CN113926443B - Multi-component composite material for removing aldehyde through visible light catalysis, preparation method and air purifier - Google Patents

Multi-component composite material for removing aldehyde through visible light catalysis, preparation method and air purifier Download PDF

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CN113926443B
CN113926443B CN202111224783.8A CN202111224783A CN113926443B CN 113926443 B CN113926443 B CN 113926443B CN 202111224783 A CN202111224783 A CN 202111224783A CN 113926443 B CN113926443 B CN 113926443B
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CN113926443A (en
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陈耀刚
杨磊
邹治学
钟丹
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Shenzhen Kanghong Intelligent Health Technology Co ltd
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    • B01D2259/802—Visible light

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Abstract

The application discloses a multi-component composite material for removing aldehyde by visible light catalysis, a preparation method and an air purifier, wherein the multi-component composite material for removing aldehyde by visible light catalysis comprises ZnO/g-C 3 N 4 /CuO X Ternary composite ZnO/g-C 3 N 4 /CuO X The photocatalytic nano material can efficiently degrade formaldehyde pollutants in the air, and has the characteristics of good stability and reusability.

Description

Multi-component composite material for removing aldehyde through visible light catalysis, preparation method and air purifier
Technical Field
The application relates to the technical field of photocatalytic materials, in particular to a multi-component composite material for removing aldehyde by visible light catalysis, a preparation method and an air purifier.
Background
Formaldehyde (HCHO) is considered as a major toxic indoor pollutant, directly affecting indoor air quality, and a good living environment is related to the physical health of all residents, and the indoor formaldehyde pollution problem is urgently needed to be explored and solved.
The existing formaldehyde removal method is to combine ZnO and graphite carbon nitride to form a heterojunction structure so as to obtain a higher visible light absorption range and higher electron transfer efficiency. As a nonmetallic organic photocatalyst, g-C 3 N 4 Extensive research has been conducted for its unique properties such as narrow energy gap (2.7 eV), rapid charge transfer, and many redox active sites. However, in the case of using carbon nitride (g-C 3 N 4 ) g-C after modification of ZnO 3 N 4 ZnO can only remove pollutants by using a small amount of visible light, and the degradation efficiency is still low.
Disclosure of Invention
The application mainly aims to provide a multi-component composite material for removing aldehyde by visible light catalysis, a preparation method and an air purifier, and aims to solve the problem that carbon nitride (g-C) 3 N 4 ) g-C after modification of ZnO 3 N 4 The ZnO can only remove pollutants by using a small amount of visible light, and the degradation efficiency is still low.
To achieve the above object, the present application provides a multi-component composite material for removing aldehyde by visible light catalysis, comprising ZnO/g-C 3 N 4 /CuO X Ternary compounding.
In order to achieve the above purpose, the application provides a preparation method of a multi-component composite material for removing aldehyde by visible light catalysis, which comprises the following steps:
s20, mixing the zinc oxide precursor with g-C 3 N 4 Dispersed in CuSO 4 Heating in water bath to obtain solid product;
s30, washing the solid product, and then drying to obtain ZnO/g-C 3 N 4 /CuO X Is a precursor of (a);
s40, calcining the precursor under vacuum condition to obtain the product ZnO/g-C 3 N 4 /CuO X 。
Optionally, step S20 further includes, before:
s101a, mixing urea aqueous solution and zinc acetate aqueous solution with the solute mass ratio of 1:2-5 to obtain solution A;
s102a, placing the solution A in an environment of 120-200 ℃ for hydrothermal reaction for 6-18h, and cooling, washing and drying to obtain a zinc oxide precursor.
Alternatively, in step S102a,
the drying temperature is 40-80 ℃ and the drying time is 10-20h.
Optionally, step S10 further includes:
s101b, calcining the carbon-nitrogen source with the carbon-nitrogen ratio of 1:2, cooling to room temperature, and grinding to obtain g-C 3 N 4 。
Alternatively, in step S101b,
the carbon and nitrogen source comprises one or more of cyanamide, dicyandiamide, melamine and urea; and/or the number of the groups of groups,
in the step S102b of the process,
when the calcination treatment is carried out, the temperature is raised to 500-600 ℃ at the temperature rising rate of 2-10 ℃/min, and then the calcination is carried out for 3-5h at the temperature of 500-600 ℃.
