CN111167478A - CdS-Bi2WO6Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene - Google Patents
CdS-Bi2WO6Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene Download PDFInfo
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- CN111167478A CN111167478A CN202010017876.2A CN202010017876A CN111167478A CN 111167478 A CN111167478 A CN 111167478A CN 202010017876 A CN202010017876 A CN 202010017876A CN 111167478 A CN111167478 A CN 111167478A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 71
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000005977 Ethylene Substances 0.000 title claims abstract description 68
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 13
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical group CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000001228 spectrum Methods 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 33
- 238000003756 stirring Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 235000012055 fruits and vegetables Nutrition 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J35/39—
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides CdS-Bi2WO6An application of a semiconductor Z-type heterojunction in photocatalytic degradation of ethylene belongs to the technical field of inorganic nano photocatalytic materials. The invention combines two narrow band gap semiconductors CdS and Bi2WO6To construct CdS-Bi2WO6The Z-shaped heterojunction of semiconductor makes full use of the strong reducibility of CdS and Bi2WO6Strong oxidizing property and simultaneously expands the absorption of the CdS-Bi in the visible light part of the solar spectrum2WO6Semiconductor Z-type heterojunctionThe catalyst has a wide response range (200-600 nm) to solar spectrum and good absorption performance to solar spectrum, and can utilize sunlight to efficiently catalyze and degrade ethylene in air, thereby achieving the purpose of purifying ethylene.
Description
Technical Field
The invention relates to the technical field of inorganic nano photocatalytic materials, in particular to CdS-Bi2WO6The application of the semiconductor Z-type heterojunction in photocatalytic degradation of ethylene.
Background
In the progress of social development and industrialization, the use of fossil fuels brings huge economic wealth for human life. However, the burning process of fossil fuels and plants in nature release ethylene gas during their growth, resulting in an increasing content of ethylene gas in the atmosphere. The trace amount of ethylene in the air is subjected to a series of evolution, and photochemical smog is finally formed, so that serious atmospheric pollution is caused. Meanwhile, the fruits and vegetables release extremely trace amount of ethylene in the storage process, so that the fruits and vegetables can be ripened, and even the fruits and vegetables are deteriorated and rotten. Therefore, the development of a technology capable of efficiently degrading trace ethylene gas in the atmosphere and in the storage process of fruits and vegetables has great scientific research, economic and practical significance.
The ethylene gas in the atmosphere has the characteristics of low concentration, difficult adsorption and high stability, so that the ethylene gas is extremely difficult to degrade. At present, the main methods for eliminating trace ethylene gas in the atmosphere include a physical adsorption method, a strong oxidant oxidation method, a thermal catalytic oxidation method and a photocatalytic oxidation method. The physical adsorption method is a method of adsorbing ethylene by using activated carbon, molecular sieves, or the like, but the amount of adsorption is limited and desorption is easy when the temperature is increased. The strong oxidation method adopts a strong oxidant to oxidize and degrade ethylene, but is easy to cause secondary pollution to the environment. The ethylene is degraded by thermal catalytic oxidation, which is an efficient and rapid method, but the thermal catalytic temperature is generally about 250 ℃, and noble metals are generally adopted as catalysts, so that the energy consumption is high, the cost is high, and the large-scale popularization and application are not facilitated. Meanwhile, extremely harsh conditions, such as low temperature, humidity and environmental protection, are required in the storage process of fruits and vegetables. These harsh conditions render physisorption, strong oxidant oxidation and thermocatalytic oxidation unusable. The photocatalytic oxidation method utilizes sunlight to carry out photocatalytic degradation on ethylene, and has the advantages of simple equipment and process, environmental protection and the like, so that the method has wide market and application prospect.
