CN113198455A - Molybdenum trioxide/molybdenum mesh photocatalyst and preparation method and application thereof - Google Patents
Molybdenum trioxide/molybdenum mesh photocatalyst and preparation method and application thereof Download PDFInfo
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 99
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 88
- 239000011733 molybdenum Substances 0.000 title claims abstract description 88
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 80
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 20
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004966 Carbon aerogel Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01D53/007—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
-
- 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
-
- B01J35/23—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
Abstract
The invention relates to the technical field of catalytic materials, and provides a molybdenum trioxide/molybdenum mesh photocatalyst as well as a preparation method and application thereof. When the molybdenum oxide/molybdenum mesh photocatalyst prepared by the invention is used for photocatalysis, under the auxiliary irradiation excitation of visible light, photogenerated carriers are generated to capture water molecules and oxygen in the air, and the photogenerated carriers are converted into active species with oxidability, namely hydroxyl radicals and superoxide radicals to react with formaldehyde molecules, so that the active species are mineralized, and further the molybdenum oxide/molybdenum mesh photocatalyst can be used for degrading formaldehyde. In addition, the molybdenum trioxide nano particles have a pistil-shaped nano structure, so that active sites can be improved, and the photocatalytic activity of the catalyst can be improved.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a molybdenum trioxide/molybdenum mesh photocatalyst and a preparation method and application thereof.
Background
With the development of society and the improvement of human living standard, the time of indoor activities of people is greatly increased, and Indoor Air Quality (IAQ) is more and more concerned by international scientific community, political organization, environmental management department and individuals. Excessive levels of Volatile Organic Compounds (VOCs) in the room can cause health problems of varying degrees. However, in the process of interior decoration, VOC mainly comes from paint, coating and adhesive, solvent-type release agent, etc., so the work of removing indoor volatile organic compounds is not slow. Among them, formaldehyde is a common VOCs. The excessive indoor formaldehyde has serious harm to human bodies: such as: sensitization, irritation and mutagenicity. At present, the means for removing formaldehyde mainly comprises an adsorption technical method, an absorption technical method, a membrane separation technical method, a biodegradation technical method, a photocatalysis technical method and the like. Among them, the photocatalytic method is favored because of its advantages of no pollution, high efficiency, convenience and the like.
MoO3Which is a typical P-type semiconductor, when excited by light, electrons in the valence band will be transferred to the conduction band, leaving holes in the valence band. The photogenerated carriers are separated and then react with oxygen and water molecules in the air to generate active species, and then the formaldehyde is mineralized. But will currently be MoO3When the photocatalyst is used as a catalyst, the photocatalyst is usually catalyst powder and is easy to agglomerate, so that the catalytic activity of the photocatalyst is lower and the recovery is difficult. To solve this technical problem, research in the prior art has shown that MoO is applied3Loaded on a carrier to increase MoO3But this scheme has a problem of complicated preparation process. For example, chinese patent CN112023915A discloses a preparation method of a carbon aerogel supported molybdenum trioxide catalyst, a product and an application thereof, and the method requires first preparing carbon aerogel and then supporting molybdenum trioxide on the carbon aerogel, which is complicated in preparation method and high in cost. Therefore, a need exists forThe preparation method of the molybdenum trioxide photocatalyst is simple to operate, and the prepared catalyst is easy to recycle and high in photocatalytic activity.
Disclosure of Invention
The preparation method provided by the invention is simple to operate, and the obtained molybdenum trioxide/molybdenum mesh photocatalyst is high in photocatalytic activity and easy to recover, and can be used as a photocatalyst for photocatalytic degradation of formaldehyde.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a molybdenum trioxide/molybdenum mesh photocatalyst, which comprises the following steps: and mixing hydrogen peroxide, ammonium sulfate and a molybdenum net, and carrying out hydrothermal reaction to obtain the molybdenum trioxide/molybdenum net photocatalyst.
