CN113893884A - Efficient and environment-friendly visible light photocatalyst and preparation method and application thereof - Google Patents
Efficient and environment-friendly visible light photocatalyst and preparation method and application thereof Download PDFInfo
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- CN113893884A CN113893884A CN202111248121.4A CN202111248121A CN113893884A CN 113893884 A CN113893884 A CN 113893884A CN 202111248121 A CN202111248121 A CN 202111248121A CN 113893884 A CN113893884 A CN 113893884A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 45
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- 239000000463 material Substances 0.000 claims abstract description 30
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005751 Copper oxide Substances 0.000 claims abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001782 photodegradation Methods 0.000 claims abstract description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
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- 238000000498 ball milling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003658 microfiber Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000031700 light absorption Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
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- 238000010276 construction Methods 0.000 abstract 1
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- 230000006870 function Effects 0.000 description 6
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- 238000006731 degradation reaction Methods 0.000 description 3
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- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 3
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- 241000233866 Fungi Species 0.000 description 1
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- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
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- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 206010039083 rhinitis Diseases 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 238000002798 spectrophotometry method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention belongs to the technical field of visible light photocatalysts, and particularly relates to a high-efficiency environment-friendly visible light photocatalyst as well as a preparation method and application thereof. The catalyst is a heterojunction colloidal solution, the heterojunction colloidal solution comprises titanium dioxide and an auxiliary metal oxide, and the auxiliary metal oxide is one or two of zinc oxide, copper oxide, manganese oxide, ferric oxide and bismuth oxide. The preparation method comprises the steps of heterojunction material preparation and heterojunction colloid solution preparation. The catalyst is applied to photodegradation of formaldehyde molecules. The technical scheme provided by the invention prepares the heterojunction material by compounding various metal oxides, and has the advantages of cheap and environment-friendly raw materials, wide visible light absorption range, high light absorption efficiency, simple preparation, easy production, convenient storage and construction and the like.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a high-efficiency environment-friendly visible light photocatalyst, and a preparation method and application thereof.
Background
Formaldehyde is a colorless, pungent and volatile gas with pungent odor. Is also a common chemical raw material in adhesives and materials, and is applied to the manufacture of indoor materials, automobile interior material adhesives, coatings and fibers. Formaldehyde was identified as a suspected carcinogen by the national institute for occupational safety and health in 1981, was identified as a suspected carcinogen by the international agency for cancer (IARC) in 1995, and was identified as a carcinogen by the WHO in 2004, WHO was able to increase the probability of developing leukemia in humans, particularly infants and the elderly. If the patient stays in an environment with excessive formaldehyde for a long time, the immunity of the patient is naturally reduced, the memory, the sensitivity, the balance function and the coordination function of the patient who contacts the formaldehyde for a long time are reduced to different degrees, and the rhinitis detectable rate is increased.
The prior formaldehyde treating agent mostly adopts a photocatalysis material. The visible light photocatalyst is a generic name of a photo-semiconductor material with a photocatalytic function represented by nano-scale titanium dioxide, which generates free hydroxyl and active oxygen with extremely strong oxidizing power under the action of ultraviolet light and visible light, has a very strong photo-oxidation-reduction function, generates a strong catalytic degradation function, can oxidize and decompose various organic compounds and partial inorganic substances, effectively degrades toxic and harmful gases in the air, kills various bacteria, and can decompose and harmlessly treat toxins released by bacteria or fungi. Meanwhile, the composite material also has the functions of removing formaldehyde, deodorizing, resisting pollution, purifying air and the like. Has important application value in the fields of medical equipment, water and soil treatment, air purification and the like.
The first generation visible light photocatalyst mainly performs crystal growth on titanium dioxide at medium and high temperature, controls the grain size, and prepares a titanium dioxide nano material with anatase phase and rutile phase structures; the second generation visible light photocatalyst framework is formed by doping titanium dioxide with noble metals such as Pt/Ag/Au to improve the photocatalytic property and efficiency. However, both methods cannot compromise the photocatalytic efficiency and cost. Although the second generation visible light photocatalyst technology has obviously improved photocatalytic degradation efficiency compared with the first generation visible light photocatalyst, the second generation visible light photocatalyst technology is complex in preparation process and correspondingly high in cost, and is not suitable for common families and large-scale planning and popularization.
Therefore, the development of the visible light photocatalyst with high degradation efficiency and low application cost has extremely important significance for improving the air quality, solving the indoor pollution, improving the life quality and improving the living environment.
Disclosure of Invention
The invention provides a high-efficiency environment-friendly visible light photocatalyst, and a preparation method and application thereof, which are used for solving the problems of complex preparation process and high cost of the existing visible light photocatalyst.
