CN109482172B - Degraded NOxBi/CeO of (A)2Composite photocatalyst and preparation method thereof - Google Patents
Degraded NOxBi/CeO of (A)2Composite photocatalyst and preparation method thereof Download PDFInfo
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 10
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B01J35/39—
-
- B01J35/40—
Abstract
The invention discloses a method for degrading NOxBi/CeO of (A)2A composite photocatalyst and a preparation method thereof belong to the technical field of photocatalysis, and the composite photocatalyst is prepared by loading Bi particles on CeO2The nano flower ball-shaped structure is formed on the nano sheet, the diameter of the formed nano flower ball is 1-4 mu m, and the visible light absorption band edge is about 510 nm; the method specifically comprises the following steps: (1) preparation of CeO2Powder; (2) adding CeO2Dissolving in glycol to prepare Bi/CeO2Composite photocatalyst, which can be used for degrading NO in airx. The composite photocatalyst has the characteristics of good stability, high separation efficiency of photo-generated electrons and good catalytic activity.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a catalyst suitable for degrading NOxBi/CeO of (A)2The nanometer flower-shaped ball composite photocatalyst and the preparation method and the application thereof.
Background
In the modern society, economy develops rapidly, but inevitably, people suffer from environmental pollution, which not only seriously hinders the rapid development of economy, but also poses great threat to the whole biological world. Gas pollution (CO, NO)2Etc.), the constant consumption of non-renewable energy sources such as fossil fuels, etc., will make us face serious challenges, and most importantly, human beings face more health crisis. In recent years, studies for removing low-concentration NOx by green light catalytic technology have been receiving more and more attention. TiO 22,CeO2The semiconductor photocatalysts such as BiOX and the like are limited in various aspects, such as: narrow light absorption range, low carrier separation and transfer efficiency, poor conductivity, weak oxidation ability and the like. Currently, an environment-friendly photocatalyst is required to be found for removing NOx in air with high efficiency.
Although these conventional photocatalysts have many disadvantages, they have a high specific surface area, are non-toxic, rich in raw materials and inexpensive and are still the focus of research. In order to put the materials into application more widely to control morphology, heterojunction is constructed, and valence band conductance is adjustedThe method comprises the steps of zone position, ion doping, introduction of a high-conductivity material, introduction of a material with strong visible light absorption, plasma metal surface modification and the like. In the case of CeO2The stability of the material is poor, and the band gap is close to TiO2The low efficiency of photogenerated electron separation greatly limits its applications.
Disclosure of Invention
In order to solve the existing CeO2The problems of poor stability, low separation efficiency of photoproduction electrons and poor catalytic activity exist, and the invention provides a method for degrading NOxBi/CeO of (A)2A composite photocatalyst is provided.
Meanwhile, the invention also provides the NO degrading agentxBi/CeO of (A)2Preparation method of composite photocatalyst and application of composite photocatalyst in degrading NOxApplication of the aspect.
The technical scheme adopted by the invention is as follows:
1. degraded NOxBi/CeO of (A)2The preparation method of the composite photocatalyst is characterized by comprising the following steps:
(1) dissolving glucose, acrylamide and cerous nitrate in deionized water, stirring, dropwise adding ammonia water to adjust the pH to 10, carrying out hydrothermal reaction in a high-pressure hydrothermal kettle at 160-200 ℃ for 70-80 h, cooling the hydrothermal reaction kettle to room temperature, washing the reaction product with deionized water and absolute ethyl alcohol for multiple times, and putting the reaction product into an oven for full drying to obtain CeO2The powder of (4);
(2) adding CeO2Dissolving in glycol at a mol ratio of CeO2: weighing Bi (HNO) in a ratio of 6-20: 13)·5H2Adding O into the solution, fully stirring, then transferring to a high-pressure hydrothermal kettle, reacting at 150-200 ℃ for 10-14 h, naturally cooling after the reaction is finished, washing the reaction product for multiple times by using deionized water and absolute ethyl alcohol, and fully drying in an oven to obtain Bi/CeO2A composite photocatalyst is provided.
Further limiting, in the step (1), the molar ratio of glucose, acrylamide and cerium nitrate is as follows: 1-3: 2-5: 1.
Further limiting, in the step (1), the molar ratio of glucose, acrylamide and cerium nitrate is as follows: 2:3:1.