Preferably, the mass concentration of the hydrogen peroxide is 0.10-0.30%.
Preferably, the ratio of the mass of the ammonium sulfate to the volume of the hydrogen peroxide is (0.050 to 0.300) g: (25-40) mL.
Preferably, the pore diameter of the molybdenum net is 80-150 meshes.
Preferably, the temperature of the hydrothermal reaction is 170-200 ℃.
Preferably, the hydrothermal reaction time is 10-13 h.
The invention also provides the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the preparation method in the technical scheme, which comprises a molybdenum mesh and a flower-pistil-shaped nano-structured MoO loaded on the surface of the molybdenum mesh3And (3) granules.
The invention also provides application of the molybdenum trioxide/molybdenum mesh photocatalyst in the technical scheme in photocatalytic degradation of formaldehyde.
The invention provides a preparation method of a molybdenum oxide/molybdenum mesh photocatalyst, which comprises the following steps: and mixing hydrogen peroxide, ammonium sulfate and a molybdenum net, and carrying out hydrothermal reaction to obtain the molybdenum trioxide/molybdenum net photocatalyst. The method takes the molybdenum net as a molybdenum source, and separates out Mo atoms on the molybdenum net in the form of ions by using hydrogen peroxide under the hydrothermal reactionThen taking ammonium sulfate as a structure directing agent to grow MoO in situ on the Mo net3Nanoparticles, and MoO3The nanoparticles exhibit pistil-like nanostructures. When the molybdenum oxide/molybdenum mesh photocatalyst prepared by the invention is used for photocatalysis, under the auxiliary irradiation excitation of visible light, photogenerated carriers are generated to capture water molecules and oxygen in the air, and the photogenerated carriers are converted into active species with oxidability, namely hydroxyl radicals and superoxide radicals to react with formaldehyde molecules, so that the active species are mineralized, and further the molybdenum oxide/molybdenum mesh photocatalyst can be used for degrading formaldehyde. The molybdenum trioxide/molybdenum mesh photocatalyst prepared by the preparation method provided by the invention is MoO comprising a molybdenum mesh and a pistil-shaped nano structure loaded on the surface of the molybdenum mesh3The particle and pistil-shaped nano structure can improve the active site and the photocatalytic activity of the catalyst. Experimental results show that when the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the preparation method provided by the invention is used for photocatalytic degradation of formaldehyde, 330mL of formaldehyde gas with the concentration of 30ppm can be completely mineralized within 30min by only utilizing visible light part, and CO with the corresponding amount is generated2And the catalytic activity is high.
The preparation method provided by the invention is simple, and the obtained molybdenum trioxide/molybdenum mesh photocatalyst is easy to recover, and can solve the problem that the powdery catalyst is difficult to recover.
Drawings
FIG. 1 is a schematic diagram of a quartz reactor used in the present invention;
FIG. 2 is an SEM image of a molybdenum trioxide/molybdenum mesh photocatalyst prepared in example 1 of the present invention at 10000 times magnification;
FIG. 3 is an SEM image of a molybdenum trioxide/molybdenum mesh photocatalyst prepared in example 1 of the present invention at 50000 times magnification;
FIG. 4 is an SEM image of 200000 times magnification of molybdenum trioxide/molybdenum mesh photocatalyst prepared in example 1 of the present invention;
fig. 5 is a degradation rate curve and a mineralization curve of the molybdenum trioxide/molybdenum mesh photocatalyst prepared in example 1 of the present invention to formaldehyde.
Detailed Description
The invention provides a preparation method of a molybdenum trioxide/molybdenum mesh photocatalyst, which comprises the following steps: and mixing hydrogen peroxide, ammonium sulfate and a molybdenum net, and carrying out hydrothermal reaction to obtain the molybdenum trioxide/molybdenum net photocatalyst.