At present, research reports on photocatalytic ethylene oxide mainly focus on TiO2The base semiconductor photocatalyst, but the optical band gap of the base semiconductor photocatalyst is up to 3.2eV, can only absorb ultraviolet light with energy of about 5% in the solar spectrum, so that the efficiency of ethylene photocatalytic degradation is low. Therefore, the development of a novel high-efficiency and stable photocatalytic material for photocatalytic purification of ethylene has great application value. According to the basic principle of photocatalytic degradation of ethylene, a semiconductor photocatalyst with high efficiency for photocatalytic degradation of ethylene must satisfy the following three conditions: 1. the position of the bottom of the semiconductor conduction band must be higher than-0.33V (NHE); 2. the position of the valence band top of the semiconductor must be below +2.59V (NHE); 3. the bandgap of the semiconductor must be greater than 2.92 eV. However, it is difficult for most of the semiconductor photocatalysts to directly satisfy the above three conditions, and even if a few of the semiconductor photocatalysts satisfy the above three conditions, since the band gap thereof must be larger than 2.92eV, the semiconductor photocatalysts satisfying the above conditions can only absorb ultraviolet light, and solar energy cannot be sufficiently utilized.
Disclosure of Invention
The invention aims to provide CdS-Bi2WO6Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene, CdS-Bi2WO6The semiconductor Z-type heterojunction has high catalytic performance and stability on ethylene.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides CdS-Bi2WO6Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene, and CdS-Bi2WO6The semiconductor Z-type heterojunction is catalytically active towards ethylene.
Preferably, the CdS-Bi2WO6CdS and Bi in semiconductor Z-type heterojunction2WO6In a mass ratio of (0.1:100) to (E)(50:50)。
Preferably, the CdS-Bi2WO6CdS and Bi in semiconductor Z-type heterojunction2WO6The mass ratio of (1:100) to (50: 100).
Preferably, the CdS-Bi2WO6The ethylene concentration degraded by the semiconductor Z-type heterojunction is 1 ppb-10000 ppm.
Preferably, the CdS-Bi2WO6The preparation method of the Z-shaped heterojunction of the semiconductor comprises the following steps:
mixing sodium tungstate, bismuth nitrate, hexadecyl trimethyl ammonium bromide and water to obtain Bi2WO6；
The Bi is added2WO6Dispersed in water to obtain Bi2WO6A dispersion liquid;
the Bi is added2WO6Mixing the dispersion, cadmium acetate and thiourea to obtain CdS-Bi2WO6A semiconductor Z-type heterojunction.
Preferably, the sodium tungstate is sodium tungstate dihydrate, the bismuth nitrate is bismuth nitrate pentahydrate, and the molar ratio of the sodium tungstate to the bismuth nitrate is 2: 1.
Preferably, the mass ratio of the sodium tungstate to the hexadecyl trimethyl ammonium bromide is 0.33: 0.05.
Preferably, the temperature is 120 ℃ and the time is 24 h.
Preferably, the temperature of the second hydrothermal reaction is 80 ℃ and the time is 10 hours.
The invention provides CdS-Bi2WO6Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene, CdS-Bi2WO6The semiconductor Z-type heterojunction has high catalytic performance and stability on ethylene. The invention combines two narrow band gap semiconductors CdS and Bi2WO6To construct CdS-Bi2WO6The Z-shaped heterojunction of semiconductor makes full use of the strong reducibility of CdS and Bi2WO6Strong oxidizing property and simultaneously expands the absorption of the CdS-Bi in the visible light part of the solar spectrum2WO6Semiconductor heterojunction pairThe solar spectrum has a wide response range (200-600 nm), has good absorption performance on the solar spectrum, and can utilize sunlight to efficiently catalyze and degrade ethylene in air, so that the purpose of purifying ethylene is achieved.
The results of the examples show that CdS-Bi2WO6The semiconductor Z-type heterojunction has high-efficiency catalytic performance and stability on ethylene under simulated sunlight, namely has good photocatalytic activity and stability on photocatalytic purification of ethylene, and the practicability of the photocatalytic purification technology of ethylene is promoted.
