CN116832837A - Flower ball-shaped TiO 2 Heterojunction material with/BiOBr core-shell structure and preparation method and application thereof - Google Patents
Flower ball-shaped TiO 2 Heterojunction material with/BiOBr core-shell structure and preparation method and application thereof Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000011258 core-shell material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004005 microsphere Substances 0.000 claims abstract description 68
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 87
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000002135 nanosheet Substances 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 32
- 235000019441 ethanol Nutrition 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 11
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
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- 238000007789 sealing Methods 0.000 description 4
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- 238000009423 ventilation Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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Abstract
The invention discloses a flower ball-shaped TiO 2 A heterojunction material with a BiOBr core-shell structure and a preparation method thereof. The invention synthesizes regular TiO by taking silicon dioxide as a template 2 Hollow microsphere, and then carrying the flaky BiOBr on TiO by an in-situ hydrothermal method 2 The surface of the hollow microsphere forms a flower-sphere-shaped grade core-shell structure TiO with strong light absorption capacity 2 BiOBr heterojunction material. The TiO 2 The BiOBr heterojunction material can utilize the characteristic that light is reflected in the hollow microsphere for multiple times so as to improve the utilization of light energy when the BiOBr heterojunction material is used as a catalyst, thereby realizing CO 2 Therefore, the method has good practical application value.
Description
Technical Field
The invention relates to the technical field of photocatalytic degradation and photocatalytic carbon dioxide reduction, in particular to flower-ball-shaped TiO 2 BiOBr core-shell structure heterojunction material, and preparation method and application thereof.
Background
With the development of society, environmental problems and energy crisis are matters that we are urgent to want to solve. To meet the demands of production and life, we need to burn fossil energy, which can generate a large amount of CO 2 The greenhouse effect is exacerbated, resulting in global warming. As a novel catalytic mode, photocatalysis can fully utilize solar energy, and provides an important opportunity for relieving global energy shortage and environmental pollution. The photocatalyst can absorb solar energy to convert CO 2 Reduction to produce fuels and chemicals has attracted considerable social attention as it provides a substitute for fossil feedstocks and allows for large scale conversion and recycle of greenhouse gases.
TiO 2 The BiOBr has the characteristics of lower cost, no toxicity, better stability and the like, and is widely applied to the field of photocatalysis. However, the light absorption capacity is weak due to the small specific surface area; smaller heterojunction interface area, limited TiO 2 Practical application of BiOBr in the field of photocatalysis.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a TiO with strong light absorption capability aiming at the defects existing in the prior art 2 A BiOBr core-shell structure heterojunction material. The material has larger specific surface area and heterojunction interface area, has more reactive sites, can improve light absorption capacity and reduce CO when used as a photocatalyst 2 And also has a greater capacity.
The invention adopts the technical proposal for solving the problems that:
flower ball-shaped TiO 2 Heterojunction material with/BiOBr core-shell structure and hollow TiO 2 Hollow microsphere as main body and BiOBr nanometer sheet growing on TiO 2 Forming a flower-sphere-shaped heterostructure with a core-shell structure on the surface of the hollow microsphere; wherein the TiO is 2 The size of the hollow microsphere is 300-600 nm, and the flower-sphere-shaped TiO 2 The overall size of the heterojunction material with the BiOBr core-shell structure is 400-800 nm; the TiO 2 The mol ratio of Ti/Bi in the BiOBr core-shell structure heterojunction material is (0.7-3): 1.
the invention also provides the TiO 2 Preparation method of/BiOBr core-shell structure heterojunction, and synthesizing TiO by taking silicon dioxide as template 2 The hollow microsphere is carried on the TiO by an in-situ hydrothermal method 2 The surface of the hollow microsphere forms a grade core-shell structure TiO with strong light absorption capacity 2 A BiOBr grade core-shell structure heterojunction material. The method comprises the following specific steps:
(1) Dissolving tetraethyl silicate in ethanol, deionized water and ammonia water solution, stirring and reacting to obtain SiO 2 A microsphere;
(2) SiO is made of 2 Dispersing the microspheres in ethanol, adding ammonia water, and stirring to obtain a dispersion; adding tetrabutyl titanate into the dispersion liquid, and performing heating treatment; the solution obtained after the heating treatment is separated to obtain a solid product and calcined to obtain SiO 2 @TiO 2 A microsphere; siO is made of 2 @TiO 2 Etching the microspheres by using hydrofluoric acid solution to obtain TiO 2 Hollow microspheres;
(3) Hollow TiO 2 Soaking microsphere in dilute sulfuric acid, washing, drying, dispersing into ethylene glycol, adding bismuth nitrate pentahydrate, cetyltrimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP), performing hydrothermal reaction, and making BiOBr nanosheet into TiO 2 The hollow microsphere grows on the surface and is uniformly coated on the TiO 2 The surfaces of the hollow microspheres are provided with TiO 2 A BiOBr core-shell structure heterojunction material.
Further, in the step (1), the volume ratio of the tetraethyl silicate to the ethanol, the deionized water and the ammonia water is 1: (10-15): (1-2): 1, a step of; the stirring time is 2-5 h.