In the present invention, the mass concentration of the hydrogen peroxide is preferably 0.10% to 0.30%, and more preferably 0.2% to 0.25%. The source of the hydrogen peroxide is not particularly limited, and the hydrogen peroxide can be a commercially available product known to those skilled in the art, or can be prepared into the hydrogen peroxide with the mass concentration by adopting high-concentration hydrogen peroxide. In the invention, the hydrogen peroxide is used as an oxidant and a solvent to separate Mo atoms on the Mo net out in the form of ions.
The source of the ammonium sulfate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the ammonium sulfate is used as a structure directing agent, so that the molybdenum trioxide formed on the surface of the molybdenum net has a pistil-shaped nano structure.
In the invention, the pore diameter of the molybdenum net is preferably 80-150 meshes, and more preferably 100 meshes. In the invention, when the pore diameter of the molybdenum mesh is in the range, the molybdenum trioxide/molybdenum mesh photocatalyst with excellent photocatalytic performance can be prepared by preventing the specific surface area from being smaller due to too low mesh number and preventing the filament diameter from being smaller due to too high mesh number, and the filament diameter is easy to corrode and destroy in the reaction process. The source of the molybdenum mesh is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, when the mass concentration of the hydrogen peroxide is 0.1% to 0.3%, the ratio of the mass of the ammonium sulfate to the volume of the hydrogen peroxide is preferably (0.050 to 0.300) g: (25-40) mL, more preferably (0.1135-0.1140) g: (30-35) mL. In the present invention, when the ratio of the mass of ammonium sulfate to the volume of hydrogen peroxide is in the above range, Mo ions precipitated as ions can be sufficiently formed into particles having a pistil-like nanostructure.
In the invention, when the high-concentration hydrogen peroxide is adopted to prepare the hydrogen peroxide with the mass concentration of 0.10-0.30%, the dosage of the water is not specially limited, and the dosage of the water is adjusted according to the dosage of the hydrogen peroxide. In the present invention, when the mass of the ammonium sulfate is preferably (0.050 to 0.300) g and the mass concentration of the high-concentration hydrogen peroxide is 30%, the volume of the water is preferably (25 to 40) mL, and more preferably 30 to 35 mL.
The operation mode of mixing the hydrogen peroxide, the ammonium sulfate and the molybdenum net is not particularly limited, and the hydrogen peroxide, the ammonium sulfate and the molybdenum net can be uniformly mixed by adopting a mixing mode well known to a person skilled in the art. In the invention, the operation mode of mixing the hydrogen peroxide, the ammonium sulfate and the molybdenum net is preferably stirring, and the stirring speed is not particularly limited, so that all the components can be uniformly mixed. In the invention, the stirring time is preferably 20-30 min, and more preferably 25-30 min. In the invention, when the stirring time is in the range, the hydrogen peroxide, the ammonium sulfate and the molybdenum net can be uniformly mixed.
According to the invention, the molybdenum net is preferably cut and washed in sequence before the hydrogen peroxide, the ammonium sulfate and the molybdenum net are mixed.
In the present invention, the cutting can cut the molybdenum net to a suitable size. The size of the molybdenum net after being cut is not particularly limited, and the size of the molybdenum net can be adjusted according to the size of a container for hydrothermal reaction. In the present invention, when the capacity of the hydrothermal reaction vessel is 50mL, the size of the molybdenum mesh after cutting is preferably 2cm × 3 cm.
In the present invention, the washing agent is preferably acetone, ethanol and deionized water. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. In the present invention, the washing is preferably performed in the following manner: and (3) carrying out ultrasonic treatment on the cut molybdenum net by using acetone and ethanol respectively, and then washing by using deionized water. The power and time of the ultrasonic wave are not specially limited, and the ultrasonic wave cleaning method can be adjusted according to the cleaning effect of the molybdenum net. In the invention, the power of the ultrasonic wave is preferably 50 kHz-80 kHz, and the time of the ultrasonic wave is preferably 10 min. In the invention, the surface of the commercial molybdenum net contains impurities, grease and the like, and the washing can remove the impurities and the grease on the surface of the molybdenum net.