Alternatively, in step S20,
g-C 3 N 4 the mass ratio of the ZnO to the zinc oxide is 1: (0.1-1), g-C 3 N 4 Mass and Cu of (2) 2+ The mass ratio of (2) is 1:0.001-0.01; and/or the number of the groups of groups,
heating in water bath, and stirring at 80-100deg.C for 0.5-3 hr.
Alternatively, in step S30,
when washing is carried out, the washing times of water washing are 6-10 times; and/or the number of the groups of groups,
when the drying treatment is carried out, the drying temperature is 60-100 ℃ and the drying time is 12-24h.
Alternatively, in step S40,
when the calcination treatment is carried out, the calcination temperature is 300-500 ℃, the calcination time is 2-5h, and the temperature rising rate is 5-15 ℃/min.
The application further provides an air purifier, which comprises the multi-component composite material for the visible light catalytic aldehyde removal prepared by the preparation method of the multi-component composite material for the visible light catalytic aldehyde removal, and the preparation method of the multi-component composite material for the visible light catalytic aldehyde removal comprises the following steps:
s20, mixing the zinc oxide precursor with g-C 3 N 4 Dispersed in CuSO 4 Heating in water bath to obtain solid product;
s30, washing the solid product, and then drying to obtain ZnO/g-C 3 N 4 /CuO X Is a precursor of (a);
s40, calcining the precursor under vacuum condition to obtain the product ZnO/g-C 3 N 4 /CuO X 。
The technical proposal of the application comprises ZnO/g-C 3 N 4 /CuO X The ternary composite multi-element composite material for removing aldehyde by visible light catalysis has higher visible light utilization rate, higher formaldehyde degradation rate under an air medium, better stability and repeated utilization.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing a multi-component composite material for visible light catalytic aldehyde removal according to the present application;
FIG. 2 is a diagram showing ZnO/g-C prepared by the preparation method of FIG. 1 3 N 4 /CuO X Compounding an SEM image of the visible light catalytic nano material;
FIG. 3 is a diagram showing ZnO/g-C prepared by the preparation method of FIG. 1 3 N 4 /CuO X An ultraviolet diffuse reflection spectrum graph of the composite visible light catalytic nano material and ZnO;
FIG. 4 is a diagram showing ZnO/g-C prepared by the preparation method of FIG. 1 3 N 4 /CuO X Composite visible light catalytic nano material N 2 Adsorption-desorption isotherm plot;
FIG. 5 is a diagram showing ZnO/g-C prepared by the preparation method of FIG. 1 3 N 4 /CuO X Composite visible light catalytic nano material, znO and g-C 3 N 4 Fourier infrared spectra of (a);
FIG. 6 is a graph showing ZnO/g-C prepared by the preparation method of FIG. 1 3 N 4 /CuO X A performance comparison diagram of photocatalytic nano material and ZnO and g-C3N4 photocatalyst for degrading formaldehyde by visible light catalysis;
FIG. 7 is ZnO/g-C 3 N 4 /CuO X And a test result diagram of stable photocatalytic performance of the photocatalytic nano material.
The achievement of the objects, functional features and advantages of the present application will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The specific conditions were not specified in the examples, and the examples were conducted under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Formaldehyde (HCHO) is considered as a major toxic indoor pollutant, directly affecting indoor air quality, and a good living environment is related to the physical health of all residents, and the indoor formaldehyde pollution problem is urgently needed to be explored and solved.
The existing formaldehyde removal method is to combine ZnO and graphite carbon nitride to form a heterojunction structure so as to obtain a higher visible light absorption range and higher electron transfer efficiency. As a nonmetallic organic photocatalyst, g-C 3 N 4 Because of its unique properties, it is possible to provide,such as a narrow energy gap (2.7 eV), rapid charge transfer and many redox active sites, have been widely studied. However, in the case of using carbon nitride (g-C 3 N 4 ) g-C after modification of ZnO 3 N 4 ZnO can only remove pollutants by using a small amount of visible light, and the degradation efficiency is still low.