CdS-Bi of the invention2WO6The semiconductor Z-type heterojunction photocatalyst has the characteristics of simple preparation and low cost, can eliminate ethylene gas in the atmosphere under the mild conditions of normal temperature and normal pressure, and has good application prospect and economic value under the low-temperature conditions of storage, preservation and the like of fruits and vegetables.
Drawings
FIG. 1 shows CdS-Bi prepared in examples 1-32WO6Semiconductor Z-type heterojunction and CdS and Bi in comparative examples 1-22WO6A graph for photocatalytic degradation of ethylene under simulated sunlight;
FIG. 2 is CdS-Bi prepared in example 12WO6And (3) a circulation stability diagram of photocatalytic degradation of ethylene by the semiconductor Z-type heterojunction under simulated sunlight.
Detailed Description
The invention provides CdS-Bi2WO6Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene, and CdS-Bi2WO6The semiconductor Z-type heterojunction is catalytically active towards ethylene.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
In the present invention, the CdS-Bi2WO6CdS and Bi in semiconductor Z-type heterojunction2WO6The mass ratio of (b) is preferably (0.1:100) - (50:50), (more preferably (0.1:99.9) - (50:100), and still more preferably (3-15): 100.
In bookIn the invention, the CdS-Bi2WO6The concentration of ethylene degraded by the semiconductor Z-type heterojunction is preferably 1ppb to 10000 ppm.
In the present invention, the CdS-Bi2WO6The method for preparing the semiconductor Z-type heterojunction preferably comprises the following steps:
mixing sodium tungstate, bismuth nitrate, hexadecyl trimethyl ammonium bromide and water, and carrying out a first hydrothermal reaction to obtain Bi2WO6；
The Bi is added2WO6Dispersed in water to obtain Bi2WO6A dispersion liquid;
the Bi is added2WO6Mixing the dispersion liquid, cadmium acetate and thiourea, and carrying out a second hydrothermal reaction to obtain CdS-Bi2WO6A semiconductor Z-type heterojunction.
In the present invention, the Bi2WO6The preparation method (D) is preferably carried out according to the method disclosed in the prior art (Nature Communications, DOI:10.1038/ncomms 9340.). In the invention, sodium tungstate, bismuth nitrate, hexadecyl trimethyl ammonium bromide and water are mixed for the first hydrothermal reaction to obtain Bi2WO6. In the present invention, the sodium tungstate is preferably sodium tungstate dihydrate, the bismuth nitrate is preferably bismuth nitrate pentahydrate, and the molar ratio of the sodium tungstate to the bismuth nitrate is preferably 2: 1. In the present invention, the mass ratio of sodium tungstate to cetyltrimethylammonium bromide is preferably 0.33: 0.05. In the invention, the water is preferably deionized water, and the using amount ratio of the water to the hexadecyl trimethyl ammonium bromide is preferably 80mL:0.5 g. The mixing process is not particularly limited in the invention, and the raw materials can be uniformly mixed by selecting the process well known in the field. After the mixing is finished, the mixture is preferably vigorously stirred for 12 hours, and then the first hydrothermal reaction is carried out; the conditions for vigorous stirring according to the present invention may be carried out according to the methods disclosed in the above-mentioned documents. In the present invention, the temperature of the first hydrothermal reaction is preferably 120 ℃ and the time is preferably 24 hours. After the first hydrothermal reaction is finished, the invention preferably naturally cools the obtained productCooling to room temperature, collecting the product by centrifugation, washing with deionized water for multiple times, and vacuum drying at 60 ℃ for 12 hours to obtain Bi2WO6And (3) powder.
