AU2020100758A4 - Oxygen-vacancy-rich z-mechanism bi2o3@ceo2 photocatalyst, and preparation method and use thereof - Google Patents
Oxygen-vacancy-rich z-mechanism bi2o3@ceo2 photocatalyst, and preparation method and use thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 64
- 230000015556 catabolic process Effects 0.000 claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 claims abstract description 34
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 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 13
- 238000004321 preservation Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- FLHWBWDRXIOUBB-UHFFFAOYSA-N cerium hexahydrate Chemical compound O.O.O.O.O.O.[Ce] FLHWBWDRXIOUBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 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 6
- 239000012456 homogeneous solution Substances 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 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000013067 intermediate product Substances 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/51—
-
- B01J35/615—
Abstract
The present invention proposes an oxygen-vacancy-rich Z-mechanism Bi20 3@CeO 2 photocatalyst, and a preparation method and use thereof, and pertains to the technical field of 5 photocatalysis. The preparation method includes 1) preparing a reaction solution; 2) preparing a catalyst precursor solution; 3) preparing an intermediate Bi@CeO2 by high temperature calcination in a tube furnace under N2 protection, and 4) obtaining the oxygen-vacancy-rich Z-mechanism Bi20 3@CeO 2 photocatalyst. The catalyst is a flower-ball-like structure formed by nanoflake-like Bi 203 attached to flower-ball-like CeO 2 particles. The oxygen-vacancy-rich 0 Z-mechanism Bi 20 3 @CeO2 photocatalyst prepared by the method of the present invention can be applied for the degradation of NO, in the air under an visible light condition. It not only has a high degradation rate and a long activity retention time, but also has a small production of an intermediate product NO2 . A product formed by the degradation is low-toxic or non-toxic, and will not cause secondary pollution to the air. pdf #27-GO50 B -BiO 4% Bi2O3/CeO2 D 20 30 40 50 60 70 80 2Theta (degree) Bi203 particle
Description
OXYGEN-VACANCY-RICH Z-MECHANISM BI2O3@CEO2 PHOTOCATALYST, AND PREPARATION METHOD AND USE THEREOF
TECHNICAL FIELD
The present invention pertains to the technical field of photocatalysis, and in particular relates to an oxygen-vacancy-rich z-mechanism Bi2C>3@CeO2 photocatalyst, and a preparation method and use thereof.
BACKGROUD
The degradation of pollutants such as SOX, NOX and CO2 in the atmosphere has always been a concern of the people, because the pollutants not only bring great challenges to the environment, but also seriously endanger the health of humans and pose great challenges to future economic development. The photocatalytic oxidation technology is one of the efficient 5 and green ways for degrading the pollutants. Generally, semiconductors such as TiO2, CeO2, ZnO, and WO3 are used as photocatalysts. However, these photocatalysts have poor conductivity and weak oxidation abilities due to their weak photoresponse capabilities and low carrier separation and transfer efficiencies.
As a traditional photocatalyst, CeO2 occupies half of the market of photocatalysts because 0 of its high efficiency, non-toxicity, easy preparation and controllable morphology, but because of its large forbidden bandwidth (about 3 eV), its photoresponse capability is seriously affected. On the other hand, in a semiconductor photocatalytic system, bismuth-based semiconductors have special electronic structures, and have good solar response capabilities and ideal photocatalytic activities, so they are widely applied in the field of photocatalysis. Among the bismuth-based 25 semiconductors, a β-Βΐ203 photocatalyst has attracted people's attention because of its small forbidden bandwidth, simple preparation method, and economy and non-toxicity. However, the β-Βΐ203 photocatalyst has a high photo-induced electron-hole recombination rate, resulting in lower utilization rate of it. Therefore, it is not sufficient for better application in the field of photocatalysis.
SUMMARY
The present invention combines the respective advantages of a CeO2 photocatalyst and a β-Βΐ203 photocatalyst, and thus proposes an oxygen-vacancy-rich Z-mechanism Bi2C>3@CeO2 photocatalyst, and a preparation method and use thereof. The catalyst prepared by the method of
2020100758 15 May 2020 the present invention not only has a good photoresponse capability, but also has a high electron-hole utilization rate, and can be used for degrading NOX in the air. The specific technical solution is as follows.
