CN111437824B - 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst and preparation method and application thereof - Google Patents
3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims description 28
- 239000000725 suspension Substances 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 6
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- 230000007935 neutral effect Effects 0.000 claims abstract description 4
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- 238000001816 cooling Methods 0.000 claims abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000007146 photocatalysis Methods 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 5
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
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- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
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- 230000015556 catabolic process Effects 0.000 abstract 1
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- 238000004519 manufacturing process Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
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- 239000007789 gas Substances 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
Abstract
The invention belongs to the technical field of catalysis, and particularly relates to a 3D layered micro-flower structure CoWO4@Bi2WO6The visible light catalyst and the preparation method and application thereof, the preparation method is that Bi (NO) is prepared3)3·5H2Dissolving O in HNO by ultrasonic3In, Na is added2WO4The solution was stirred to form a white suspension, and CoWO was added4Stirring, transferring to a high-pressure autoclave for reaction, cooling to room temperature, collecting a sample, washing until the pH value of a supernatant is neutral, and drying to obtain a target product. 3D layered micro-flower structure CoWO4@Bi2WO6Catalytic synthesis of H within 90min without any carbon emissions or pollutants and any co-catalyst involvement2O2The yield reaches 67 mu mol/L. The method has the characteristics of simplicity, convenience, high efficiency, low cost and high visible light absorption degree, and can be applied to the fields of photocatalytic preparation of hydrogen peroxide, degradation of organic matters and the like.
Description
Technical Field
The invention relates to a visible light response 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst and preparation of H in photocatalysis by using same2O2The application of the aspect is mainly aimed at industrial large-scale production of H2O2Belonging to the field of high value-added chemical production.
Background
The photocatalysis technology is a mature green technology which has low cost and high performance and can not cause secondary pollution, has potential application prospect in the aspects of green oxidative degradation and green synthesis, has obvious removal effect on pollutants seriously threatening the health of human beings in the natural environment, relieves the problem of insufficient energy demand, and has been generally concerned by researchers at home and abroad.
Hydrogen peroxide (H)2O2) Is one of the most important 100 chemical substances in the world, and is an eco-friendly energy carrier, an oxidant and an environment restoration agent. Conventional H2O2The industrial synthesis methods of (a) have limited practical applications due to the complex processes, high costs and the production of large amounts of waste toxic by-products. In recent years, photocatalytic production of H2O2The method has received more and more attention from people because the process only needs water, oxygen and sunshine as raw materials, converts low-density solar energy into storable chemical energy, and has the advantages of no secondary pollution, simple equipment, less investment, high yield and the like. In this solar-fueled process, the catalyst, driven by the sun's light, produces photoexcited electrons that reduce oxygen and produce H2O2This can be accomplished by a multi-step single electron or one-step dual electron type process. In early attempts, inorganic semiconductor photocatalysts have been widely used for producing H2O2E.g. TiO2Systems, usually by being at O2Carrying out O on a conduction band under the irradiation of ultraviolet light in saturated water2Reduction to form H2O2. Photo-generated electron promoted O2Reduction of two electrons and generation of H2O2. However, due to TiO2To H2O2Is low and in the course of the photocatalytic reaction, H is produced2O2Irradiated ultraviolet ray (lambda)<400nm) and thus the production efficiency is very low. In addition, the recombination of photogenerated electrons and electron holes results in low photon yield, and the practical application of the photoelectrocatalysis technology is limited.
Research shows that the n-type semiconductor Bi2WO6Due to the characteristics of low cost, proper band gap energy, good light stability and the like, the material becomes one of the best candidates for reducing environmental pollution, producing and storing energy sources and various scientific activities of various devices. But of Bi alone2WO6The semiconductor still has the phenomenon that photogenerated charges are easy to recombine, and in order to reduce the recombination probability and enhance the light absorption capacity, designing and constructing a good conduction-valence band matching photocatalytic heterostructure is a very effective strategy.
Disclosure of Invention
One of the purposes of the invention is to provide a 3D layered micro-flower structure CoWO with visible light response and improved photo-generated electrons and photo-generated holes4@Bi2WO6A Z-type heterojunction catalyst and a preparation method thereof.
Another purpose of the invention is to provide CoWO using 3D layered floret structure4@Bi2WO6Photocatalytic preparation of H by Z-type heterojunction catalyst2O2The method of (1).