In view of the above, the application provides a preparation method of a multi-component composite material for removing aldehyde by visible light catalysis, which aims to prepare the multi-component composite material for removing aldehyde by visible light catalysis.
The application provides a multi-component composite material for removing aldehyde by visible light catalysis, which comprises ZnO/g-C 3 N 4 /CuO X Ternary compounding.
The technical proposal of the application comprises ZnO/g-C 3 N 4 /CuO X The ternary composite multi-element composite material for removing aldehyde by visible light catalysis has higher visible light utilization rate, higher formaldehyde degradation rate under an air medium, better stability and repeated utilization.
Referring to fig. 1, the present application further provides a preparation method of the multi-component composite material for removing aldehyde by visible light catalysis, which comprises the following steps:
s20, mixing the zinc oxide precursor with g-C 3 N 4 Dispersed in CuSO 4 Heating in water bath to obtain solid product;
specifically, in step S20, g-C 3 N 4 The mass ratio of the ZnO to the zinc oxide is 1: (0.1-1), g-C 3 N 4 Mass and Cu of (2) 2+ The mass ratio of the zinc oxide precursor and the g-C is 1:0.001-0.01, and the zinc oxide precursor and the g-C are heated and stirred for 0.5-3h at 80-100 ℃ when heated in water bath 3 N 4 CuSO 4 Can fully react.
Specifically, step S20 further includes, before:
s101a, mixing urea aqueous solution and zinc acetate aqueous solution with the solute mass ratio of 1:2-5 to obtain solution A;
s102a, placing the solution A in an environment of 120-200 ℃ for hydrothermal reaction for 6-18h, and cooling, washing and drying to obtain a zinc oxide precursor.
The drying temperature is 40-80 ℃ and the drying time is 10-20h, so that the drying efficiency of the zinc oxide precursor is improved and the dryness of the zinc oxide precursor is ensured.
Specifically, during washing, centrifugal washing is carried out for 6-10 times at 8000-10000 rpm, so that washing is more sufficient, and impurities in the prepared zinc oxide precursor are avoided.
Specifically, step S20 further includes, before:
s101b, calcining the carbon-nitrogen source with the carbon-nitrogen ratio of 1:2, cooling to room temperature, and grinding to obtain g-C 3 N 4 。
Specifically, the carbon-nitrogen source comprises one or more of cyanamide, dicyandiamide, melamine and urea.
Preferably, in step S101b, the temperature is raised to 500-600deg.C at a rate of 2-10deg.C/min and then calcined at 500-600deg.C for 3-5h, thereby increasing g-C 3 N 4 Is improved.
Preferably, the carbon and nitrogen source is selected from dicyandiamide, and when the dicyandiamide is calcined, the dicyandiamide is placed in an alumina crucible with a cover, and the dicyandiamide is calcined by a muffle furnace, so that the g-C is improved 3 N 4 Is improved.
S30, washing the solid product, and then drying to obtain ZnO/g-C 3 N 4 /CuO X Is a precursor of (a);
specifically, in step S30, the washing times with water is 6-10 times, so that impurities in the solid product are sufficiently washed away, and in the drying process, the drying temperature is 60-100 ℃ and the drying time is 12-24 hours, so that the moisture in the solid product is sufficiently removed, and the dryness of the solid product is ensured.
It should be noted that, in the drying process, the drying device is an oven, and in other embodiments, the drying device may be a hot air blower, a dryer, or the like, which is not limited in the present application.
S40, calcining the precursor under vacuum condition to obtain the product ZnO/g-C 3 N 4 /CuO X 。
Specifically, in step S40, during the calcination treatment, the calcination temperature is 300-500 ℃, the calcination time is 2-5h, and the temperature rising rate is 5-15 ℃/min, so that the calcination efficiency is improved, and the treatment time is greatly shortened.
