CN113198455B - 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 PDF

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CN113198455B
CN113198455B CN202110532735.9A CN202110532735A CN113198455B CN 113198455 B CN113198455 B CN 113198455B CN 202110532735 A CN202110532735 A CN 202110532735A CN 113198455 B CN113198455 B CN 113198455B
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CN113198455A (en
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杨丽霞
刘威
代威力
张�杰
罗胜联
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Nanchang Hangkong University
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
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    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/20Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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

Molybdenum trioxide/molybdenum mesh photocatalyst and preparation method and application thereof
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. The excessive content of Volatile Organic Compounds (VOCs) in the room can cause various health problems. 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 overproof 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.
MoO 3 Which 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 MoO 3 When 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 applied 3 Loaded on a carrier to increase MoO 3 But 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 needs to prepare the carbon aerogel first and then load molybdenum trioxide on the carbon aerogel, which is complex in preparation method and high in cost. Therefore, a method for preparing a molybdenum trioxide photocatalyst, which is simple to operate, is needed, and the prepared catalyst is easy to recover and has high 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 mesh is 80-150 meshes.
Preferably, the temperature of the hydrothermal reaction is 170-200 ℃.
Preferably, the hydrothermal reaction time is 10 to 13 hours.
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 MoO with a pistil-shaped nano structure loaded on the surface of the molybdenum mesh 3 And (3) particles.
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 utilizes a molybdenum net as a molybdenum source, utilizes hydrogen peroxide to separate Mo atoms on the Mo net out in the form of ions under the hydrothermal reaction, and then utilizes ammonium sulfate as a structure directing agent to grow MoO in situ on the Mo net 3 Nanoparticles, and MoO 3 The nanoparticles exhibit a pistil-like nanostructure. 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 mesh 3 The 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 generated 2 And 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 magnified 10000 times for the molybdenum trioxide/molybdenum mesh photocatalyst prepared in example 1 of the invention;
FIG. 3 is an SEM image at 50000 times magnification of a molybdenum trioxide/molybdenum mesh photocatalyst prepared in example 1 of the present invention;
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 present invention, the pore diameter of the molybdenum mesh is preferably 80 to 150 mesh, and more preferably 100 mesh. 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 solution is 0.1% to 0.3%, the ratio of the mass of the ammonium sulfate to the volume of the hydrogen peroxide solution 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 solution is 30%, the volume of the water is preferably (25 to 40) mL, and more preferably 30 to 35mL.
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 present invention, the stirring time is preferably 20 to 30min, more preferably 25 to 30min. 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 × 3cm.
In the present invention, the washing reagent 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 are not specially limited, and the ultrasonic 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 10min. 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 hydrothermal reaction time is preferably 10 to 13 hours, and more preferably 11 to 12 hours. 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 operation manner of the washing and drying is not particularly limited in the present invention, and the washing and drying operation manner known to those skilled in the art may be adopted. 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-like nano structure grows in situ on the Mo net by using ammonium sulfate as a structure directing agent 3 And (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 mesh 3 And (3) granules. In the present invention, the MoO 3 The 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 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. The present invention does not specifically limit the operation of the gas chromatography measurement, and the operation known to those skilled in the art may be adopted.
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 mesh 3 The 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 should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. 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.
Placing the clean molybdenum net at a concentration of 0.235% H by mass of 30mL 2 O 2 (0.235%H 2 O 2 Composed of 30% by mass of H 2 O 2 Prepared) is added into a beaker, 0.0114g of ammonium sulfate is used as a structure and guiding agent, the mixture is stirred for 20-30 min, the medicine is dissolved and mixed evenly, and the mixture is transferred into a reaction kettle with a Teflon lining for reaction for 12h at 180 ℃, and hydrothermal reaction is carried out, so that the molybdenum trioxide/molybdenum mesh photocatalyst is obtained. Wherein the ratio of the mass of the ammonium sulfate to the volume of the hydrogen peroxide is 0.0114g:30mL.
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 structure of the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the embodiment of the invention is molybdenum trioxide particles supported 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 6cm 2 Put into a 330ml self-made reactor. 1.5 microliter of formaldehyde solution is transferred into a 330 milliliter reactor from analytically pure formaldehyde solution (37 to 40 percent), and the concentration of formaldehyde in the reactor is 30ppm after the formaldehyde is volatilized. Turning on xenon lamp light source(power is 300W), cutting off ultraviolet light by using an optical filter, enabling the catalyst to be 10-20 cm away from a light source, extracting 0.2 ml of gas in the 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: column box 80 ℃, detector 180 ℃, auxiliary furnace 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 fact that the molybdenum trioxide/molybdenum mesh photocatalyst prepared by the method has very characteristic microscopic morphology, each pistil-shaped nano structure is an activation center, and a photogenerated carrier finishes 'petal' transfer 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: mixing hydrogen peroxide, ammonium sulfate and a molybdenum net, and carrying out hydrothermal reaction to obtain a molybdenum trioxide/molybdenum net photocatalyst;
the molybdenum trioxide/molybdenum mesh photocatalyst comprises a molybdenum mesh and a flower-shaped nano-structured MoO loaded on the surface of the molybdenum mesh 3 And (3) granules.
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 method according to claim 1, wherein the mesh has a pore size of 80 to 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 method according to claim 1 or 5, wherein the hydrothermal reaction is carried out for 10 to 13 hours.
7. The molybdenum trioxide/molybdenum mesh photocatalyst prepared by the preparation method according to any one of claims 1 to 6, which comprises a molybdenum mesh and a flower-bud-shaped nano-structured MoO supported on the surface of the molybdenum mesh 3 And (3) granules.
8. The use of the molybdenum trioxide/molybdenum mesh photocatalyst of claim 7 in the photocatalytic degradation of formaldehyde.
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