In order to achieve the purpose, the invention adopts the technical scheme that: 3D layered micro-flower structure CoWO4@Bi2WO6The preparation method of the Z-type heterojunction composite catalyst comprises the following steps: adding Bi (NO)3)3·5H2Dissolving O in HNO by ultrasonic3In, Na is slowly added2WO4The solution is stirred vigorously to form a white suspension, and CoWO is added4Stirring for 30min, transferring the suspension into a Teflon-lined autoclave for reaction, cooling to room temperature, collecting the obtained light yellow sample, washing with deionized water for several times until the pH value of the supernatant is neutral, and drying in an oven at 60 ℃ for 8h to obtain the target product.
Preferably, the 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst in mass ratio, CoWO4：Bi(NO3)3·5H2O is 58: 485.
preferably, the 3D layered micro-flower structure CoWO4@Bi2WO6The Z-type heterojunction composite catalyst is heated at 160 ℃ for 20 hours.
Preferably, the 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst, and a process for producing the sameThe CoWO mentioned4The preparation method comprises the following steps: separately taking Na2WO4·2H2O、CoCl2·6H2O、KNO3And NaNO3Mixing, grinding the mixture for 30min, placing into a crucible with a cover, transferring into a muffle furnace for calcining to obtain gray powder, washing with deionized water for 5 times, and drying in an oven at 60 deg.C for 8 hr to obtain CoWO4。
Preferably, the 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst, in molar ratio, Na2WO4·2H2O：CoCl2·6H2O：KNO3：NaNO3＝1:1:30:30。
Preferably, the 3D layered micro-flower structure CoWO4@Bi2WO6And the Z-type heterojunction composite catalyst is calcined in air at 500 ℃ for 6 hours.
The 3D layered micro-flower structure CoWO4@Bi2WO6The application of the Z-type heterojunction composite catalyst in preparing hydrogen peroxide by photocatalysis.
Preferably, the above application, method is as follows: the 3D layered micro-flower structure CoWO is adopted4@Bi2WO6Adding Z-type heterojunction composite catalyst into deionized water, performing ultrasonic treatment for 10min, adjusting pH to acidity, and adding O2Introducing into the suspension, bubbling in the solution continuously and uniformly, magnetically stirring in dark for 60min to reach adsorption-desorption equilibrium before irradiation, and irradiating with light source for reaction.
Preferably, for the above applications, the pH is adjusted by HClO4The pH of the suspension was adjusted to 3.
Preferably, in the application, a 300W xenon lamp is used as a light source for illumination, and the lambda of the xenon lamp is more than or equal to 420 nm.
The invention has the beneficial effects that: the invention passes through CoWO4And Bi2WO6The two materials are compounded, so that the photoresponse range and the photocatalytic performance are further improved, and the photocatalytic performance is improvedThe efficiency of capturing photons is improved, the recombination of electron hole pairs is inhibited, the utilization rate of transition of electrons from a valence band to a conduction band is improved, and the photocatalytic activity is improved. With the process of the present invention, there is a high hydrogen peroxide (H) without any carbon emissions or pollutants and any co-catalyst involved2O2) Yield, within 90min, H2O2The yield reaches 67 mu mol/L, for producing H2O2Provides a green synthetic route and sustainable technology.
The method has the characteristics of simplicity, convenience, high efficiency, low cost and high visible light absorption, and the prepared 3D layered micro-flower structure CoWO4@Bi2WO6The catalytic material has the characteristics of narrow band gap, large specific surface area and high catalytic activity, has good visible light absorption performance and stability, high photoinduced charge transfer efficiency and good effect of preparing hydrogen peroxide by photocatalysis, and can be applied to the fields of preparing hydrogen peroxide by photocatalysis, degrading organic matters and the like.
Drawings
FIG. 1 is a 3D layered micro-floral structure CoWO4@Bi2WO6SEM image of heterojunction composite catalyst, wherein a is overall view, b is detail enlargement
FIG. 2 is Bi2WO6、CoWO4And CoWO4@Bi2WO6XRD pattern of (a).
FIG. 3 is a graph of different gas environments vs. H2O2The resulting effect.
FIG. 4 is the different pH vs. H2O2The resulting effect.
FIG. 5 shows Bi under irradiation of visible light2WO6、CoWO4And CoWO4@Bi2WO6Yielding a hydrogen peroxide concentration.
