CN112121791B - Photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters, and preparation method and application thereof - Google Patents
Photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters, and preparation method and application thereof Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 34
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 5
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- 239000000243 solution Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 cleaners Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 231100000378 teratogenic Toxicity 0.000 description 1
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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Abstract
The invention provides a photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atom clusters, which is prepared by mixing chloroplatinic acid into P25 titanium dioxide aqueous solution, adopting sodium borohydride to perform in-situ reduction to generate platinum atom clusters under the action of polyvinylpyrrolidone protective agent, washing with water and drying. The preparation method increases the specific surface area of the catalyst activity by preparing the platinum atomic clusters, improves the catalytic activity and stability of the catalyst, has the characteristics of simple preparation method, no need of high-temperature calcination, less platinum consumption, low cost and the like, and can obviously improve the indoor formaldehyde removal rate. The invention adopts a simple one-step in-situ reduction deposition preparation technology, the preparation method is simple, the improvement space is large, and the formaldehyde removal rate of the prepared titanium dioxide/platinum atomic cluster catalyst is still more than 98% after the catalyst is continuously used for 180 days.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters, and a preparation method and application thereof.
Background
Various chemical agents such as indoor building materials, finishing materials, decorative materials, cleaners, pesticides, disinfectants, etc. are filled in the aspects of life, which generates organic matters mainly comprising formaldehyde. Formaldehyde is colorless and transparent gas, has pungent smell, and has serious harm to eyes, nose, throat, lung, liver, immune system and the like. Formaldehyde is highly toxic and has been identified by the world health organization as a highly carcinogenic and teratogenic substance. Therefore, the removal of formaldehyde in indoor or enclosed environments is a long-felt need for a solution in the future.
The photocatalytic degradation technology is a new technology which is rapidly developed in recent years and can directly utilize solar energy to perform environmental purification. The technology uses photocatalysis principle and uses nano semiconductor TiO 2 The material is a catalyst, and ultraviolet rays are utilized to excite the catalyst, so that organic pollutants adsorbed on the surface of the catalyst are degraded into carbon dioxide, water and inorganic substances. The formaldehyde and other pollutants are fundamentally eliminated by photolysis, so that the method is the most effective method for eliminating indoor pollutants. Meanwhile, ultraviolet light can kill harmful bacteria and viruses in indoor air while exciting the catalyst. Noble metals are the most active class of catalytic formaldehyde-degrading materials, such as Pt, pd, ag, au, and are typically supported on inert oxides such as porous alumina, silica, titania, and the like. Noble metal catalysts tend to fully oxidize formaldehyde gas to CO at room temperature 2 And H 2 O. The composite material catalyst prepared by compounding nano titanium dioxide and nano platinum has the advantages of rapid and efficient reaction, no secondary pollution and the like compared with other indoor formaldehyde removal technologies. Compared with a platinum nano material catalyst, the platinum single-atom catalyst has the advantages of large specific surface area, high catalytic activity and the like, but has poor stability in air atmosphere; the platinum monoatomic cluster has the advantages of high specific surface area, high catalytic activity and good stability of the platinum nanomaterial, and has wide development prospect and application market in the formaldehyde removal field.
Disclosure of Invention
The invention aims to provide a photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters, and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention is realized by adopting the following technical scheme:
the invention provides a preparation method of a photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters, which comprises the following steps:
(1) Preparing an aqueous solution of chloroplatinic acid, an aqueous solution of titanium dioxide and an aqueous solution of polyvinylpyrrolidone;
(2) Mixing the chloroplatinic acid aqueous solution, the titanium dioxide aqueous solution and the polyvinylpyrrolidone aqueous solution in the step (1) under stirring, and performing ultrasonic dispersion to obtain a mixed solution;
(3) Dropwise adding the sodium borohydride aqueous solution into the mixed solution in the step (2) under continuous stirring;
(4) Continuously stirring, and then standing for sedimentation to obtain sediment;
(5) Filtering the sediment in the step (4), and cleaning the sediment with deionized water to obtain a filtered substance;
(6) And (5) drying the filter material obtained in the step (5) to obtain the photocatalyst formaldehyde removal catalyst.