In the invention, the temperature of the hydrothermal reaction is preferably 170-200 ℃, and more preferably 180-190 ℃; the time of the hydrothermal reaction is preferably 10-13 h, and more preferably 11-12 h. In the present invention, when the temperature and time of the hydrothermal reaction are within the above ranges, the hydrothermal reaction is more advantageously carried out.
The apparatus for the hydrothermal reaction in the present invention is not particularly limited, and an apparatus for hydrothermal reaction known to those skilled in the art may be used. In the present invention, the hydrothermal reaction apparatus is preferably a teflon-lined reaction vessel.
After the hydrothermal reaction is finished, the product obtained after the hydrothermal reaction is preferably washed and dried to obtain the molybdenum trioxide/molybdenum mesh photocatalyst. The washing and drying operation method of the present invention is not particularly limited, and a washing and drying operation method known to those skilled in the art may be used. In the present invention, the washing reagent is preferably deionized water; the drying is preferably air drying or oven drying, more preferably air drying. In the invention, the airing can prevent the molybdenum trioxide/molybdenum mesh photocatalyst from being denatured.
According to the preparation method provided by the invention, under the hydrothermal reaction, Mo atoms on the Mo net are separated out in the form of ions by using hydrogen peroxide, and then the MoO with a pistil-shaped nano structure grows in situ on the Mo net by using ammonium sulfate as a structure directing agent3And (3) nanoparticles.
The invention also provides the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the preparation method in the technical scheme, which comprises a molybdenum mesh and a flower-pistil-shaped nano-structured MoO loaded on the surface of the molybdenum mesh3And (3) granules. In the present invention, the MoO3The particles are in a pistil-shaped nano structure, have larger specific surface area and can be used for improving the catalytic activity of the catalyst.
The invention also provides application of the molybdenum trioxide/molybdenum mesh photocatalyst in the technical scheme in photocatalytic degradation of formaldehyde.
The application of the molybdenum trioxide/molybdenum mesh photocatalyst in the photocatalytic degradation of formaldehyde is not particularly limited, and a photocatalyst application method well known to those skilled in the art can be adopted. In the invention, the method for applying the molybdenum trioxide/molybdenum mesh photocatalyst in the photocatalytic degradation of formaldehyde is preferably carried out in a self-made quartz reactor. The physical diagram of the quartz reactor is preferably as shown in fig. 1.
The method for degrading the formaldehyde by the molybdenum trioxide/molybdenum mesh photocatalyst is not particularly limited, and a test method well known to those skilled in the art can be adopted. In the invention, the method for degrading formaldehyde by using the molybdenum trioxide/molybdenum mesh photocatalyst is preferably gas chromatography. In the present invention, the operation method of the gas chromatography measurement is not particularly limited, and an operation method known to those skilled in the art may be used.
The molybdenum trioxide/molybdenum mesh photocatalyst provided by the invention is MoO comprising a molybdenum mesh and a pistil-shaped nano structure loaded on the surface of the molybdenum mesh3The particle and pistil-shaped nano structure can improve the active site and the catalytic activity of the photocatalyst, and can be used for efficiently catalyzing and degrading formaldehyde.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Selecting a commercial black molybdenum net with the specification of 100 meshes, cutting the commercial black molybdenum net into small pieces with the size of 2 multiplied by 3cm, and respectively and sequentially ultrasonically cleaning the small pieces for 10min by using acetone, ethanol and deionized water, wherein the ultrasonic power is 50 kHz-80 kHz so as to remove impurities such as oil stains on the surface. And finally, drying the molybdenum net by cold air of a blower to obtain a clean molybdenum net.