Further limiting, the temperature of the hydrothermal reaction of the high-pressure hydrothermal kettle in the step (1) is 180 ℃, and the time is 72 hours; the temperature of the hydrothermal reaction of the high-pressure hydrothermal kettle in the step (2) is 160 ℃, and the time is 12 hours.
Further defined, CeO in the step (2)2：Bi＝10:1。
Further defined by degrading NO as described abovexBi/CeO of (A)2Preparation method of composite photocatalyst prepared from Bi/CeO2A composite photocatalyst is provided.
Further defined, the catalyst is prepared by loading Bi particles on CeO2The diameter of the formed nano flower ball is 1-4 mu m, and the visible light absorption band edge is 510 nm.
Further defined, the CeO2The thickness of the nano-sheet is 0.5-2.5 nm, and the diameter of the Bi particles is about 50-200 nm.
Further defined, the above-mentioned Bi/CeO2Composite photocatalyst for degrading NO in air under visible light conditionxApplication of the aspect.
Further defined, the Bi/CeO of claim 62The composite photocatalyst is coated on a wall, a road surface or trees as a coating, and can play a role of dyeing inorganic dye and simultaneously carry out NO dyeing on the wall, the road surface or the trees under the condition of visible lightxAnd carrying out catalytic degradation.
The degraded NO provided by the inventionxBi/CeO of (A)2The composite photocatalyst is formed by attaching Bi particles to CeO2Surface to CeO2The surface is modified by plasma, and the existence of Bi nano particles greatly improves the CeO2In particular with respect to NOxAnd the presence of Bi particles greatly reduces the secondary pollutant NO2The invention greatly improves the charge separation efficiency, inhibits the recombination of photon-generated carriers, improves the photoresponse capability and greatly improves the photocatalytic activity of the photon-generated carriers, and the invention adopts a hydrothermal and reduction method to synthesize the compound so that Bi/CeO2The composite material shows excellent photocatalytic activity, is light green and isAn inorganic dye can be used as substitute for chemical dye to reduce environmental pollution, especially NOx, and has low NO content when degrading NO2Production, when in water, of 3NO2+2H2O＝＝2HNO3+ NO, 1 part NO 21/3 NO is generated after dissolving in water, and the catalyst can be used for catalytic degradation again, and the cycle is repeated, so that the concentration of NO and NO are finally obtained2And (4) infinitely diluting. And NO adsorbed on the surface of the catalyst3 -And the catalyst can continuously recover the original activity through the washing of rainwater and the like, manual cleaning is not needed, the degradation problem of outdoor air pollution is well solved, and the preparation method disclosed by the invention also has the advantages of low price, no toxicity, simplicity, high safety coefficient and the like.
Drawings
FIG. 1 shows Bi/CeO prepared in example 1 of the present invention2Composite photocatalyst and CeO2An XRD pattern of (a);
FIG. 2 shows Bi/CeO prepared in example 1 of the present invention2Composite photocatalyst and CeO2SEM image of (a);
FIG. 3 shows Bi/CeO prepared in example 1 of the present invention2Composite photocatalyst and CeO2UV-vis DRS map of (1);
FIG. 4 shows Bi/CeO prepared in example 1 of the present invention2Composite photocatalyst and CeO2NO removal rate profile;
FIG. 5 shows Bi/CeO prepared in example 1 of the present invention2Composite photocatalyst and CeO2By-product NO2And (4) concentration graph.
Detailed Description
The technical solution of the present invention will be further explained with reference to the drawings and examples, but the present invention is not limited to the following implementation cases.
Example 1
Degraded NOxBi/CeO of (A)2The preparation method of the composite photocatalyst is specifically realized by the following steps:
(1) dissolving 0.01mol of glucose, 0.015mol of acrylamide and 0.005mol of cerium nitrate in 60mL of deionized water, and stirringStirring for 15min, gradually adding ammonia water to adjust pH to about 10, stirring for 3h, performing hydrothermal reaction in a high-pressure hydrothermal kettle at 180 ℃ for 72h, cooling the hydrothermal reaction kettle to room temperature, washing the reaction product with deionized water and absolute ethyl alcohol for 3 times, putting the reaction product into an oven, and fully drying to obtain CeO2The powder of (4).
