CN111939949A - Bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst and preparation method thereof - Google Patents
Bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 69
- 239000002071 nanotube Substances 0.000 title claims abstract description 62
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
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- 239000010936 titanium Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 9
- 229930195725 Mannitol Natural products 0.000 claims description 9
- 235000010355 mannitol Nutrition 0.000 claims description 9
- 239000000594 mannitol Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
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- 101100460704 Aspergillus sp. (strain MF297-2) notI gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B01J35/39—
Abstract
The invention belongs to the technical field of catalysts. The invention discloses a bismuth oxybromide/titanium dioxide nanotube composite photocatalyst, which is prepared by compounding bismuth oxybromide and a titanium dioxide nanotube; the invention also discloses a preparation method of the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst, which comprises two parts of preparation of the titanium dioxide nanotube and preparation of the bismuth oxybromide/titanium dioxide nanotube composite. The bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared by the synthesis method provided by the invention has higher photocatalytic activity, and particularly under the driving condition of visible light, the unique structure of the photocatalyst endows the photocatalyst with the capability of effectively inhibiting the recombination of photo-generated electron-hole pairs so as to remarkably improve the utilization efficiency of the visible light. The synthesis method provided by the invention has the characteristics of mild conditions, good purity and the like, and is suitable for industrial large-scale production and application.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst and a preparation method thereof.
Background
In recent years, the problems of environmental pollution and energy shortage have become increasingly serious, and people concentrate on research and development of various novel energiesSource technology and devices. The photocatalytic technology has the advantages of environmental friendliness, high chemical energy and the like, and is widely considered as an important way for solving the problems of environmental pollution and energy crisis. TiO 22Is one of the most promising photocatalysts at present. Due to excellent photocatalytic activity, environmental friendliness and stability, the photocatalyst can decompose water to produce hydrogen and CO2And the method is widely applied to the fields of pollutant degradation and the like.
However, TiO2The photo-generated electron-hole pair is easy to rapidly recombine, seriously influences the photocatalytic performance and becomes the most main defect of the photo-generated electron-hole pair as a photocatalyst; in addition, TiO2The forbidden band is wider (3.2 ev), the electron-hole pair can be generated only by excitation under ultraviolet illumination, the utilization efficiency of sunlight is extremely low, and the TiO is prevented2Large-scale application in the field of photocatalysis. To improve TiO2Photocatalytic property of (1), one is on TiO2The photocatalyst is subjected to modification treatment, wherein the modification treatment comprises precious metal deposition modification, semiconductor composite modification, anion and cation doping modification and the like. Among these methods, co-catalysts have been successfully developed for enhancing TiO2Photocatalytic activity of (1). However, their use is limited by the disadvantages of expensive price, uncontrollable content and destructive conjugation systems. Therefore, there is a need to find suitable cocatalysts to improve their photocatalytic performance.
BiOBr is a novel narrow-band-gap semiconductor material, and has good response to visible light due to the advantages of unique layered structure, proper forbidden band width, good optical performance, good catalytic activity and the like. In the case where the wide band gap photocatalyst and the narrow band gap photocatalyst are matched in their valence band structures with each other, if they can form a heterojunction, TiO can be significantly enlarged2The utilization range of visible light and the suppression of electron-hole recombination to improve photocatalytic activity. At present, the application of the composition of BiOBr and inorganic semiconductor materials in the field of photocatalysis is concerned. However, it is currently about TiO2The research of preparing the photocatalyst by compounding with BiOBr is basically TiO2Particles, a lower specific surface area has a greater influence on the formation of the schottky barrier, notIs favorable for improving the visible light photocatalytic activity of the composite material.
Disclosure of Invention
In order to solve the problems, the invention provides a bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst with higher photocatalytic activity,
the invention also provides a preparation method of the bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a bismuth oxybromide/titanium dioxide nanotube composite photocatalyst is prepared by compounding bismuth oxybromide and a titanium dioxide nanotube.
Preferably, the molar ratio of the Bi/Ti element in the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst is (3: 1) - (1: 3).