A method for preparing an oxygen-vacancy-rich Z-mechanism Bi2Os@CeO2 photocatalyst 5 is disclosed, which includes the following steps:
1) preparing a reaction solution
a. dissolving cerium hexahydrate in deionized water to form a homogeneous solution, then adding acrylamide and glucose, and stirring well to prepare a cerium nitrate solution;
b. dissolving BifNCfk/SHoO in an ethylene glycol solution, and stirring until the solution is 0 homogeneous, so as to prepare a bismuth nitrate solution;
2) adding the bismuth nitrate solution dropwise into the cerium nitrate solution according to a ratio of Ce:Bi = 1:0.03-0.05, stirring to mix well, adjusting the pH of the mixture with an aqueous ammonia until the pH = 9-11, additionally stirring for 2-3 hours, and then transferring the mixture into a reaction kettle for a hydrothermal reaction, so as to prepare a catalyst 5 precursor solution;
3) placing the catalyst precursor solution prepared in the step 2) into a tube furnace and introducing N2 as a protective gas into the tube furnace for heat preservation treatment, and then naturally cooling the catalyst precursor solution to room temperature in the tube furnace, so as to prepare an intermediate Bi@CeC>2; and
4) heating the intermediate Bi@CeC>2 in the atmosphere to a temperature of 300-450°C, and keeping at this temperature for 3-5 hours to obtain the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst.
As further defined, the acrylamide and glucose added in the a of the step 1) have a mass ratio of 1:1.6-2.5.
As further defined, the condition for the hydrothermal reaction in the step 2) is that the reaction is conducted at 160-190°C for 48-72 hours.
As further defined, the condition for the heat preservation treatment in the step 3) is that the heat preservation is conducted at 550-650°C for 6-8 hours.
Also disclosed is an oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst 30 prepared by the aforementioned preparation method. The oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst is a flower-ball-like composite material with a diameter of 2-2.5 pm as formed by attaching nanoflake-like B12O3 onto the outer surfaces of nano-spherical CeC>2 particles.
As further defined, the B12O3 nanosheet has a thickness of 250-400 nm, and the 35 nano-spherical CeC>2 particle has a sphere diameter of 2-2.5 nm.
2020100758 15 May 2020
As further defined, the oxygen-vacancy-rich Z-mechanism EffiCffyCcCh photocatalyst has a specific surface area of more than 107 m /g.
The aforementioned oxygen-vacancy-rich Z-mechanism EffiOsifyCeCh photocatalyst can be applied for catalytic degradation of NOX, and its catalytic degradation activity is: under a visible 5 light condition, it can degrade more than 40% of NOX with a concentration of 430 ppb within 8 min.
Also disclosed is use of the aforementioned oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst in the degradation of NOX in the air under a visible light condition.
A method of applying the aforementioned oxygen-vacancy-rich Z-mechanism Bi2Os@CeO2 0 photocatalyst in the degradation of NOX includes allowing the oxygen-vacancy-rich Z-mechanism Bi2Os@CeO2 photocatalyst to act on NOX under a visible light condition, and the corresponding amount of the oxygen-vacancy-rich Z-mechanism Bi2Os@CeO2 photocatalyst per degradation of 430 ppb of NOX is 0.08 - 0.1 g, and the degradation rate is still no less than 40% after 50 min of continuous degradation.
Compared with the prior art, the present invention has the following advantages.
1. In the present invention, the bismuth nitrate solution is slowly added dropwise into the cerium nitrate solution and then stirred for the hydrothermal reaction to prepare the catalyst precursor solution, and then the catalyst precursor solution is transferred into a tube furnace for the heat preservation treatment with N2 as the protective gas. By using the method of the 0 hydrothermal reaction plus the heat preservation treatment, the preparation method is simple, and the operation process is easy and controllable. The CeC>2 and β-Βΐ2θ3 are modified separately to change their forbidden bandwidths and overcome their respective deficiencies in application, such that they can function synergistically and exert better conductive properties when recombined. Furthermore, in the present invention the preparation process does not incorporate 25 any impurity, has less pollution, and has a higher degree of recombination.