In order to solve the technical problems, the technical scheme of the invention is as follows: the efficient and environment-friendly visible light photocatalyst is a heterojunction colloidal solution, the heterojunction colloidal solution comprises titanium dioxide and an auxiliary metal oxide, and the auxiliary metal oxide is one or two of zinc oxide, copper oxide, manganese oxide, ferric oxide and bismuth trioxide.
Optionally, the auxiliary metal oxide is zinc oxide and manganese oxide.
A heterogeneous structure is formed by utilizing a multi-molecular compound, and the forbidden bandwidth of a single oxide is reduced, so that the catalytic action of photocatalysis in a visible light range is improved.
Optionally, the efficient and environment-friendly visible light photocatalyst further comprises a surfactant, a dispersant and deionized water.
The invention also provides a preparation method of the efficient and environment-friendly visible light photocatalyst, which comprises the following steps: .
S1, heterojunction material preparation: adding titanium dioxide, auxiliary metal oxide, a first surfactant and a first dispersing agent into deionized water, carrying out ball milling for 5-12h, filtering, drying and roasting to obtain a heterojunction material;
s2 preparation of the heterojunction colloidal solution: and mixing the heterojunction material prepared in the S1, a second surfactant, a second dispersing agent and deionized water, then carrying out ultrasonic oscillation for 0.3-1h, heating and stirring for 1-5h to prepare a heterojunction colloidal solution, namely the efficient and environment-friendly visible light photocatalyst.
Optionally, the first surfactant or the second surfactant is selected from one or more of ethylene glycol, propylene glycol, sodium dodecyl benzene sulfonate and sodium hexadecylbenzene sulfonate.
Optionally, the first surfactant is ethylene glycol and the second surfactant is sodium hexadecylbenzene sulfonate.
Optionally, the first dispersant or the second dispersant is one or more selected from polyethylene glycol, polypropylene glycol, sodium lignosulfonate and natural fiber microfiber.
Optionally, the first dispersant is polyethylene glycol and sodium lignosulfonate, and the second dispersant is natural fiber microfiber.
Optionally, in the S1, the components are as follows in parts by weight:
optionally, in the S2, the components are as follows in parts by weight:
optionally, in the step S1, the ball milling rotation speed in the ball milling process is 300 to 600 r/min.
Optionally, in the S1, the roasting temperature is 300-500 ℃, and the roasting time is 2-10 h.
Optionally, in the step S2, the heating and stirring temperature is 50-80 ℃.
The invention also provides application of the efficient and environment-friendly visible light photocatalyst in photodegradation of formaldehyde molecules.
The technical scheme provided by the invention prepares the heterojunction material by compounding a plurality of metal oxides, and compared with the prior art, the heterojunction material has the following advantages:
(1) the used raw materials are low in price, green and environment-friendly, are suitable for being used in closed spaces in a room and an automobile, and cannot bring harm to human bodies and secondary pollution to the environment;
(2) the formaldehyde slow-release agent has the characteristics of wide visible light absorption range and high light absorption efficiency, is beneficial to being used in indoor and automobile visible light irradiation environments, has good durability, and has continuous degradation efficiency on slow-release formaldehyde molecules;
(3) the preparation method has the advantages of simple preparation process and easy industrial production, and the prepared colloidal solution is easy to store and construct and has excellent photodegradability on formaldehyde.
Detailed Description
For the convenience of understanding, the following examples are provided to illustrate the efficient and environmentally friendly visible light photocatalyst, and the preparation method and application thereof, and it should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
In the specific embodiment, the raw materials and reagents are all commercial products except special instructions, and the used equipment or process is common technology except special instructions.
Example 1
S1, sequentially adding 200g of titanium dioxide, 200g of zinc dioxide, 2g of ethylene glycol, 5g of polyethylene glycol and 5g of sodium lignosulfonate into 588g of deionized water, performing ball milling treatment at normal temperature at the rotating speed of 450r/h for 8h to prepare a heterojunction precursor material, filtering and drying the heterojunction precursor material, and roasting at 400 ℃ for 5h to prepare the heterojunction material;
s2 adding 20g of heterojunction material, 2g of sodium hexadecylbenzene sulfonate and 2g of natural fiber microfiber into 456g of deionized water, carrying out ultrasonic oscillation for 0.5h, and then heating and stirring at 60 ℃ for 2h to prepare a well-dispersed heterojunction colloidal solution, namely the high-efficiency environment-friendly visible light photocatalyst.
Example 2:
s1, sequentially adding 200g of titanium dioxide, 200g of copper oxide, 3g of ethylene glycol, 5g of polyethylene glycol and 3g of sodium lignin sulfonate into 584g of deionized water, performing ball milling treatment at the normal temperature and the rotation speed of 450r/h for 8h to obtain a heterojunction precursor material, filtering and drying the heterojunction precursor material, and roasting at the temperature of 400 ℃ for 5h to obtain the heterojunction material;
s2 adding 20g of heterojunction material, 2g of sodium hexadecylbenzene sulfonate and 2g of natural fiber microfiber into 456g of deionized water, carrying out ultrasonic oscillation for 0.5h, and then heating and stirring at 60 ℃ for 2h to prepare a well-dispersed heterojunction colloidal solution, namely the high-efficiency environment-friendly visible light photocatalyst.