(2) Adding CeO2Dissolving in 50mL of glycol at a mol ratio of CeO2: weighing Bi (HNO) according to the proportion of 10:13)·5H2Adding O into the solution, fully stirring, then transferring to a high-pressure hydrothermal kettle, reacting at 160 ℃ for 12h, waiting for the reaction to be finished and naturally cooling, washing the reaction product for multiple times by using deionized water and absolute ethyl alcohol, putting into an oven for fully drying, taking out the dried precipitate, and grinding to obtain light green Bi/CeO2A composite photocatalyst is provided.
Example 2
Degraded NOxBi/CeO of (A)2The preparation method of the composite photocatalyst is specifically realized by the following steps:
(1) dissolving 0.005mol of glucose, 0.01mol of acrylamide and 0.005mol of cerium nitrate in 60mL of deionized water, stirring for 30min, dropwise adding ammonia water to adjust the pH value to about 10, stirring for 3h, carrying out hydrothermal reaction for 80h at 160 ℃ in a high-pressure hydrothermal kettle, cooling the temperature of the hydrothermal reaction kettle to room temperature, washing the reaction product for 5 times with deionized water and absolute ethyl alcohol, putting the reaction product into an oven, and fully drying to obtain CeO2The powder of (4).
(2) Adding CeO2Dissolving in 50mL of glycol at a mol ratio of CeO2: weighing Bi (HNO) according to the proportion of Bi 6:13)·5H2Adding O into the solution, fully stirring, then transferring to a high-pressure hydrothermal kettle, reacting for 14h at 150 ℃, after the reaction is finished and the temperature is naturally reduced, cleaning the reaction product for multiple times by using deionized water and absolute ethyl alcohol, putting the reaction product into an oven for full drying, taking out the dried precipitate, and grinding to obtain light green Bi/CeO2A composite photocatalyst is provided.
Example 3
Degraded NOxBi/CeO of (A)2The preparation method of the composite photocatalyst is specifically realized by the following steps:
(1) dissolving 0.015mol of glucose, 0.025mol of acrylamide and 0.005mol of cerium nitrate in 60mL of deionized water, stirring for 20min, dropwise adding ammonia water to adjust the pH value to about 10, stirring for 3h, carrying out hydrothermal reaction in a high-pressure hydrothermal kettle at 200 ℃ for 70h, cooling the temperature of the hydrothermal reaction kettle to room temperature, washing the reaction product for 3 times by using the deionized water and absolute ethyl alcohol, putting the reaction product into an oven, and fully drying to obtain CeO2The powder of (4).
(2) Adding CeO2Dissolving the mixture in 80mL of glycol according to the molar ratio of CeO2: weighing Bi (HNO) according to the proportion of 20:13)·5H2Adding O into the solution, fully stirring, then transferring to a high-pressure hydrothermal kettle, reacting at 200 ℃ for 10h, waiting for the reaction to be finished and naturally cooling, washing the reaction product for multiple times by using deionized water and absolute ethyl alcohol, putting into an oven for fully drying, taking out the dried precipitate, and grinding to obtain light green Bi/CeO2A composite photocatalyst is provided.
Example 4
Degraded NOxBi/CeO of (A)2The preparation method of the composite photocatalyst is specifically realized by the following steps:
(1) dissolving 0.01mol of glucose, 0.02mol of acrylamide and 0.005mol of cerium nitrate in 60mL of deionized water, stirring for 15min, dropwise adding ammonia water to adjust the pH value to about 10, stirring for 2h, carrying out hydrothermal reaction at 180 ℃ for 75h in a high-pressure hydrothermal kettle, cooling the temperature of the hydrothermal kettle to room temperature, washing the reaction product with deionized water and absolute ethyl alcohol for 3 times, putting the reaction product into an oven, and fully drying to obtain CeO2The powder of (4).
(2) Adding CeO2Dissolving the mixture in 80mL of glycol according to the molar ratio of CeO2: weighing Bi (HNO) according to the proportion of Bi 12:13)·5H2Adding O into the solution, fully stirring, then transferring to a high-pressure hydrothermal kettle, reacting at 180 ℃ for 12h, waiting for the reaction to be finished and naturally cooling, washing the reaction product for multiple times by using deionized water and absolute ethyl alcohol, putting into an oven for fully drying, taking out the dried precipitate, and grinding to obtain light green Bi/CeO2A composite photocatalyst is provided.
To further understand the Bi/CeO obtained by the above method2Composite photocatalystThe following experiments were used as examples for the analysis of (1):
1. XRD analysis
Example 1 was used to treat the Bi/CeO thus obtained2XRD analysis of the composite photocatalyst is carried out, and the result is shown in figure 1.