2. The oxygen-vacancy-rich Z-mechanism Bi2Os@CeO2 photocatalyst prepared by the method of the present invention is flower-ball-like nanoparticles formed by attaching nanoflake-like B12O3 particles onto spherical CeC>2 particles. The oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst fully combines the high electron-hole utilization rate 30 of CeC>2 and the strong photoresponse capability and good stability of β-Βΐ203, such that it has a higher carrier separation and transfer efficiency and a large specific surface area. The photocatalyst has improved electrical conductivity and oxidizing capacity, and thus it can respond to NOX under the visible light condition and exert high catalytic degradation activity.
3. The oxygen-vacancy-rich Z-mechanism Bi2O3@CeC>2 photocatalyst prepared by the 35 method of the present invention can be applied for degrading NOX in the air under the visible
2020100758 15 May 2020 light condition. It not only has a fast degradation rate, a high degradation efficiency and a low production of the intermediate product NO2, but also has a degradation activity that can be maintained after 50 minutes of continuous degradation, and the product formed by the degradation is low-toxic or non-toxic, and will not cause secondary pollution to the air.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a XRD pattern of the Bi2Os@CeO2 photocatalyst of Example 1;
FIG. 2 is an SEM pattern of the Bi2Os@CeO2 photocatalyst of Example 1;
FIG. 3 is a diagram showing the specific surface area and particle size distribution of the 0 Bi2O3@CeO2 photocatalyst of Example 1;
FIG. 4 is a UV-vis pattern of CeC>2, β-Βΐ2θ3, and the Bi2O3@CeO2 photocatalyst of Example i;
FIG. 5(a) is a graph of the NOX degradation rates of CeC>2, β-Βΐ203, and the Bi2O3@CeO2 photocatalyst of Example 1 under visible light; and FIG. 5(b) shows the amount of the 5 by-product NO2 generated as catalyzed by CeC>2, β-Βΐ2θ3 and the Bi2O3@CeO2 photocatalyst of Example 1 under visible light.
DESCRIPTION OF THE EMBODIMENTS
The technical solution and implementation of the present invention will be described in detail hereafter with reference to accompanying drawings and examples, but the present invention is not limited to the embodiments described hereafter.
Example 1
A method for preparing an oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst, 25 included the following steps:
1) preparing a reaction solution
a. 2 g of cerium hexahydrate was dissolved in 60 mL of deionized water to form a homogeneous solution, then added with 0.8 g of acrylamide and 1.8 g of glucose, and stirred well for 20 minutes to prepare a cerium nitrate solution;
b. Bi(NO3)3*5H2O was dissolved in an ethylene glycol solution, and stirred for 20 minutes until the solution was homogeneous, so as to prepare a bismuth nitrate solution;
2) the bismuth nitrate solution prepared in the b of the step 1) was slowly added dropwise into the cerium nitrate solution prepared in the a of the step 1) according to an atom ratio of Ce:Bi = 1:0.04, stirred for 20 minutes, adjusted with an aqueous ammonia at a volume
2020100758 15 May 2020 concentration of 5% until the pH is 10, additionally stirred for 3 hours, and then transferred into a reaction kettle to conduct a hydrothermal reaction at 180°C for 72 hours, so as to prepare a catalyst precursor solution;
3) the catalyst precursor solution prepared in the step 2) was placed into a tube furnace, and 5 N2 was introduced as a protective gas into the tube furnace for heat preservation at 600°C for 6 hours, and then the catalyst precursor solution was naturally cooled to room temperature in the tube furnace, so as to prepare an intermediate Bi@CeO2; and
4) the intermediate Bi@CeO2 was heated in the atmosphere to a temperature of 400°C, and kept at this temperature for 4 hour to obtain the oxygen-vacancy-rich Z-mechanism 0 Bi2O3@CeO2 photocatalyst.