Putting a clean molybdenum net in a container containing 30mL of H with the mass concentration of 0.235 percent2O2(0.235％H2O2Composed of 30% by mass of H2O2Prepared) adding 0.0114g of ammonium sulfate as a structure and guiding agent into the beaker, stirring for 20-30 min to dissolve and mix the medicines uniformly, and transferring the medicines to TeflonAnd (3) reacting for 12 hours at 180 ℃ in a reaction kettle with a lining to perform hydrothermal reaction to obtain the molybdenum trioxide/molybdenum mesh photocatalyst. Wherein the ratio of the mass of the ammonium sulfate to the volume of the hydrogen peroxide is 0.0114 g: 30 mL.
A scanning electron microscope is adopted to test the molybdenum trioxide/molybdenum mesh photocatalyst prepared in the embodiment, and an SEM image amplified by 10000 times is shown in FIG. 2; an SEM image at 50000 Xmagnification is shown in FIG. 3; an SEM image magnified 200000 is shown in FIG. 4.
As can be seen from fig. 2 to 4, the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the embodiment of the invention has a structure of molybdenum trioxide particles loaded on the surface of a molybdenum mesh, wherein the molybdenum trioxide has a pistil-like nanostructure.
Example 2
Formaldehyde degradation experiment: the molybdenum trioxide/molybdenum mesh photocatalyst prepared in example 1 is 6cm2Put into a 330ml self-made reactor. 1.5 microliter of formaldehyde solution was transferred from the analytically pure formaldehyde solution (37% -40%) and injected into a 330ml reactor, after formaldehyde volatilized, the concentration of formaldehyde in the reactor was 30 ppm. Turning on a xenon lamp light source (power is 300W), cutting off ultraviolet light by using an optical filter, enabling a catalyst to be 10-20 cm away from the light source, extracting gas in a 0.2 ml reactor by using an injector every 5min, and injecting the gas into a gas chromatograph to detect the concentration change of carbon dioxide in the reactor (Fuligas chromatograph, FID hydrogen flame ionization detector; test temperature: a column box is 80 ℃, a detector is 180 ℃, and an auxiliary furnace is 360 ℃). The formaldehyde was mineralized to generate carbon dioxide, and the performance of the catalyst was evaluated according to the increase of carbon dioxide, and a curve of formaldehyde degradation rate versus mineralization rate was obtained as shown in fig. 5.
As can be seen from FIG. 5, the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the invention can remove formaldehyde with the concentration of 30ppm within 30min and convert the formaldehyde into pollution-free carbon dioxide, which shows that the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the invention has excellent photocatalytic performance. The reason is probably that the micro morphology of the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the invention is very characteristic, each pistil-shaped nano structure is an activation center, and the 'petals' of a photo-generated carrier are transferred to a substrate material, so that the carrier separation capability is greatly promoted, and the photocatalytic capability is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a molybdenum trioxide/molybdenum mesh photocatalyst comprises the following steps: and mixing hydrogen peroxide, ammonium sulfate and a molybdenum net, and carrying out hydrothermal reaction to obtain the molybdenum trioxide/molybdenum net photocatalyst.
2. The preparation method according to claim 1, wherein the mass concentration of the hydrogen peroxide is 0.1-0.3%.
3. The method according to claim 2, wherein the ratio of the mass of ammonium sulfate to the volume of hydrogen peroxide is (0.050 to 0.300) g: (25-40) mL.
4. The preparation method according to claim 1, wherein the pore size of the molybdenum mesh is 80-150 mesh.
5. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 170 to 200 ℃.
6. The preparation method according to claim 1 or 5, wherein the hydrothermal reaction time is 10-13 h.
7. The molybdenum trioxide/molybdenum mesh photocatalyst prepared by the preparation method of any one of claims 1 to 6, which comprises a molybdenum mesh and a flower-core-shaped nano-structured MoO loaded on the surface of the molybdenum mesh3And (3) granules.
8. Use of the molybdenum trioxide/molybdenum mesh photocatalyst of claim 7 in the photocatalytic degradation of formaldehyde.
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