Further, the concentration of the chloroplatinic acid aqueous solution in the step (1) is 0.2 mmol/L-1 mmol/L.
Further, the titanium dioxide in the step (1) is P25 nanometer titanium dioxide powder.
Further, the concentration of the titanium dioxide aqueous solution in the step (1) is 5 mg/L-10 mg/L.
Further, the concentration of the polyvinylpyrrolidone aqueous solution in the step (1) is 5 mg-15 mg/mL.
Further, the concentration of the sodium borohydride aqueous solution in the step (3) is 0.05mol/L to 0.1mol/L.
Further, the stirring time in the step (4) is 1-3 hours, and then the standing sedimentation time is 0.5-2 hours.
The photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters is prepared by the preparation method.
Furthermore, the formaldehyde removal rate of the photocatalyst based on the titanium dioxide/platinum atomic clusters is 99% under standard sunlight, the formaldehyde removal rate in a dark environment is more than 75%, and the formaldehyde removal rate is still more than 98% after the photocatalyst is continuously used for 180 days.
The invention also provides application of the titanium dioxide/platinum atom cluster photocatalyst catalyst in formaldehyde removing agents for home, automobiles, air conditioners, fans, coatings and adhesives.
Further, the concentration of the aqueous solution of chloroplatinic acid was 0.5mmol/L, the solubility of the aqueous solution of titanium dioxide was 8mg/L, and the concentration of the aqueous solution of polyvinylpyrrolidone was 10mg/mL.
Further, the temperature of the deionized water in the step (5) is 70-90 ℃.
Further, the drying method in the step (6) is to dry in the air at 80-85 ℃.
Compared with the prior art, the invention has the advantages and technical effects that:
1. the invention fully utilizes the unique photoelectric characteristic of titanium dioxide and the high catalytic activity of platinum atom clusters, and prepares the titanium dioxide/platinum atom cluster catalyst by a simple in-situ reduction deposition technology. The platinum atom clusters are introduced through the accurate regulation and control of the preparation conditions, so that the activity of the catalyst under irrelevant conditions is improved, and the consumption of noble metal platinum is reduced; the use of nano titanium dioxide improves the concentration of photo-generated carriers of the catalyst in the illumination environment and further improves the catalytic performance of formaldehyde. Under the standard sunlight, the formaldehyde removal rate of the titanium dioxide/platinum atomic cluster catalyst is 99 percent, and the formaldehyde removal rate in a dark environment is more than 75 percent.
2. The formaldehyde-removing catalyst prepared by the invention takes platinum atom clusters as active substances, avoids the use of a large amount of noble metal platinum, and reduces the production cost. In addition, the invention adopts a simple one-step in-situ reduction deposition preparation technology, the preparation method is simple, and the improvement space is larger. The formaldehyde removal rate of the prepared titanium dioxide/platinum atom cluster catalyst is still maintained to be more than 98% after 180 days of continuous use.
3. Compared with the conventional platinum nano material, the platinum atomic cluster adopted by the invention has the characteristics of good stability, and also has higher specific surface area and catalytic activity, and is important for improving the formaldehyde removal rate and the service life of the catalyst.
Drawings
FIG. 1 shows formaldehyde removal rates of the titanium dioxide/platinum cluster catalysts prepared according to the present invention at different temperatures and different humidities.
FIG. 2 is a graph showing formaldehyde removal and carbon dioxide production of the titanium dioxide/platinum cluster catalyst prepared in accordance with the present invention.
FIG. 3 is a graph showing the stability of titanium dioxide/platinum cluster catalysts prepared in accordance with the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments.