XRD and SEM analysis were conducted on the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this example. As could be seen in connection with FIGs. 1-3, the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this example was a flower-ball-like composite material with an outer surface diameter of 2 pm as formed by 5 attaching nanoflake-like B12O3 onto nano-flower-ball-like CeO2, wherein the B12O3 nanosheet had a thickness of 250 nm, the CeO2 had a flower-ball diameter of 2 nm, and the specific surface area of the nanosheets in the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst was more than 107 m /g.
UV-vis pattern analysis was conducted on the oxygen-vacancy-rich Z-mechanism 0 Bi2O3@CeO2 photocatalyst prepared in this example and commercially available CeO2 and B12O3 materials. The results were shown in FIG. 4. It could be seen from FIG. 4 that, the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this example had a significant red shift in the absorption of visible light, and its response to the visible light was greatly improved, while each of the CeO2 material and the β-Βΐ2θ3 material had less absorption 25 of visible light.
Example 2
Different from Example 1, the method for preparing the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this example included the following steps:
1) preparing a reaction solution
a. 2.5 g of cerium hexahydrate was dissolved in 50 mL of deionized water to form a homogeneous solution, then added with 1 g of acrylamide and 1.6 g of glucose, and stirred well for 28 minutes to prepare a cerium nitrate solution;
b. Bi(NO3)3*5H2O was dissolved in an ethylene glycol solution, and stirred for 26 minutes until the solution was homogeneous, so as to prepare a bismuth nitrate solution;
2) the bismuth nitrate solution prepared in the b of the step 1) was slowly added dropwise
2020100758 15 May 2020 into the cerium nitrate solution prepared in the a of the step 1) according to an atom ratio of Ce:Bi = 1:0.04, stirred for 26 minutes, adjusted with an aqueous ammonia at a volume concentration of 7% until the pH is 10, additionally stirred for 2.5 hours, and then transferred into a reaction kettle to conduct a hydrothermal reaction at 170°C for 60 hours, so as to prepare a 5 catalyst precursor solution;
3) the catalyst precursor solution prepared in the step 2) was placed into a tube furnace, and N2 was introduced as a protective gas into the tube furnace for heat preservation at 650°C for 7 hours, and then the catalyst precursor solution was naturally cooled to room temperature in the tube furnace, so as to prepare an intermediate Bi@CeC>2; and
4) the intermediate Bi@CeC>2 was heated in the atmosphere to a temperature of 400°C, and kept at this temperature for 5 hour to obtain the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst.
The oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this example was a flower-ball-like composite material with an outer surface diameter of 2.5 pm as 5 formed by attaching nanoflake-like B12O3 onto nano-flower-ball-like CeC>2, wherein the B12O3 nanosheet had a thickness of 250 nm, the CeC>2 had a ball diameter of 2.5 nm, and the specific surface area of the nanosheets in the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst was more than 107 m /g.
Example 3
Different from Examples 1 and 2, the method for preparing the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this example included the following steps:
1) preparing a reaction solution
a. 3 g of cerium hexahydrate was dissolved in 60 mL of deionized water to form a homogeneous solution, then added with 1.2 g of acrylamide and 2 g of glucose, and stirred well 25 for 30 minutes to prepare a cerium nitrate solution;
b. Bi(NC>3)3*5H2O was dissolved in an ethylene glycol solution, and stirred for 30 minutes until the solution was homogeneous, so as to prepare a bismuth nitrate solution;
2) the bismuth nitrate solution prepared in the b of the step 1) was slowly added drop wise into the cerium nitrate solution prepared in the a of the step 1) according to an atom ratio of 30 Ce:Bi = 1:0.05, stirred for 30 minutes, adjusted with an aqueous ammonia at a volume concentration of 5.5% until the pH is 11, additionally stirred for 3 hours, and then transferred into a reaction kettle to conduct a hydrothermal reaction at 190°C for 72 hours, so as to prepare a catalyst precursor solution;
3) the catalyst precursor solution prepared in the step 2) was placed into a tube furnace, and 35 N2 was introduced as a protective gas into the tube furnace for heat preservation at 650°C for 8
2020100758 15 May 2020 hours, and then the catalyst precursor solution was naturally cooled to room temperature in the tube furnace, so as to prepare an intermediate Bi@CeC>2; and
4) the intermediate Bi@CeC>2 was heated in the atmosphere to a temperature of 450°C, and kept at this temperature for 5 hour to obtain the oxygen-vacancy-rich Z-mechanism 5 Bi2O3@CeO2 photocatalyst.