The preparation method of the multi-element composite material for removing the formaldehyde by the visible light catalysis provided by the application obviously improves the preparation success rate of the multi-element composite material for removing the formaldehyde by the visible light catalysis by controlling the preparation conditions, and the prepared multi-element composite material for removing the formaldehyde by the visible light catalysis can efficiently degrade formaldehyde pollutants in the air and has the characteristics of good stability and reusability.
In addition, the air purifier provided by the application comprises the multi-component composite material for the visible light catalytic aldehyde removal, which is prepared by the preparation method of the multi-component composite material for the visible light catalytic aldehyde removal, so that the air purifier has all the beneficial effects of the multi-component composite material for the visible light catalytic aldehyde removal, and the multi-component composite material for the visible light catalytic aldehyde removal is not repeated herein.
An example of the preparation method of the multi-component composite material for visible light catalytic formaldehyde removal according to the present application is given below:
(1) Mixing urea aqueous solution and zinc acetate aqueous solution with the solute mass ratio of 1:2-5 to obtain solution A, placing the solution A in an environment of 120-200 ℃ for hydrothermal reaction for 6-18 hours, and cooling, washing and drying to obtain a zinc oxide precursor, wherein the zinc oxide precursor is centrifugally washed for 6-10 times at 8000-10000 rpm, and the drying temperature is 40-80 ℃ and the drying time is 10-20 hours; calcining carbon-nitrogen source with carbon-nitrogen ratio of 1:2, cooling to room temperature, and grinding to obtain g-C 3 N 4 The carbon nitrogen source comprises one or more of cyanamide, dicyandiamide, melamine and urea, and when the calcination treatment is carried outHeating to 500-600 ℃ at a heating rate of 2-10 ℃/min, and calcining for 3-5h at the temperature of 500-600 ℃;
(2) Combining a zinc oxide precursor with g-C 3 N 4 Dispersed in CuSO 4 Heating in water bath to obtain solid product, wherein g-C 3 N 4 The mass ratio of the zinc oxide precursor to the zinc oxide precursor is 1:0.1-1, g-C 3 N 4 Mass and Cu of (2) 2+ The mass ratio of (2) is 1:0.001-0.01, and heating and stirring for 0.5-3h at 80-100 ℃ when heating in water bath;
(3) Washing the solid product, and then drying to obtain ZnO/g-C 3 N 4 /CuO X The precursor of (2) is washed by water for 6-10 times, and is dried at 60-100deg.C for 12-24h;
(4) Calcining the precursor under vacuum condition to obtain ZnO/g-C product 3 N 4 /CuO X When the calcination treatment is carried out, the calcination temperature is 300-500 ℃, the calcination time is 2-5h, and the temperature rising rate is 5-15 ℃/min.
The following description of the embodiments of the present application will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present application and not limiting.
Example 1
(1) Mixing a zinc acetate aqueous solution with a solute of 3.596g and a urea aqueous solution with a solute of 0.984g to obtain a solution A, subjecting the solution A to hydrothermal reaction at 160 ℃ for 10 hours, cooling, centrifugally washing at 8000rpm for 6 times, drying at a drying temperature of 40 ℃ for 10 hours to obtain a zinc oxide precursor, placing 5g of dicyandiamide into a covered alumina crucible, heating to 550 ℃ at a heating rate of 5 ℃/min in a muffle furnace, calcining at 550 ℃ for 3 hours, cooling to room temperature, and grinding to obtain g-C 3 N 4 ；
(2) Mixing 0.4g of zinc oxide precursor with 1g of g-C 3 N 4 CuSO dispersed in 50ml 4 In the aqueous solution, cu 2+ Relative to g-C 3 N 4 The mass of the mixture is 0.5 weight percent, a solid product is obtained by water bath heating, and the mixture is heated and stirred for 1h at 90 ℃ when the mixture is heated in the water bath;
(3) The solid product was washed 6 times with deionized water and dried in an oven at 70℃for 24 hours to give ZnO/g-C 3 N 4 /CuO X Is a precursor of (a).