To obtain Bi2WO6Then, the invention uses the Bi2WO6Dispersed in water to obtain Bi2WO6A dispersion liquid; the Bi is added2WO6Mixing the dispersion liquid, cadmium acetate and thiourea, and carrying out a second hydrothermal reaction to obtain CdS-Bi2WO6A semiconductor Z-type heterojunction. In the present invention, the dispersion is preferably carried out under ultrasonic and stirring conditions, and the ultrasonic and stirring conditions are not particularly limited in the present invention, and a process well known in the art may be selected. The invention is directed to the Bi2WO6The dosage ratio of the cadmium acetate and the thiourea has no special requirement, and meets the CdS-Bi2WO6CdS and Bi in semiconductor Z-type heterojunction2WO6The mass ratio of (A) to (B) is in the range of 0.1:100 to 50: 50. In the present invention, the mixing process is preferably performed by adding cadmium acetate to the Bi first2WO6Stirring the dispersion liquid for 2 hours, then adding thiourea, and uniformly stirring to perform the second hydrothermal reaction; the stirring process is not particularly limited in the present invention, and a process known in the art may be selected. In the present invention, the temperature of the second hydrothermal reaction is preferably 80 ℃ and the time is preferably 10 hours. After the second hydrothermal reaction is finished, the obtained product is preferably naturally cooled to room temperature, washed clean by clear water and dried for 12 hours in vacuum at the temperature of 60 ℃ to obtain CdS-Bi2WO6A semiconductor Z-type heterojunction.
In the preparation of CdS-Bi2WO6The specific role of the reagents used in the semiconductor Z-type heterojunction process is understood in accordance with well known roles in the art and will not be described in detail herein.
The invention pairs the CdS-Bi2WO6The method for photocatalytic degradation of ethylene by using the semiconductor Z-type heterojunction is not particularly limited, and a method well known in the art can be selected. In the test example of the invention, particularly in the simulation of the sunLight utilization of CdS-Bi2WO6Carrying out a catalytic performance test of photocatalytic degradation of trace ethylene gas in the atmosphere by using a semiconductor Z-shaped heterojunction; the specific implementation method comprises the following steps: CdS-Bi2WO6And the semiconductor Z-type heterojunction powder is paved at the bottom of the quartz reactor, and the reactor is sealed. Then, injecting ethylene gas by adopting a valve type micro-injector; placing the reactor in a dark place for 1 hour to ensure that the ethylene gas reaches adsorption-desorption balance on the surface of the photocatalyst; then, a simulated sunlight light source of a 300W xenon lamp is turned on for illumination, sampling is carried out once every 3 minutes, and the concentration of ethylene in the reactor is detected at any time by utilizing a gas chromatograph.
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
0.3300g of sodium tungstate dihydrate [ Na ] was added2WO4·2H2O]0.9700g of bismuth nitrate pentahydrate [ Bi (NO)3)3·5H2O]And 0.05g of cetyltrimethylammonium bromide [ CTAB: C16H33(CH3)3NBr]Adding the mixture into 80mL of deionized water, stirring vigorously for 12 hours, transferring the obtained solution into a 100 mL reaction kettle, carrying out a first hydrothermal reaction for 24 hours at 120 ℃, naturally cooling to room temperature, collecting the product by a centrifugal method, washing with deionized water for multiple times, and finally carrying out vacuum drying for 12 hours at 60 ℃ to obtain Bi2WO6Powder;
0.6978g of the Bi2WO6Ultrasonically dispersing the powder in 80ml of deionized water and violently stirring to obtain Bi2WO6The dispersion was then charged with 0.0416g of cadmium acetate [ Cd (CH)3CO2)2]After stirring thoroughly for 2 hours, 0.0119g of thiourea [ CH ] was added4N2S]Fully stirring, transferring to a 100 ml reaction kettle, carrying out a second hydrothermal reaction for 10 hours at 80 ℃, naturally cooling to room temperature, washing with clear water, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain CdS-Bi2WO6Semiconductor Z-type heterojunction powder, wherein CdS and Bi2WO6Is 3:100 and is marked as 3-CdS-Bi2WO6。
Example 2
In this example, Bi2WO6The preparation method of the powder is the same as that of example 1;