The oxygen-vacancy-rich Z-mechanism Bi2O3@CeC>2 photocatalyst prepared in this example was a flower-ball-like composite material with an outer surface diameter of 2.2 pm as formed by attaching nanoflake-like B12O3 onto nano-flower-ball-like CeC>2, wherein the B12O3 nanosheet had a thickness of 350 nm, the CeC>2 had a ball diameter of 2 nm, and the specific 0 surface area of the nanosheets in the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst was more than 107 m /g.
Example 4
Different from Examples 1-3, the method for preparing the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this example included the following steps: 5 1) preparing a reaction solution
a. 2 g of cerium hexahydrate was dissolved in 40 mL of deionized water to form a homogeneous solution, then added with 0.8 g of acrylamide and 1.5g of glucose, and stirred well for 20 minutes to prepare a cerium nitrate solution;
b. Bi(NC>3)3*5H2O was dissolved in an ethylene glycol solution, and stirred for 20 minutes 0 until the solution was homogeneous, so as to prepare a bismuth nitrate solution;
2) the bismuth nitrate solution prepared in the b of the step 1) was slowly added dropwise into the cerium nitrate solution prepared in the a of the step 1) according to an atom ratio of Ce:Bi = 1:0.03, stirred for 20 minutes, adjusted with an aqueous ammonia at a volume concentration of 3% until the pH is 9, additionally stirred for 2 hours, and then transferred into a 25 reaction kettle to conduct a hydrothermal reaction at 160°C for 48 hours, so as to prepare a catalyst precursor solution;
3) the catalyst precursor solution prepared in the step 2) was placed into a tube furnace, and N2 was introduced as a protective gas into the tube furnace for heat preservation at 550°C for 6 hours, and then the catalyst precursor solution was naturally cooled to room temperature in the 30 tube furnace, so as to prepare an intermediate Bi@CeC>2; and
4) the intermediate Bi@CeC>2 was heated in the atmosphere to a temperature of 300°C, and kept at this temperature for 3 hour to obtain the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst.
The oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in this 35 example was a flower-ball-like composite material with an outer surface diameter of 2.4 pm as
2020100758 15 May 2020 formed by attaching nanoflake-like B12O3 onto nano-flower-ball-like CeCh, wherein the B12O3 nanosheet had a thickness of 400 nm, the CeC>2 had a ball diameter of 2.3 nm, and the specific surface area of the nanosheets in the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst was more than 107 m /g.
In order to verify the catalytic degradation characteristic of the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in the present invention, the following experiment was conducted for illustration.
Each 100 g of the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in Example 1 and commercially available CeC>2 and B12O3 materials were taken and placed in 3 0 clean vessels, and meanwhile the photocatalyst in each vessel was washed away with 30 mL of deionized water. The vessels were then dried by baking, respectively put into the working chambers of 3 NO-NC>2-NOX analyzers with a NO-NC>2-NOX concentration of 430 ppb, and kept in the NO-NC>2-NOX environment under dark conditions for 30 minutes to achieve desorption equilibrium. Then a xenon lamp with a power of 300 watt and equipped with a 420 nm high-pass 5 filter was used as the visible light source to irradiate each of the working chambers of the 3 analyzers for 30 minutes. Referring to FIGs. 5(a) and 5(b), it was concluded from analysis that, the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst of the present invention had a NOX degradation rate up to 43%, and the concentration of the corresponding intermediate product NO2 is 8.8 ppb; the oxygen-vacancy-rich CeC>2 photocatalyst had a NOX degradation rate 0 of 27% and the concentration of the corresponding intermediate product NO2 is 13 ppb; and the β-Βΐ2θ3 photocatalyst had a NOX degradation rate of 17% and the concentration of the corresponding intermediate product NO2 is 48 ppb. By comparison with the CeC>2 material and the β-Βΐ2θ3 material, it could be seen that the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst of the present invention had a higher NOX degradation rate and the concentration of 25 the corresponding intermediate product NO2 was significantly reduced.