(4) The precursor is placed in a muffle furnace to be heated to 300 ℃ at a heating rate of 5 ℃/min, and calcined for 5 hours at 300 ℃ to obtain the ZnO/g-C product 3 N 4 /CuO X 。
Example 2
(1) Mixing urea aqueous solution with solute of 1g and zinc acetate aqueous solution with solute of 2g to obtain solution A, placing the solution A in 120 ℃ environment to perform hydrothermal reaction for 6h, cooling, centrifugally washing for 10 times at 10000rpm, drying for 20h at a drying temperature of 80 ℃ to obtain zinc oxide precursor, placing 7g melamine into an alumina crucible with a cover, heating to 500 ℃ at a heating rate of 2 ℃/min in a muffle furnace, calcining for 5h at a temperature of 500 ℃, cooling to room temperature, and grinding to obtain g-C 3 N 4 ；
(2) Mixing 0.1g of zinc oxide precursor with 1g of g-C 3 N 4 CuSO dispersed in 60ml 4 In the aqueous solution, cu 2+ Relative to g-C 3 N 4 The mass of the mixture is 0.1 weight percent, a solid product is obtained by water bath heating, and the mixture is heated and stirred for 0.5h at 80 ℃ during the water bath heating;
(3) The solid product was washed 10 times with deionized water and dried in an oven at 60℃for 12 hours to give ZnO/g-C 3 N 4 /CuO X Is a precursor of (a).
(4) The precursor is placed in a muffle furnace to be heated to 500 ℃ at a heating rate of 15 ℃/min, and calcined for 2 hours under the condition of 500 ℃ to obtain the ZnO/g-C product 3 N 4 /CuO X 。
Example 3
(1) Mixing urea aqueous solution with solute of 2g and zinc acetate aqueous solution with solute of 10g to obtain solution A, and placing the solution A at 200deg.CAfter hydrothermal reaction for 18 hours in the environment, cooling, centrifugally washing at 9000rpm for 8 times, drying at a drying temperature of 60 ℃ for 15 hours to obtain a zinc oxide precursor, putting 6.5g of urea into an alumina crucible with a cover, heating to 600 ℃ in a muffle furnace at a heating rate of 10 ℃/min, calcining at 600 ℃ for 4 hours, cooling to room temperature, and grinding to obtain g-C 3 N 4 ；
(2) 2g of zinc oxide precursor and 2g of g-C 3 N 4 CuSO dispersed in 70ml 4 In the aqueous solution, cu 2+ Relative to g-C 3 N 4 The mass of the mixture is 1 weight percent, a solid product is obtained by water bath heating, and the mixture is heated and stirred for 3 hours at 100 ℃ during the water bath heating;
(3) The solid product was washed 8 times with deionized water and dried in an oven at 100℃for 18 hours to give ZnO/g-C 3 N 4 /CuO X Is a precursor of (a).
(4) The precursor is placed in a muffle furnace to be heated to 400 ℃ at a heating rate of 10 ℃/min, and calcined for 3.5h under the condition of 400 ℃ to obtain the ZnO/g-C product 3 N 4 /CuO X 。
Example 4
(1) Mixing urea aqueous solution with solute of 1g and zinc acetate aqueous solution with solute of 3g to obtain solution A, placing the solution A in 170 ℃ environment to carry out hydrothermal reaction for 12h, cooling, centrifugally washing for 7 times at 8500rpm, drying for 14h at a drying temperature of 50 ℃ to obtain zinc oxide precursor, mixing 8.5g of cyanamide and dicyandiamide, placing into an alumina crucible with a cover, heating to 580 ℃ at a heating rate of 6 ℃/min in a muffle furnace, calcining for 3.5h at a temperature of 580 ℃, cooling to room temperature, and carrying out grinding treatment to obtain g-C 3 N 4 ；
(2) 0.5g of zinc oxide precursor is mixed with 1g of g-C 3 N 4 CuSO dispersed in 35ml 4 In the aqueous solution, cu 2+ Relative to g-C 3 N 4 The mass of the mixture is 0.55 weight percent, a solid product is obtained by water bath heating, and the mixture is heated and stirred for 2 hours at 85 ℃ when the mixture is heated in the water bath;
(3) The solid product was washed 9 times with deionized water and dried in an oven at 75℃for 20 hours to give ZnO/g-C 3 N 4 /CuO X Is a precursor of (a).