Detailed Description
Example 13D lamellar micro-floral Structure CoWO4@Bi2WO6Preparation of Z-type heterojunction composite catalyst
(I) 3D lamellar micro-flower Structure CoWO4Preparation of
1mol of Na was weighed out separately2WO4·2H2O, 1mol of CoCl2·6H2O, 30mol KNO3And 30mol of NaNO3Are mixed together. The mixture was then ground for 30min, placed in a covered crucible, transferred to a muffle furnace and calcined in air at 500 ℃ for 6 h. Finally obtaining gray powder, washing the gray powder for 5 times by using deionized water, and drying the gray powder in an oven at the temperature of 60 ℃ for 8 hours to obtain CoWO4。
(II) 3D layered micro-flower structure CoWO4@Bi2WO6Preparation of Z-type heterojunction composite catalyst
Weigh 1.94g Bi (NO)3)3·5H2Dissolving O in 60mL of 0.4mol/L HNO by ultrasonic3In (1). Then 20mL of 0.05mol/L Na was slowly added2WO4The solution was vigorously stirred to form a white suspension, and 0.232g of CoWO was added4And stirring for 30 min. Finally, the suspension was transferred to a teflon-lined autoclave, heated at 160 ℃ for 20h, cooled to room temperature and the resulting pale yellow sample collected, washed several times with deionized water until the pH of the supernatant was neutral, dried in an oven at 60 ℃ for 8h to give CoWO4@Bi2WO6A composite material.
As can be seen from FIG. 1a, the composite material is a 3D layered micro-flower structure; further magnification (FIG. 1b) shows that CoWO4The nano particles are embedded in Bi2WO6The surface of the petal forms a heterojunction, and the XRD spectrum of figure 2 confirms that the composite material is CoWO4@Bi2WO6。
Example 2 different gas Environment Pair H2O2Influence of generation
The method comprises the following steps: weighing 3D layered floret structure CoWO4@Bi2WO6And adding 50mg of Z-type heterojunction composite catalyst into 50mL of deionized water, and carrying out ultrasonic treatment for 10 min. Then using HClO4The pH of the suspension was adjusted to 3. Respectively adding N2Air and O2The suspension was passed through to allow continuous uniform bubbling through the solution. Magnetic stirring was then carried out in the dark for 60min to reach the adsorption-desorption equilibrium before irradiation. Using 300W xenon lamps(lambda is more than or equal to 420nm) as a light source to irradiate the mixture for reaction. During the reaction, 4mL of the suspension was extracted from the reaction cell every 30min and centrifuged at 10000rpm for 1 min. Reuse KMnO4Redox titration method for H determination2O2The amount of production of (c).
Testing of CoWO in Nitrogen, air and oxygen environments, respectively4@Bi2WO6Photocatalytic production of H2O2The performance, results are shown in FIG. 3. CoWO when replacing oxygen environment with air4@Bi2WO6H of (A) to (B)2O2The production of (2) is reduced, which indicates that oxygen conditions are for photocatalytic H2O2Is facilitated. When using N2In place of oxygen atmosphere, CoWO4@Bi2WO6Above only a small amount of H2O2And (4) generating. Meanwhile, H cannot be detected without visible light radiation or photocatalyst2O2This indicates that the photocatalyst, visible light irradiation and oxygen all produce H2O2Are important factors of.
Example 3 pH vs H2O2Influence of generation
The method comprises the following steps: weighing 3D layered floret structure CoWO4@Bi2WO6And adding 50mg of Z-type heterojunction composite catalyst into 50mL of deionized water, and carrying out ultrasonic treatment for 10 min. Then using HClO4The pH values of the suspensions were adjusted to 1, 3 and 5, respectively. Then adding O2The suspension was passed through to allow continuous uniform bubbling through the solution. Magnetic stirring was then carried out in the dark for 60min to reach the adsorption-desorption equilibrium before irradiation. The mixture was irradiated with a 300W xenon lamp (. lamda. gtoreq.420 nm) as a light source to carry out the reaction. During the reaction, 4mL of the suspension was extracted from the reaction cell every 30min and centrifuged at 10000rpm for 1 min. Reuse KMnO4Redox titration method for H determination2O2The amount of production of (c).
Testing CoWO separately in different pH systems4@Bi2WO6Photocatalytic production of H2O2The performance, results are shown in figure 4. When pH is 3, H within 90min2O2Is produced in a large amountTo 67. mu. mol. L-1When the pH is 1, only 35. mu. mol. L is formed in 90min-1H of (A) to (B)2O2This may be due to H being generated2O2Is gradually oxidized to H by excess protons2O(H2O2+2H ++2e-＝2H2O). When the pH was further increased to 5, H2O2The amount of the produced (C) is remarkably reduced. The above results indicate that pH 3 is photocatalytic H production2O2The optimum pH value of (1).