The NOX catalytic degradation characteristics of the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared in other examples were measured by the same method for comparison, and the results were the same as the aforementioned experimental results. That is, when the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst of the present 30 invention acts on NOX under the visible light condition, 0.08-0.1 g of the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst has a degradation rate of more than 40% on the NOX with a concentration of 430 ppb within 8 min, indicating that it has a fast degradation speed and a high degradation rate. Furthermore, the retention time of its activity is longer, and the degradation rate is still no less than 40% after 50 min of continuous degradation.
Claims (5)
1) preparing a reaction solution
a. dissolving cerium hexahydrate in deionized water to form a homogeneous solution, then adding acrylamide and glucose, and stirring well to prepare a cerium nitrate solution;
b. dissolving Bi(NO3)3*5H2O in an ethylene glycol solution, and stirring until the solution is homogeneous, so as to prepare a bismuth nitrate solution;
1. A method for preparing an oxygen-vacancy-rich Z-mechanism 812()3 @CeC>2 photocatalyst, comprising the following steps:
2. The method for preparing an oxygen-vacancy-rich Z-mechanism 812()3 @CeC>2 photocatalyst according to claim 1, wherein the acrylamide and glucose added in the a of the step 1) have a mass ratio of 1:1.6-2.5, wherein the condition for the hydrothermal reaction in the step 2) is that the reaction is conducted at 160-190°C for 48-72 hours, wherein the condition for the heat preservation treatment in the step 3) is that the heat preservation is conducted at 550-650°C for 6-8 hours.
2) adding the bismuth nitrate solution dropwise into the cerium nitrate solution according to a ratio of Ce:Bi = 1:0.03-0.05, stirring to mix well, adjusting the pH of the mixture with an aqueous ammonia until the pH = 9-11, additionally stirring for 2-3 hours, and then transferring the mixture into a reaction kettle for a hydrothermal reaction, so as to prepare a catalyst precursor solution;
3. An oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst prepared by the preparation method of any one of claims 1-2, wherein the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst is a flower-ball-like composite material with a diameter of 2-2.5 pm as formed by attaching nanoflake-like B12O3 onto the outer surfaces of nano-spherical CeC>2 particles.
3) placing the catalyst precursor solution prepared in the step 2) into a tube furnace and introducing N2 as a protective gas into the tube furnace for heat preservation treatment, and then naturally cooling the catalyst precursor solution to room temperature in the tube furnace, so as to prepare an intermediate Bi@CeC>2; and
4. The oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst according to claim 3, wherein the B12O3 nanosheet has a thickness of 250-400 nm, and the nano-spherical CeC>2
2020100758 15 May 2020 particle has a sphere diameter of 2-2.5 nm, wherein the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst has a specific surface area of more than 107 m /g, wherein the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst has a catalytic degradation activity for NOX: under a visible light condition, it can degrade more than 40% of NOX with a concentration of 430 ppb within 8 min.
4) heating the intermediate Bi@CeC>2 in the atmosphere to a temperature of 300-450°C, and keeping at this temperature for 3-5 hours to obtain the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst.
5. Use of the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst according to claim 3 in the degradation of NOX in the air under a visible light condition, wherein the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst acts on NOX under a visible light condition, and the corresponding amount of the oxygen-vacancy-rich Z-mechanism Bi2O3@CeO2 photocatalyst per degradation of 430 ppb of NOX is 0.08-0.1 g, and the degradation rate is still no less than 40% after 50 min of continuous degradation.
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| CN110124660B (en) | 2022-02-01 |
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