(4) The precursor is placed in a muffle furnace to be heated to 450 ℃ at the heating rate of 8 ℃/min, and calcined for 4.5 hours under the condition of 450 ℃ to obtain the ZnO/g-C product 3 N 4 /CuO X 。
ZnO/g-C prepared in the embodiment of the application 3 N 4 /CuO X SEM test of composite visible light catalytic nanomaterial and FIG. 2 shows ZnO/g-C prepared in example 1 3 N 4 /CuO X SEM image of composite visible light catalytic nanomaterial, znO/g-C shown in FIG. 2 3 N 4 /CuO X The materials are in the form of sheets stacked on top of each other.
FIG. 3 is ZnO and ZnO/g-C prepared in example 1 3 N 4 /CuO X And compositing an ultraviolet diffuse reflection spectrogram of the visible light catalytic nano material. As shown in the figure, the light absorption edge of the ZnO photocatalyst is about 380nm, namely zinc oxide only responds to ultraviolet light, and the ZnO/g-C composite material 3 N 4 /CuO X In due to CuO X The doping of the (C) is stronger in light absorption edge and stronger in light absorption edge, obvious light absorption is expanded to full visible spectrum, znO/g-C 3 N 4 /CuO X The absorption peak for visible light demonstrates successful synthesis of the composite.
FIG. 4 shows ZnO/g-C as an example of the present application 3 N 4 /CuO X N of (2) 2 Adsorption-desorption isotherm diagram, the specific surface area of the composite material is 48.2m 2 And/g, the adsorption performance to formaldehyde is weaker, and the formaldehyde is reacted and degraded mainly due to the fact that persistent free radicals are generated through photocatalysis.
FIG. 5 is ZnO, g-C 3 N 4 And ZnO/g-C prepared in example 1 3 N 4 /CuO X Is a fourier infrared spectrum of (a). To study the composition and structure of the synthesized samples, FTIR analysis was used, as shown in FIG. 5, for ZnO at 3500cm -1 Has strong broadband absorption peak at 442cm -1 The Zn-O bond stretching vibration absorption peakThe method comprises the steps of carrying out a first treatment on the surface of the For g-C 3 N 4 At 810cm -1 ，1150-1700cm -1 ，3100-3300cm -1 A strong absorption band appears at each location. It is worth mentioning that pure ZnO and g-C 3 N 4 The main typical absorption peak of (C) is present in ZnO/g-C 3 N 4 /CuO X In the sample, this further indicates ZnO/g-C 3 N 4 /CuO X Successful synthesis of the composite catalyst. Due to CuO X Less doping of CuO is not observed in fourier infrared spectra X Obvious functional groups.
Application example 1
(1) In a 1.5L quartz photocatalytic reactor, formaldehyde was photocatalytically removed with a 5W fan at room temperature under visible light irradiation. A 350W xenon lamp was placed vertically outside the photoreactor. Ultraviolet rays were removed using an ultraviolet cut filter (420 nm). The average light intensity of the surface of the reaction solution in the reaction solution was measured by a photon densitometer to be 200mW/cm 2 I.e. 2 standard solar light intensities (AM 3G), 0.1G ZnO/G-C 3 N 4 /CuO X Photocatalytic nanomaterial and 15ml deionized water were sonicated in a petri dish (diameter 7.0 cm) for 25min to form a suspension. The dish was dried under vacuum at 60℃for 1 hour, and a uniform photocatalyst film was formed at the bottom of the dish.
(2) The petri dish was placed in a photocatalytic reactor. A quantity of 38% aqueous formaldehyde solution was injected into the photoreactor and the initial concentration of evaporated HCHO after reaching the adsorption-desorption equilibrium in the dark was 100ppm. During the irradiation process, formaldehyde and CO in the reactor 2 And H 2 The O concentration was monitored online by a photoacoustic infrared multiple gas monitor (inova Air Tech 95 Instruments model 1412). The formaldehyde removal rate (Y) was calculated as Y (%) = (1-C/C) 0 ) X 100%, where C and C 0 Formaldehyde concentrations at 0min and t min, respectively.