Example 3:
s1, sequentially adding 200g of titanium dioxide, 100g of zinc dioxide, 100g of manganese oxide, 2g of ethylene glycol, 5g of polyethylene glycol and 5g of sodium lignosulfonate into 588g of deionized water, performing ball milling treatment for 8 hours at normal temperature and at the rotating speed of 450r/h to obtain a heterojunction precursor material, filtering and drying the heterojunction precursor material, and roasting at 400 ℃ for 5 hours to obtain the heterojunction material;
s2 adding 20g of heterojunction material, 2g of sodium hexadecylbenzene sulfonate and 2g of natural fiber microfiber into 456g of deionized water, carrying out ultrasonic oscillation for 0.5h, and then heating and stirring at 60 ℃ for 2h to prepare a well-dispersed heterojunction colloidal solution, namely the high-efficiency environment-friendly visible light photocatalyst.
Comparison example:
on the basis of example 1, 200g of titanium dioxide and 200g of zinc dioxide are replaced by 400g of titanium dioxide, and other preparation components and processes are unchanged.
Comparative test
100g of each of the products of the above examples and comparative examples was sprayed into a 20-cubic-meter sealed room, and the initial concentration of formaldehyde in the sealed room was 50mg/m3The indoor formaldehyde concentration is periodically detected by using a common fluorescent lamp and sunlight irradiation and a spectrophotometry detector.
TABLE 1 Table of measured data of examples and comparative examples
| Observation time | 2h | 8h | 24h | 48h |
| Example 1 | 62.0％ | 85.3％ | 95.8％ | 98.7％ |
| Example 2 | 56.7％ | 79.5％ | 90.6％ | 96.2％ |
| Example 3 | 65.4％ | 89.1％ | 97.8％ | 99.0％ |
| Comparative example | 25.1％ | 40.4％ | 57.2％ | 62.8％ |
As can be seen from the above table, the visible light photocatalyst of the present application has a better formaldehyde removal effect, and particularly, the treatment effect of the heterojunction material prepared by using three metal oxides in example 3 is significantly better than that of other heterojunction materials. And the formaldehyde removal effect of the photocatalytic material prepared by using only titanium dioxide as a comparative example is relatively poor.
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and such modifications or replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The efficient and environment-friendly visible light photocatalyst is characterized by being a heterojunction colloidal solution, wherein the heterojunction colloidal solution comprises titanium dioxide and an auxiliary metal oxide, and the auxiliary metal oxide is one or two of zinc oxide, copper oxide, manganese oxide, ferric oxide and bismuth oxide.
2. The efficient and environmentally friendly visible light photocatalyst as claimed in claim 1, wherein the auxiliary metal oxide is zinc oxide and manganese oxide.
3. The preparation method of the high-efficiency environment-friendly visible light photocatalyst as claimed in claim 1 or 2, characterized by comprising the following steps: .
S1, heterojunction material preparation: adding titanium dioxide, auxiliary metal oxide, a first surfactant and a first dispersing agent into deionized water, carrying out ball milling for 5-12h, filtering, drying and roasting to obtain a heterojunction material;
s2 preparation of the heterojunction colloidal solution: and mixing the heterojunction material prepared in the S1, a second surfactant, a second dispersing agent and deionized water, then carrying out ultrasonic oscillation for 0.3-1h, heating and stirring for 1-5h to prepare a heterojunction colloidal solution, namely the efficient and environment-friendly visible light photocatalyst.
4. The method according to claim 3, wherein the first surfactant or the second surfactant is one or more selected from the group consisting of ethylene glycol, propylene glycol, sodium dodecylbenzenesulfonate and sodium hexadecylbenzenesulfonate.
5. The method of claim 4, wherein the first surfactant is ethylene glycol and the second surfactant is sodium hexadecylbenzene sulfonate.
6. The method according to claim 3, wherein the first dispersant or the second dispersant is one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, sodium lignosulfonate, and natural fiber microfiber.
7. The method according to claim 6, wherein the first dispersant is polyethylene glycol and sodium lignosulfonate, and the second dispersant is natural fiber microfiber.
8. The method according to claim 3, wherein in S1, the calcination temperature is
The roasting time is 2-10 h at 300-500 ℃.
9. The method according to claim 3, wherein the heating and stirring temperature in S2 is 50-80 ℃.
10. The use of the highly efficient and environmentally friendly visible light photocatalyst as defined in claim 1 or 2 for the photodegradation of formaldehyde molecules.
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