A method for preparing a bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst,
a) preparing a titanium dioxide nanotube:
dispersing P25 powder in a sodium hydroxide solution, stirring, reacting for 20-28 hours at 125-135 ℃, centrifuging a reaction product, washing a precipitate with water and absolute ethyl alcohol in sequence, drying, mixing the dried product with 0.01mol/L hydrochloric acid solution, acidifying, centrifuging the acidified product, washing the precipitate with water and absolute ethyl alcohol in sequence, drying to obtain a precursor, calcining the precursor for 3.5-5.5 hours at 400-450 ℃, and cooling to room temperature to obtain a titanium dioxide nanotube;
b) preparing a bismuth oxybromide/titanium dioxide nanotube composite material:
dissolving mannitol in water, and adding Bi (NO) thereto3)3·5H2Stirring O until the mixture is clear, adding titanium dioxide nanotubes into the mixture according to the molar ratio of Bi/Ti elements, uniformly mixing, dropwise adding a saturated KBr solution, continuously stirring to prepare a mixed solution, placing the mixed solution into a reaction kettle for reaction at 150-160 ℃ for 3 hours, taking out a product after the reaction is finished, centrifuging to take out a precipitate, sequentially cleaning the precipitate with water and ethanol, and drying the precipitateThe bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst is prepared.
Preferably, in the step a), the concentration of the sodium hydroxide solution is 8-12 mol/L.
Preferably, in the step a), the concentration of the hydrochloric acid solution is 10-12 mol/L; the weight ratio of the hydrochloric acid solution to the dried product is 190-210: 1.
preferably, in the step b), the mannitol is dissolved in water to prepare a mannitol aqueous solution with the concentration of 0.08-0.13 mol/L, and Bi (NO)3)3·5H2After the O is added, the Bi in the solution is 0.8-1.2 mol/L.
Preferably, the titanium dioxide nanotubes are added in the step b), and then are uniformly mixed by magnetic stirring, wherein the magnetic stirring time is not less than 1 hour.
Preferably, the amount of the saturated KBr solution added dropwise in step b) is 1/5 based on the weight of water in step b).
Preferably, in step b), water and ethanol are washed at least three times each.
Therefore, the invention has the following beneficial effects:
the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared by the synthesis method provided by the invention has higher photocatalytic activity, and particularly under the driving condition of visible light, the unique structure of the photocatalyst endows the photocatalyst with the capability of effectively inhibiting the recombination of photo-generated electron-hole pairs so as to remarkably improve the utilization efficiency of the visible light. The synthesis method provided by the invention has the characteristics of mild conditions, good purity and the like, and is suitable for industrial large-scale production and application.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of a bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in embodiments 1-5 of the invention;
FIG. 2 is a micro-topography of the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in example 1 of the present invention at different scales;
FIG. 3 is a diagram of the ultraviolet-visible absorption spectra of the photocatalyst of bismuth oxybromide/titanium dioxide nanotube composite material prepared in example 1 of the present invention, titanium dioxide, and bismuth oxybromide;
FIG. 4 is a band gap diagram of titanium dioxide;
FIG. 5 is a band gap diagram of bismuth oxybromide;
FIG. 6 is a band gap diagram of the photocatalyst of the bismuth oxybromide/titanium dioxide nanotube composite material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. 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.
General examples
A bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst is prepared by compounding bismuth oxybromide and a titanium dioxide nanotube; the molar ratio of Bi/Ti elements in the bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst is (3: 1) - (1: 3).
A method for preparing a bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst,
a) preparing a titanium dioxide nanotube:
dispersing P25 powder into 8-12 mol/L sodium hydroxide solution, stirring, reacting at 125-135 ℃ for 20-28 hours, centrifuging the reaction product, washing the precipitate with water and absolute ethyl alcohol in sequence, drying, mixing the dried product with 0.01 mol/L10-12 mol/L hydrochloric acid solution, and acidifying, wherein the weight ratio of the hydrochloric acid solution to the dried product is 190-210: 1, centrifuging the acidified product, washing the precipitate with water and absolute ethyl alcohol in sequence, drying to obtain a precursor, calcining the precursor at 400-450 ℃ for 3.5-5.5 hours, and cooling to room temperature to obtain a titanium dioxide nanotube;
b) preparing a bismuth oxybromide/titanium dioxide nanotube composite material:
dissolving mannitol in water to obtain a solution with a concentration of 0.08-0.13 mol/LMannitol aqueous solution, and Bi (NO) is added thereto3)3·5H2Stirring O until the solution is clarified to ensure that Bi in the solution is 0.8-1.2 mol/L, adding titanium dioxide nanotubes into the solution according to the molar ratio of Bi to Ti elements, uniformly stirring and mixing by adopting magnetic force, wherein the magnetic stirring time is not less than 1 hour, dropwise adding 1/5 saturated KBr solution in weight of water, continuously stirring to prepare a mixed solution, placing the mixed solution into a reaction kettle for reaction at 150-160 ℃ for 3 hours, taking out a product after the reaction is finished, centrifuging to obtain a precipitate, sequentially washing the precipitate by using water and ethanol for at least three times respectively, and drying to prepare the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst.