0.6978g of the Bi2WO6Ultrasonically dispersing the powder in 80ml of deionized water and violently stirring to obtain Bi2WO6The dispersion was then charged with 0.0970g of cadmium acetate [ Cd (CH)3CO2)2]After stirring thoroughly for 2 hours, 0.0277g of thiourea [ CH ] was added4N2S]Fully stirring, transferring to a 100 ml reaction kettle, carrying out a second hydrothermal reaction for 10 hours at 80 ℃, naturally cooling to room temperature, washing with clear water, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain CdS-Bi2WO6Semiconductor Z-type heterojunction powder, wherein CdS and Bi2WO6Is 7:100 and is marked as 7-CdS-Bi2WO6。
Example 3
In this example, Bi2WO6The preparation method of the powder is the same as that of example 1;
0.6978g of the Bi2WO6Ultrasonically dispersing the powder in 80ml of deionized water and violently stirring to obtain Bi2WO6The dispersion was then charged with 0.2079g of cadmium acetate [ Cd (CH)3CO2)2]After stirring thoroughly for 2 hours, 0.0594g of thiourea [ CH ] was added4N2S]Fully stirring, transferring to a 100 ml reaction kettle, carrying out a second hydrothermal reaction at 80 ℃ for 10 hours, naturally cooling to room temperature, washing with clear water, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain CdS-Bi2WO6Semiconductor Z-type heterojunction powder, wherein CdS and Bi2WO6Is 15:100 and is marked as 15-CdS-Bi2WO6。
Comparative example 1
1.3330g of cadmium acetate [ Cd (CH) ]3CO2)2]Added to 80ml of deionized water and stirred vigorously, and then 0.3810g of thiourea [ CH ] was added4N2S]Adding the solution into the solution, continuously stirring, fully stirring, transferring to a 100 ml reaction kettle, carrying out hydrothermal reaction for 10 hours at 80 ℃, then naturally cooling to room temperature, washing with clear water, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain the nano CdS powder.
And taking the CdS powder as a comparative example 1 to perform subsequent photocatalytic degradation performance research.
Comparative example 2
Bi prepared in example 12WO6The powder was used as comparative example 2 for subsequent photocatalytic degradation performance study.
Test example
1) For CdS-Bi in simulated sunlight2WO6The catalytic performance of the semiconductor Z-type heterojunction powder for photocatalytic degradation of trace ethylene gas in the atmosphere is tested:
the implementation process is as follows: 0.3g CdS-Bi are weighed2WO6The semiconductor Z-shaped heterojunction powder is paved at the bottom of a quartz reactor with the volume of 500 ml, and the reactor is sealed; then, 50. mu.l of ethylene gas was injected using a valve-type microinjector so that the ethylene concentration in the reactor became 100 ppm. Placing the reactor in a dark place for 1 hour to ensure that the ethylene gas reaches adsorption-desorption balance on the surface of the photocatalyst; then, a simulated sunlight light source of a 300W xenon lamp is turned on for illumination, sampling is carried out once every 3 minutes, and the concentration of ethylene in the reactor is detected at any time by utilizing a gas chromatograph.
The test results are shown in FIG. 1, where curve 1 represents CdS (comparative example 1) and curve 2 represents Bi2WO6(comparative example 2), Curve 3 represents 3-CdS-Bi2WO6A semiconductor Z-type heterojunction (example 1),curve 4 represents 7-CdS-Bi2WO6Semiconductor Z-type heterojunction (example 2), Curve 5 represents 15-CdS-Bi2WO6Semiconductor Z-type heterojunctions (example 3). As can be seen from the figure, under the irradiation of simulated sunlight, when the curve 1 shows that only CdS exists (comparative example 1), the ethylene concentration in the reactor is 80ppm after 15 minutes, and the ethylene degradation rate is only 20%; curve 2 is Bi alone2WO6In the presence (comparative example 2), the ethylene concentration in the reactor was still 100ppm after 15 minutes, without any degradation of ethylene at all; curve 3 is 3-CdS-Bi2WO6When the semiconductor heterojunction exists, the ethylene concentration in the reactor is reduced to 10.2ppm after 15 minutes, and the degradation rate of ethylene reaches about 90%; curve 4 is 7-CdS-Bi2WO6In the presence of a semiconductor heterojunction, the ethylene concentration in the reactor after 15 minutes was reduced to 0ppm (already below the detection limit of gas chromatography by 0.1ppm), and ethylene was completely degraded; curve 5 is 15-CdS-Bi2WO6In the presence of a semiconductor heterojunction, the ethylene concentration in the reactor dropped to 64.7ppm after 15 minutes, and the ethylene degradation rate was about 35%. Thus, CdS-Bi2WO6The semiconductor Z-type heterojunction shows excellent performance of photocatalysis purification of low-concentration ethylene in air under simulated sunlight, and has very strong practical application value.