(3) After the first degradation reaction is completed, drying the culture dish containing the photocatalyst at 60 ℃ for 0.5 hour, and then putting the culture dish into a reactor again to carry out the next formaldehyde removal reaction, wherein the reaction conditions are consistent with the first reaction except for materials; after the second reaction is completed, repeating the steps, and carrying out a third degradation experiment.
The detection result shows that under the irradiation of 2 standard solar light intensity visible lights (lambda > 400 nm), the catalyst dosage is 0.1g, the initial concentration of formaldehyde is 100ppm, and the initial temperature is room temperature, znO/g-C 3 N 4 /CuO X The degradation efficiency of the photocatalytic nano material on formaldehyde after 180min is up to 96.5%.
The air pollutants include, but are not limited to, formaldehyde, SO 2 Ammonia, NO -X Etc. Preferably, the ZnO/C of the application 3 N 4 /CuO X Under the photocatalysis condition, the catalyst has an excellent degradation effect on formaldehyde. Formaldehyde is firstly absorbed in ZnO/C 3 N 4 /CuO X When the ZnO/C is excited by the visible light 3 N 4 /CuO X At the time, electrons are taken from C 3 N 4 Is transferred to the ZnO conduction band, and holes are left at C 3 N 4 At the same time CuOx on ZnO has high redox reversibility between Cu (II) and Cu (I) and greatly promotes separation of holes and electrons, formaldehyde is easily oxidized by surface active oxygen or hydroxyl groups, and finally water and carbon dioxide are generated.
FIG. 6 is a ZnO/g-C prepared in example 1 3 N 4 /CuO X Photocatalytic nanomaterial with ZnO and g-C 3 N 4 And (3) comparing the performances of the photocatalyst in the visible light catalytic degradation of formaldehyde. As can be seen, since ZnO does not absorb visible light, formaldehyde is hardly degraded after 180min of illumination, and g-C 3 N 4 The nano particles can only remove about 20% of ZnO/g-C after 180min 3 N 4 /CuO X The degradation efficiency of the photocatalytic nano material on formaldehyde is up to 96.5% in 180 min.
FIG. 7 shows ZnO/g-C 3 N 4 /CuO X The photocatalytic nano material has stable photocatalytic performance. After the first degradation reaction is completed, drying the culture dish containing the photocatalyst at 60 ℃ for 0.5 hour, and then putting the culture dish into a reactor again to carry out the next formaldehyde removal reaction, wherein the reaction conditions are consistent with the first reaction except for materials; after the second reaction is completedRepeating the steps, and carrying out a third degradation experiment. The formaldehyde degradation efficiency in three continuous degradation experiments is over 90 percent, which shows that ZnO/g-C 3 N 4 /CuO X The photocatalytic activity of the photocatalytic nanomaterial remained good after three cycles.
Application example 2
The procedure is the same as in application example 1, except that ZnO/g-C 3 N 4 /CuO X The addition amount of the photocatalytic nano material is replaced by 0.5g/L.
The detection result shows that after 180min of illumination, the formaldehyde degradation efficiency is over 90% in three continuous degradation experiments.
Application example 3
The procedure is the same as in application example 1, except that ZnO/g-C 3 N 4 /CuO X The addition amount of the photocatalytic nano material is replaced by 2g/L.
The detection result shows that after 180min of illumination, the formaldehyde degradation efficiency is over 90% in three continuous degradation experiments.
Comparative example 1
The procedure is the same as in application example 1, except that ZnO/g-C 3 N 4 /CuO X The photocatalytic nanomaterial is replaced with ZnO.
The detection result shows that after 180min of illumination, formaldehyde is hardly degraded in three continuous degradation experiments.
Comparative example 2
The procedure is the same as in application example 1, except that ZnO/g-C 3 N 4 /CuO X Substitution of photocatalytic nanomaterial to g-C 3 N 4 And (3) nanoparticles.
The detection result shows that about 20% of formaldehyde is removed in three continuous degradation experiments after 180min of illumination.