As can be seen from FIG. 1, the phase of the photocatalyst prepared in this example 1 is Bi/CeO2The composite photocatalyst can obviously see the diffraction peak of Bi, which shows that Bi particles are successfully loaded on 3D nanosheet CeO2Forming a nano-sphere structure.
2. SEM analysis
For the Bi/CeO obtained in inventive example 12The SEM analysis of the composite photocatalyst is shown in FIG. 2.
As can be seen from FIG. 2, the Bi/CeO prepared in this example2The photocatalyst is in a flower ball shape formed by assembling ultrathin sheets, and Bi particles are dispersed in CeO as can be seen from a high-magnification SEM picture2The outer end of the nano sheet, the thickness of the nano sheet is 1.5nm, the diameter of the Bi particle is about 160nm, and the diameter of the nano ball is 1.5 μm.
3. UV-vis analysis
For the Bi/CeO obtained in example 12The ultraviolet-visible diffuse reflection (UV-vis) analysis of the composite photocatalyst is shown in FIG. 3, and FIG. 3 shows the Bi/CeO prepared in example 1 of the present invention2And CeO2UV-vis spectrum of the nano flower ball shaped photocatalyst.
As shown by the results in FIG. 3, CeO was obtained2The absorption band edge of the photocatalyst is about 457nm and is in the visible light absorption range, but the absorption width is narrow, and Bi/CeO2The visible light absorption band edge of the film is greatly widened to about 510 nm.
4. Comparison of the Activity of the photocatalyst
The Bi/CeO prepared in the invention example 12Photocatalytic activity of composite photocatalyst and simple CeO2The photocatalytic activity of the compounds is compared, and the specific process is as follows:
under the condition of room temperature, 0.1g of Bi/CeO2And CeO2Uniformly dispersing the photocatalyst in 30mL of deionized water to obtainBi/CeO2And CeO2Dripping the aqueous solution of the photocatalyst into glassware with the diameter of 10cm respectively, putting the glassware into a 70 ℃ oven for full drying to obtain a film sample, and putting the film sample into NO-NO2In the NOx analyzer, 420ppb of NOx (mostly NO) is continuously introduced into the NOx analyzer to make it reach adsorption equilibrium. A xenon lamp with power of 300 watts and a 420nm optical filter is adopted as a visible light source, and Bi/CeO2And CeO2The photocatalyst is used for catalytic activity analysis, a xenon lamp with power of 300 watts and a 420nm optical filter is used as a simulated visible light source to continuously irradiate the film sample for 30min, and at the moment, the analyzer can record NO and NO in real time2To the corresponding concentration of (c). FIG. 4 shows Bi/CeO prepared in example 1 of the present invention2And CeO2And (5) testing the catalytic performance of the photocatalyst.
From FIG. 4 and calculation, CeO prepared in step (1) of example 1 was obtained2The degradation rate of the photocatalyst to NO under visible light reaches 26 percent, and the harmful byproduct NO is generated2The concentration of (B) is about 15.03 ppb. And the Bi/CeO prepared in the step (2)2The degradation rate of the photocatalyst to NO under visible light reaches 47.4 percent, and the photocatalyst has toxic and harmful by-product NO2Has a concentration of 4.27ppb, indicating that Bi/CeO was prepared in this example 12Degradation rate of flower ball shaped photocatalyst to NO is compared with CeO2The degradation rate of NO is obviously much higher, and the intermediate product NO2The yield of (B) is obviously reduced, which shows that the Bi/CeO of the invention2The photocatalyst has strong visible light photocatalytic activity, and the existence of Bi nano particles greatly improves the CeO2The photocatalytic activity of the catalyst and the appearance of Bi particles greatly reduce the secondary pollutant NO2The preparation method is simple and convenient, and is easy to apply to actual life.
From FIG. 5 and calculation, CeO prepared in step (1) of example 1 was obtained2Photocatalyst remaining NO after degradation2Is about 15.03ppb, and the Bi/CeO prepared in step (2)2Residual NO of composite photocatalyst after degradation2Is about 4.27ppb, so that Bi/CeO is used2The photocatalyst can well reduce the NO of an intermediate product2The yield of (2).