Example 1
a) Preparing a titanium dioxide nanotube:
1) preparing 40ml of NaOH solution with the concentration of 10mol/L for later use;
2) dispersing 1.6g of P25 powder into the beaker, stirring for 1 hour under magnetic stirring at normal temperature, transferring the powder into a high-pressure reaction kettle after stirring uniformly, putting the kettle into an oven, and reacting for 24 hours at the reaction temperature of 130 ℃;
3) centrifuging the reacted product at the rotating speed of 4000rpm by using a high-speed centrifuge to obtain a precipitate, repeatedly washing the precipitate with water to be neutral, washing the precipitate with absolute ethyl alcohol for 3 times, and then placing a sample in a vacuum oven to dry the sample for 12 hours at the temperature of 60 ℃;
4) taking 0.5g of the dried sample, placing the sample in a beaker, adding a prepared 0.01M hydrochloric acid solution to enable the pH of the mixed solution to reach 3.5, covering a sealing film, and acidifying at room temperature for 6 hours;
5) centrifuging the acidified product at the rotating speed of 4000rpm by using a high-speed centrifuge to obtain a precipitate, repeatedly washing the precipitate with water until the precipitate is neutral, washing the precipitate with absolute ethyl alcohol for 3 times, and then placing the precipitate in a vacuum oven to dry the precursor for 12 hours at the temperature of 60 ℃;
6) calcining the precursor by a tube furnace, controlling the heating rate to be 5 ℃/min, heating for 80 minutes to 400 ℃, calcining for 4 hours in air, and naturally cooling to obtain the final product, namely the titanium dioxide nanotube;
b) preparing a bismuth oxybromide/titanium dioxide nanotube composite material:
1) 0.4555g of mannitol (0.0025 mol) is added into a beaker, 25mL of distilled water is added, and the mixture is stirred until the mannitol is completely dissolved;
2) take 0.486gBi (NO)3)3·5H2O (0.001 mol) is added into the solution and stirred until the solution is clear;
3) according to different molar ratios of Bi element and Ti element 3: 1, respectively adding 0.026g of TiO2Stirring for 1 hour by using a magnetic stirrer until the mixture is uniformly mixed;
4) slowly dripping 5mL of saturated KBr solution into each beaker, and continuously stirring for 30 min;
5) adding the solution in the beaker into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, and controlling the reaction temperature to be about 160 ℃ for reaction for 3 hours;
6) and taking out a product after reaction, centrifuging at the rotating speed of 4000rpm by adopting a high-speed centrifuge to obtain a precipitate, repeatedly washing for 3 times by using water, washing for 3 times by using absolute ethyl alcohol, and drying for 12 hours at the temperature of 60 ℃ in a vacuum oven to obtain the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst.
Examples 2 to 5
In examples 2 to 5, the conditions of other parameters were the same except that the amount of titanium dioxide added in step b) was different.
Wherein in example 2, according to different molar ratios of Bi element and Ti element, 2: 1, 0.039g of TiO are added respectively2；
Wherein in example 3, according to different molar ratios of Bi element and Ti element, 1: 1, adding 0.078g of TiO respectively2；
Wherein in example 4, according to different molar ratios of Bi element and Ti element, 1: 2, adding 1.56g of TiO respectively2；
Wherein in example 5, the molar ratio of Bi element to Ti element is 1: 3, adding 2.34g of TiO respectively2；
And (3) performance characterization:
XRD tests are respectively carried out on the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in the embodiments 1-5, the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in the embodiment 1 of the invention is selected to observe the micro morphology, and the ultraviolet visible absorption spectrum is tested on the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in the embodiment 1 of the invention, titanium dioxide and bismuth oxybromide to obtain corresponding band gap diagrams.