As can be seen from the comparison of the above application examples 1 to 3 with comparative examples 1 to 2, the ZnO photocatalyst hardly degraded formaldehyde after 180 minutes of illumination, g-C 3 N 4 The nano particles remove about 20 percent of formaldehyde after illumination for 180 minutes,whereas ZnO/g-C prepared in the examples of the present application 3 N 4 /CuO X The degradation efficiency of the photocatalytic nano material on formaldehyde after 180min is up to 96.5%.
As can be seen from the comparison of the above application example 1 and application example 3, the ZnO/g-C prepared in the examples of the present application 3 N 4 /CuO X The photocatalytic nano material has good stability, higher visible light utilization rate, higher formaldehyde degradation rate under an air medium, better stability and repeated use.
The foregoing is merely a preferred embodiment of the present application and is not intended to limit the scope of the present application, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the present application.

Claims (6)

1. The application of the multi-element composite material in the visible light catalytic formaldehyde removal is characterized in that under the irradiation of 2 standard solar light intensities, the catalyst dosage is 0.1g, the initial concentration of formaldehyde is 100ppm, and the initial temperature is room temperature, znO/g-C 3 N 4 /CuO X The degradation efficiency of the photocatalytic nano material on formaldehyde reaches 96.5% after 180min, and the preparation method of the multi-element composite material comprises the following steps:
s101a, the solute mass ratio is 1: mixing the urea aqueous solution of (2-5) with a zinc acetate aqueous solution to obtain a solution A;
s102a, placing the solution A in an environment of 120-200 ℃ for hydrothermal reaction for 6-18h, and cooling, washing and drying to obtain a zinc oxide precursor;
s20, mixing the zinc oxide precursor with g-C 3 N 4 Dispersed in CuSO 4 Heating in water bath to obtain solid product;
s30, washing the solid product, and then drying to obtain ZnO/g-C 3 N 4 /CuO X Is a precursor of (a);
s40, calcining the precursor under vacuum conditionFiring to obtain the product ZnO/g-C 3 N 4 /CuO X；
Wherein, in step S20, g-C 3 N 4 The mass ratio of ZnO to ZnO is 1: (0.1-1), g-C 3 N 4 Mass and Cu of (2) 2+ The mass ratio of (1) (0.001-0.01), heating and stirring for 0.5-3h at 80-100 ℃ when heating in water bath;
in step S40, the calcination temperature is 300-500 ℃, the calcination time is 2-5h, and the temperature rising rate is 5-15 ℃/min when the calcination treatment is performed.
2. The use of the multi-component composite according to claim 1 for the catalytic removal of aldehydes in the visible light, wherein, in step S102a,
the drying temperature is 40-80 ℃ and the drying time is 10-20h.
3. The use of the multi-component composite according to claim 1 for visible light catalytic aldehyde removal, further comprising, prior to step S20:
s101b, the carbon to nitrogen ratio is 1:2, calcining the carbon-nitrogen source, cooling to room temperature, and grinding to obtain g-C 3 N 4 。
4. The use of the multi-component composite according to claim 3 for the catalytic removal of aldehydes in the visible light, wherein, in step S101b,
the carbon and nitrogen source comprises one or more of cyanamide, dicyandiamide, melamine and urea; and/or the number of the groups of groups,
when the calcination treatment is carried out, the temperature is raised to 500-600 ℃ at the temperature rising rate of 2-10 ℃/min, and then the calcination is carried out for 3-5 hours at the temperature of 500-600 ℃.
5. The use of the multi-component composite according to claim 1 for the catalytic removal of aldehydes in the visible light, wherein, in step S30,
when washing is carried out, the washing times of water washing are 6-10 times; and/or the number of the groups of groups,
when the drying treatment is carried out, the drying temperature is 60-100 ℃ and the drying time is 12-24h.
6. The use of the multi-component composite according to claim 1 for the catalytic removal of aldehydes in the visible light, wherein, in step S40,
when the calcination treatment is carried out, the calcination temperature is 300-500 ℃, the calcination time is 2-5h, and the temperature rising rate is 5-15 ℃/min.
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