By the same method as above for the othersExamples prepared Bi/CeO2And CeO2The characteristics and performance of the photocatalyst are verified, and the result is similar to the result, wherein Bi particles are dispersed in CeO2The thickness of the nanosheets is 0.5-2.5 nm at the outer ends of the nanosheets, the diameter of Bi particles is about 50-200 nm, the diameter of nanospheres is 1-4 mu m, the visible light absorption band edge is about 510nm, the degradation rate of the nanosheets to NO under visible light can reach more than 45%, and toxic and harmful byproducts NO are generated2Can be reduced 2/3.
The experiments prove that the Bi/CeO of the invention2The composite photocatalyst is used for NO and NO under the condition of visible light2Has obvious degradation efficiency, particularly the load of Bi, greatly reduces NO2The secondary pollution to the environment is greatly reduced, and the Bi/CeO of the invention is observed by naked eyes2The composite photocatalyst is light green, so that the composite photocatalyst can be used as an inorganic dye to be applied to urban roads, walls, billboards, tree protection and the like, replaces partial chemical organic dye, reduces environmental pollution, and can be used as a photocatalyst to perform catalytic degradation on nitrogen oxides in the air under the condition of visible light to achieve the aim of air purification.
Claims (10)
1. Degraded NOxBi/CeO of (A)2 The preparation method of the composite photocatalyst is characterized by comprising the following steps:
(1) dissolving glucose, acrylamide and cerous nitrate in deionized water, stirring, dropwise adding ammonia water to adjust the pH to 10, carrying out hydrothermal reaction in a high-pressure hydrothermal kettle at 160-200 ℃ for 70-80 h, cooling the hydrothermal reaction kettle to room temperature, washing the reaction product with deionized water and absolute ethyl alcohol for multiple times, putting the reaction product into an oven, and fully drying to obtain CeO2The powder of (4);
(2) adding CeO2Dissolving in glycol at a mol ratio of CeO2: weighing Bi (NO) according to the proportion of Bi = 6-20: 13)3·5H2Adding O into the solution, fully stirring, transferring to a high-pressure hydrothermal kettle, reacting at 150-200 ℃ for 10-14 h, naturally cooling after the reaction is finished, and using deionized waterWashing the reaction product with water and anhydrous ethanol for multiple times, and drying in an oven to obtain Bi/CeO2 A composite photocatalyst is provided.
2. Degraded NO according to claim 1xBi/CeO of (A)2 The preparation method of the composite photocatalyst is characterized in that the molar ratio of glucose, acrylamide and cerium nitrate in the step (1) is as follows: 1-3: 2-5: 1.
3. Degraded NO according to claim 2xBi/CeO of (A)2 The preparation method of the composite photocatalyst is characterized in that the molar ratio of glucose, acrylamide and cerium nitrate in the step (1) is as follows: 2:3:1.
4. Degraded NO according to claim 1xBi/CeO of (A)2 The preparation method of the composite photocatalyst is characterized in that the temperature of the hydrothermal reaction of the high-pressure hydrothermal kettle in the step (1) is 180 ℃, and the time is 72 hours; the temperature of the hydrothermal reaction of the high-pressure hydrothermal kettle in the step (2) is 160 ℃, and the time is 12 hours.
5. Degraded NO according to claim 1xBi/CeO of (A)2 The preparation method of the composite photocatalyst is characterized in that CeO in the step (2)2：Bi=10:1。
6. Degrading NO with the method according to any of the preceding claims 1 to 5xBi/CeO of (A)2 Preparation method of composite photocatalyst prepared from Bi/CeO2 A composite photocatalyst is provided.
7. The Bi/CeO according to claim 62 The composite photocatalyst is characterized in that the catalyst is prepared by loading Bi particles on CeO2The diameter of the formed nano flower ball is 1-4 mu m, and the visible light absorption band edge is 510 nm.
8. The Bi/CeO according to claim 72 Composite photocatalyst, characterized in that, the CeO2The thickness of the nano-sheet is 0.5-2.5 nm, and the diameter of the Bi particles is 50-200 nm.
9. The Bi/CeO according to claim 62 Composite photocatalyst for degrading NO in air under visible light conditionxReduction of secondary pollutants NO2And (5) application of the generation aspect.
10. The use of claim 9, wherein: the Bi/CeO of claim 62 The composite photocatalyst is coated on a wall, a road surface or trees as a coating, and can play a role of dyeing inorganic dye and simultaneously carry out NO dyeing on the wall, the road surface or the trees under the condition of visible lightxCatalytic degradation is carried out, and secondary pollutant NO is reduced2And (4) generating.
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