2) And (3) testing the cycling stability:
CdS-Bi prepared in example 1) according to the procedure of test example 1)2WO6The semiconductor Z-type heterojunction is continuously subjected to three photocatalytic degradation experiments under the same conditions, and the CdS-Bi is directly subjected to the first photocatalytic degradation experiment without any treatment after the first photocatalytic degradation experiment2WO6The semiconductor Z-type heterojunction is used for the next test, and the cycle stability result is shown in figure 2, and the graph shows that CdS-Bi2WO6The Z-type heterojunction of the semiconductor shows good stability in three-time cyclic degradation tests, and provides good guarantee for the practical application of the Z-type heterojunction.
As can be seen from the above examples, the present invention provides CdS-Bi2WO6Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene, and CdS-Bi2WO6Semiconductor device and method for manufacturing the sameThe Z-type heterojunction has high-efficiency catalytic performance and stability on ethylene under simulated sunlight, namely has good photocatalytic activity and stability on photocatalytic purification of ethylene, and the practicability of the photocatalytic purification technology of ethylene is promoted.
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 (9)
1. CdS-Bi2WO6The application of the semiconductor Z-type heterojunction in photocatalytic degradation of ethylene is characterized in that CdS-Bi2WO6The semiconductor Z-type heterojunction is catalytically active towards ethylene.
2. Use according to claim 1, wherein the CdS-Bi is2WO6CdS and Bi in semiconductor Z-type heterojunction2WO6The mass ratio of (1:100) to (50: 50).
3. Use according to claim 1, wherein the CdS-Bi is2WO6CdS and Bi in semiconductor Z-type heterojunction2WO6The mass ratio of (1:100) to (20: 100).
4. Use according to claim 1, wherein the CdS-Bi is2WO6The ethylene concentration degraded by the semiconductor Z-type heterojunction is 1 ppb-10000 ppm.
5. Use according to any one of claims 1 to 4, wherein the CdS-Bi2WO6The preparation method of the Z-shaped heterojunction of the semiconductor comprises the following steps:
mixing sodium tungstate, bismuth nitrate, hexadecyl trimethyl ammonium bromide and water, and carrying out a first hydrothermal reaction to obtain Bi2WO6；
The Bi is added2WO6Dispersed in water to obtain Bi2WO6A dispersion liquid;
the Bi is added2WO6Mixing the dispersion liquid, cadmium acetate and thiourea, and carrying out a second hydrothermal reaction to obtain CdS-Bi2WO6A semiconductor Z-type heterojunction.
6. The use of claim 5, wherein the sodium tungstate is sodium tungstate dihydrate, the bismuth nitrate is bismuth nitrate pentahydrate, and the molar ratio of the sodium tungstate to the bismuth nitrate is 2: 1.
7. Use according to claim 5 or 6, wherein the mass ratio of sodium tungstate to cetyltrimethylammonium bromide is 0.33: 0.05.
8. The use according to claim 5, wherein the first hydrothermal reaction is carried out at a temperature of 120 ℃ for a period of 24 hours.
9. The use according to claim 5, wherein the temperature of the second hydrothermal reaction is 80 ℃ and the time is 10 h.
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