And (3) performance characterization results:
1. as can be seen from FIG. 1, the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in the embodiments 1 to 5 of the present invention has good crystallinity, no other impurities are generated, and the purity is high;
2. as can be seen from fig. 2, the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in example 1 of the present invention has a good micro-morphology, wherein the flaky bismuth oxybromide and the tubular titanium dioxide are uniformly distributed and well combined;
3. as can be seen from fig. 3, the spectral response range of the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in example 1 of the present invention is significantly enhanced compared with that of pure titanium dioxide or bismuth oxybromide;
4. as can be seen from fig. 4 to 6, the forbidden bandwidth of the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst prepared in embodiment 1 of the present invention is 2.61eV, which is much lower than 3.21eV of titanium dioxide and 2.82eV of bismuth oxybromide; after the material is compounded, the forbidden band width is reduced, so that the light driving force required by the material in photocatalysis is reduced, and the photocatalytic reaction is facilitated to be carried out.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (9)
1. A bismuth oxybromide/titanium dioxide nanotube composite photocatalyst is characterized in that:
it is prepared by compounding bismuth oxybromide and a titanium dioxide nanotube.
2. The bismuth oxybromide/titanium dioxide nanotube composite photocatalyst of claim 1, which is characterized in that:
the molar ratio of Bi/Ti element is (3: 1) - (1: 3).
3. A method for preparing the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst according to claim 1 or 2, which is characterized in that:
a) preparing a titanium dioxide nanotube:
dispersing P25 powder in a sodium hydroxide solution, stirring, reacting for 20-28 hours at 125-135 ℃, centrifuging a reaction product, washing a precipitate with water and absolute ethyl alcohol in sequence, drying, mixing the dried product with 0.01mol/L hydrochloric acid solution, acidifying, centrifuging the acidified product, washing the precipitate with water and absolute ethyl alcohol in sequence, drying to obtain a precursor, calcining the precursor for 3.5-5.5 hours at 400-450 ℃, and cooling to room temperature to obtain a titanium dioxide nanotube;
b) preparing a bismuth oxybromide/titanium dioxide nanotube composite material:
dissolving mannitol in water, and adding Bi (NO) thereto3)3·5H2Stirring O until the mixture is clear, adding titanium dioxide nanotubes into the mixture according to the molar ratio of Bi/Ti elements, uniformly mixing, dropwise adding a saturated KBr solution, continuously stirring to prepare a mixed solution, placing the mixed solution into a reaction kettle, reacting for 3 hours at 150-160 ℃, taking out a product after the reaction is finished, centrifuging to obtain a precipitate, sequentially cleaning the precipitate with water and ethanol, and drying to prepare the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst.
4. The method for preparing the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst according to claim 3, which is characterized in that:
in the step a), the concentration of the sodium hydroxide solution is 8-12 mol/L.
5. The method for preparing the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst according to claim 3, which is characterized in that:
in the step a), the concentration of the hydrochloric acid solution is 10-12 mol/L; the weight ratio of the hydrochloric acid solution to the dried product is 190-210: 1.
6. the method for preparing the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst according to claim 3, which is characterized in that:
in the step b), the mannitol is dissolved in water to prepare a mannitol aqueous solution with the concentration of 0.08-0.13 mol/L, and Bi (NO)3)3·5H2After the O is added, the Bi in the solution is 0.8-1.2 mol/L.
7. The method for preparing the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst according to claim 3, which is characterized in that:
and b), adding the titanium dioxide nanotubes in the step b), and then uniformly mixing by adopting magnetic stirring, wherein the magnetic stirring time is not less than 1 hour.
8. The method for preparing the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst according to claim 3, which is characterized in that:
the dropping amount of the saturated KBr solution in the step b) is 1/5 of the weight of water in the step b).
9. The method for preparing the bismuth oxybromide/titanium dioxide nanotube composite photocatalyst according to claim 3, which is characterized in that:
in step b), water and ethanol are washed at least three times each.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371144A (en) * | 2020-11-27 | 2021-02-19 | 盐城工学院 | Preparation method of self-dispersion reactive titanium dioxide-bismuth oxybromide composite photocatalyst |
| CN113600161A (en) * | 2021-08-09 | 2021-11-05 | 大连海事大学 | Preparation method of titanium dioxide nanotube network catalytic plate and application of catalytic plate in sludge antibiotic resistance gene treatment |
| CN113813971A (en) * | 2021-10-14 | 2021-12-21 | 内蒙古农业大学 | Preparation method and application of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst |
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| CN113813971B (en) * | 2021-10-14 | 2023-08-22 | 内蒙古农业大学 | Preparation method and application of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst |
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