 4:1 solution of methanol and water.
[0066] See also Figure 4 The catalyst prepared by directly adsorbing platinum ions on wool and then reducing it was used to catalyze formaldehyde. The formaldehyde concentration in the sample room was reduced by about 20%. After adding thiol groups, the formaldehyde concentration could be reduced by 42%. After grafting amine oxime groups, the formaldehyde concentration was further reduced compared to the catalyst with added thiol groups.
[0067] See also Figure 5 The concentration of carbon dioxide increases synchronously with the decrease of formaldehyde concentration, indicating that the method of adsorbing ions and then reducing them is more suitable for preparing platinum-loaded catalysts. At the same time, increasing the thiol, amino and hydroxyl groups can promote the adsorption of formaldehyde.
[0068] The above are only preferred embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention description and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.
Claims
1. A wool powder material for absorbing and catalyzing formaldehyde, characterized in that: include: Wool powder, including micronized wool; The noble metal catalyst is loaded on the surface of the wool powder and is used for catalyzing formaldehyde.
2. The wool powder material according to claim 1, characterized in that: The noble metal catalyst includes platinum.
3. The wool powder material according to claim 1, characterized in that: The wool powder includes mercapto-modified wool powder.
4. The wool powder material according to claim 3, characterized in that: The mercapto-modified wool powder also includes wool powder modified with amidoxime groups.
5. A method for preparing a wool powder material, for preparing the wool powder material according to any one of claims 1 to 4, characterized in that: The following steps are involved: Adjust the pH value of the aqueous solution to less than 4.2; Add wool powder and chloroplatinic acid solution into water to allow chloroplatinate ions to adsorb onto the wool surface; Sodium borohydride is added to water to reduce the platinum ligands into platinum nanoparticles, thereby obtaining platinum-loaded wool powder.
6. The method for preparing the wool powder material according to claim 5, characterized in that: Before the step of adding wool and chloroplatinic acid solution into water, the method further comprises: crushing wool fibers into wool powder; Adding the wool powder to the L-cysteine solution and stirring; The wool powder is centrifuged and washed to obtain thiol-modified wool powder.
7. The method for preparing the wool powder material according to claim 6, characterized in that: After the step of centrifugally washing the wool powder to obtain the thiol-modified wool powder, the method further comprises: Adding tris(2-carbonylethyl)phosphine hydrochloride to the first prepared solution of ethanol and water; adding the thiol-modified wool powder to the first configuration solution; Prepare a sodium carbonate and sodium bicarbonate buffer solution, add the buffer solution to the mixed solution, and adjust the pH value to 7; Add acrylonitrile and treat the reaction under nitrogen; The wool powder after the reaction was washed by centrifugation with ethanol and water; Dissolve hydroxylamine hydrochloride and sodium hydroxide in a second solution of methanol and water; Add the washed wool powder to the second solution and heat and stir; After the reaction is completed, the wool powder is washed with a third solution of methanol and water to obtain wool powder modified with amidoxime groups.