Example 1
The preparation method of the photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters comprises the following steps:
1. preparing an aqueous solution of chloroplatinic acid with the concentration of 0.5mmol/L, preparing an aqueous solution of P25 titanium dioxide with the solubility of 8mg/L, and preparing an aqueous solution of polyvinylpyrrolidone with the concentration of 10 mg/mL;
2. mixing the chloroplatinic acid aqueous solution, the P25 titanium dioxide aqueous solution and the polyvinylpyrrolidone aqueous solution in the step 1 under magnetic stirring, and performing ultrasonic dispersion;
3. dropwise adding 2mL of sodium borohydride aqueous solution with the concentration of 0.08mol/L into the mixed solution in the step 2 under continuous stirring;
4. continuously stirring the reaction solution in the step 3 for 2 hours, and standing for sedimentation for 1 hour to obtain sediment;
5. filtering the sediment in the step 4, and cleaning the sediment by hot deionized water with the temperature of 80 ℃ to remove chloride ions, thereby obtaining a filtered substance;
6. and 5, drying the filter material obtained in the step 5 in the air with the temperature of 80 ℃ to obtain the photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters.
Through the method, as shown in fig. 1-3, the titanium dioxide/platinum atom cluster formaldehyde-removing catalyst with the formaldehyde removal rate of 99% under standard sunlight, the formaldehyde removal rate of more than 75% in dark environment and the formaldehyde removal rate of more than 98% after continuous use for 180 days is obtained. The photocatalyst formaldehyde-removing catalyst based on titanium dioxide/platinum atomic clusters can be applied to household formaldehyde-removing agents, automobiles, air conditioners, fans, coatings, binders and the like.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (5)
1. The preparation method of the photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters is characterized by comprising the following steps:
(1) Preparing an aqueous solution of chloroplatinic acid, an aqueous solution of titanium dioxide and an aqueous solution of polyvinylpyrrolidone; the titanium dioxide is P25 nano titanium dioxide powder, and the concentration of the titanium dioxide aqueous solution is 5 mg/L-10 mg/L; the concentration of the polyvinylpyrrolidone aqueous solution is 5 mg-15 mg/mL;
(2) Mixing the chloroplatinic acid aqueous solution, the titanium dioxide aqueous solution and the polyvinylpyrrolidone aqueous solution in the step (1) under stirring, and performing ultrasonic dispersion to obtain a mixed solution;
(3) Dropwise adding the sodium borohydride aqueous solution into the mixed solution in the step (2) under continuous stirring; the concentration of the sodium borohydride aqueous solution is 0.05 mol/L-0.1 mol/L;
(4) Continuously stirring, and then standing for sedimentation to obtain sediment;
(5) Filtering the sediment in the step (4), and cleaning the sediment with deionized water to obtain a filtered substance;
(6) And (5) drying the filter material obtained in the step (5) to obtain the photocatalyst formaldehyde removal catalyst.
2. The method for preparing the photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters according to claim 1, which is characterized in that: the concentration of the chloroplatinic acid aqueous solution in the step (1) is 0.2 mmol/L-1 mmol/L.
3. The method for preparing the photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters according to claim 1, which is characterized in that: and (3) stirring time in the step (4) is 1-3 hours, and then standing and settling time is 0.5-2 hours.
4. The photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters prepared by the preparation method of any one of claims 1 to 3, which is characterized in that: the photocatalyst based on the titanium dioxide/platinum atomic clusters has the formaldehyde removal rate of 99% under standard sunlight, the formaldehyde removal rate in dark environment is more than 75%, and the formaldehyde removal rate is still more than 98% after the photocatalyst is continuously used for 180 days.
5. The use of the titanium dioxide/platinum atom cluster photocatalyst according to claim 4 in formaldehyde scavengers for homes, automobiles, air conditioners, fans, paints, adhesives.
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| CN114768519A (en) * | 2021-05-07 | 2022-07-22 | 浙江施维康生物医学材料有限公司 | Long-acting environment-friendly formaldehyde removing agent and preparation method thereof |
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