Example 43D lamellar micro-floral Structure CoWO4@Bi2WO6Preparation of H by catalysis of Z-type heterojunction composite catalyst2O2
Separately weighing Bi2WO6、CoWO4And CoWO4@Bi2WO650mg each was added to 50mL of deionized water and sonicated for 10 min. Then using HClO4The pH of the suspension was adjusted to 3. Mixing O with2The suspension was passed through to allow continuous uniform bubbling through the solution. Magnetic stirring was then carried out in the dark for 60min to reach the adsorption-desorption equilibrium before irradiation. The mixture was irradiated with a 300W xenon lamp (. lamda. gtoreq.420 nm) as a light source to carry out the reaction. During the reaction, 4mL of the suspension was extracted from the reaction cell every 30min and centrifuged at 10000rpm for 1 min. Reuse KMnO4Redox titration method for H determination2O2The amount of production of (c).
Adopts different photocatalysts to test the photocatalytic H production2O2Performance, results are shown in FIG. 5, CoWO4@Bi2WO6Z-type heterojunction composite catalyst photocatalysis H production2O2The effect of (A) is better than that of a single-component photocatalyst. After reaction for 90min, CoWO4@Bi2WO6H of (A) to (B)2O2The yield reaches a maximum of about 67. mu. mol/L, which is Bi alone2WO6H of (A) to (B)2O21.8 times the amount produced.
Claims (10)
1. 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction recombinationThe catalyst is characterized in that the preparation method comprises the following steps: adding Bi (NO)3)3·5H2Dissolving O in HNO by ultrasonic3In, Na is slowly added2WO4The solution is stirred vigorously to form a white suspension, and CoWO is added4Stirring for 30min, transferring the suspension into a Teflon-lined autoclave for reaction, cooling to room temperature, collecting the obtained light yellow sample, washing with deionized water for several times until the pH value of the supernatant is neutral, and drying in an oven at 60 ℃ for 8h to obtain the target product.
2. 3D lamellar micro-floral structure CoWO according to claim 14@Bi2WO6Z-type heterojunction composite catalyst, characterized in that, in terms of mass ratio, CoWO4：Bi(NO3)3·5H2O is 58: 485.
3. 3D lamellar micro-floral structure CoWO according to claim 14@Bi2WO6The Z-type heterojunction composite catalyst is characterized in that the reaction is carried out by heating at 160 ℃ for 20 hours.
4. 3D lamellar micro-floral structure CoWO according to claim 14@Bi2WO6Z-type heterojunction composite catalyst, characterized in that the CoWO4The preparation method comprises the following steps: separately taking Na2WO4·2H2O、CoCl2·6H2O、KNO3And NaNO3Mixing, grinding the mixture for 30min, placing into a crucible with a cover, transferring into a muffle furnace for calcining to obtain gray powder, washing with deionized water for 5 times, and drying in an oven at 60 deg.C for 8 hr to obtain CoWO4。
5. 3D lamellar micro-floral structure CoWO according to claim 44@Bi2WO6Z-type heterojunction composite catalyst characterized in that Na is added in a molar ratio2WO4·2H2O：CoCl2·6H2O：KNO3：NaNO3＝1:1:30:30。
6. 3D lamellar micro-floral structure CoWO according to claim 44@Bi2WO6The Z-type heterojunction composite catalyst is characterized in that the calcination is carried out in air at 500 ℃ for 6 h.
7. 3D lamellar micro-floral structure CoWO according to claim 14@Bi2WO6The application of the Z-type heterojunction composite catalyst in preparing hydrogen peroxide by photocatalysis.
8. Use according to claim 7, characterized in that the method is as follows: the 3D layered micro-flower structure CoWO of claim 14@Bi2WO6Adding Z-type heterojunction composite catalyst into deionized water, performing ultrasonic treatment for 10min, adjusting pH to acidity, and adding O2Introducing into the suspension, bubbling in the solution continuously and uniformly, magnetically stirring in dark for 60min to reach adsorption-desorption equilibrium before irradiation, and irradiating with light source for reaction.
9. The use of claim 8, wherein the pH is adjusted using HClO4The pH of the suspension was adjusted to 3.
10. The application of claim 9, wherein the light source is a 300W xenon lamp with a lambda of 420nm or more.
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| CN113173665B (en) * | 2021-03-31 | 2022-10-04 | 沈阳化工大学 | ZnWO 4 /MgWO 4 Method for degrading organic wastewater by using composite semiconductor material |
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