Further, in the step (2), the SiO 2 The dispersion concentration of the microspheres in the ethanol is 0.5-2 mg/mL, and the volume ratio of ammonia water to ethanol is 1: (100-200), the volume ratio of butyl titanate to ethanol is 1: (50-100); the heating temperature is 40-50 ℃ and the heating time is 20-30 hours; the calcination temperature is 500-600 ℃, and the calcination time is 1-4 h; the volume concentration of the hydrofluoric acid solution is 2-5%.
Further, in the step (3), the concentration of the dilute sulfuric acid is 1.5-2.5 mol/L, and the soaking time is 2-3 hours; hollow TiO 2 The dispersion concentration of the microsphere in glycol is 0.015-0.05 mol/L, and the mole ratio of bismuth nitrate pentahydrate to CTAB is (0.7-3) according to Ti/Bi: 1, bi/Br molar ratio of 1: (1-1.5) feeding; PVP concentration in glycol is 0.1-5 g/L; the hydrothermal reaction temperature is 120-180 ℃ and the hydrothermal time is 0.5-2 h.
The TiO of the invention 2 the/BiOBr core-shell structure heterojunction material can be used for photocatalytic carbon dioxide reduction, photocatalytic degradation and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The TiO of the invention 2 Heterojunction material with/BiOBr core-shell structure, and hollow spherical TiO (titanium dioxide) surrounded by BiOBr nano sheet 2 The surface forms each independent flower ball, ensures the larger BiOBr and TiO 2 Thereby constructing a perfect heterostructure to enhance the migration rate of photo-generated carriers and obtain high-efficiency CO 2 Reducing power. Further, the material TiO 2 The BiOBr core-shell structure heterojunction material has a hierarchical structure, and has larger specific surface area when used as a catalyst, thereby exposing more reactive sites and exposing CO 2 To have adsorption sites for CO 2 High-efficiency stable reduction performance of the catalyst.
(2) The TiO provided by the invention 2 Preparation method of BiOBr core-shell structure heterojunction material, and uniform and regular TiO (titanium dioxide) is prepared by using hard template method 2 Hollow microsphere and hollow spherical TiO by in-situ hydrothermal method 2 The BiOBr nano-sheet grows on the surface to form a core-shell structureIs a heterojunction material of (a). The core-shell structure not only can enhance the repeated reflection of light in the spherical material, but also can improve the absorption capacity of the spherical material to visible light, and can obtain CO 2 High-efficiency stable reduction performance of the catalyst.
Drawings
FIG. 1 is a TiO prepared in example 1 2 Wide angle diffraction XRD pattern of the BiOBr core-shell structure heterojunction material.
FIG. 2 is a hollow TiO prepared in example 1 2 Scanning Electron Microscope (SEM) image of the microspheres.
FIG. 3 is a TiO prepared in example 1 2 Scanning Electron Microscope (SEM) image of the BiOBr core-shell structure heterojunction material.
FIG. 4 is a TiO prepared in example 1 2 High angle annular dark field image (HAADF-STEM) plot of a BiOBr core-shell structure heterojunction material.
FIG. 5 shows hollow TiO according to the different Ti/Bi preparations in examples 1, 2 and 3 2 Heterojunction material with BiOBr core-shell structure and Bulk-TiO prepared in comparative example 1 2 The BiOBr heterojunction material is used for preparing CO under the same condition 2 A comparison of the conversion to CO.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
In the following examples, the ammonia water was commercial ammonia water, and the concentration was 25% to 28%.
Example 1
Flower ball-shaped TiO 2 The preparation method of the BiOBr core-shell structure heterojunction material mainly comprises the following steps:
(1) Measuring tetraethyl silicate, ammonia water, deionized water and ethanol by a measuring cylinder, mixing in a beaker, stirring for 3 hours at room temperature, cleaning for 3-5 times by the deionized water, and drying to obtain SiO 2 Microspheres for standby; wherein, the volume ratio of tetraethyl silicate, ammonia water, deionized water and ethanol is 1:1:2:15;
(2) Weighing 0.2g of SiO synthesized in step (1) with an electronic balance 2 The microspheres were dispersed in 150mL of ethanol,obtaining a suspension;
(3) Measuring 1mL of ammonia water and 2mL of tetrabutyl titanate by using a measuring cylinder, adding the 1mL of ammonia water and 2mL of tetrabutyl titanate into the suspension in the step (2), heating to 45 ℃, stirring for 24 hours, cooling the obtained solution to room temperature, centrifugally drying, washing with absolute ethyl alcohol and deionized water for 3-5 times, and then drying in a 60 ℃ oven to obtain amorphous SiO 2 @TiO 2 Standby; wherein, the volume ratio of the ammonia water, the tetrabutyl titanate and the ethanol in the suspension is controlled to be 1:2:150.
(4) The amorphous SiO obtained in the step (3) is treated 2 @TiO 2 Transferring to a muffle furnace, heating at 550 ℃ for 2 hours, cooling to room temperature along with the furnace to obtain SiO 2 @TiO 2 A microsphere;
(5) The SiO obtained in the step (4) is reacted with 2 @TiO 2 Etching the microspheres in hydrofluoric acid solution with volume concentration of 5%, respectively washing the microspheres with absolute ethyl alcohol and deionized water for 3-5 times, and then drying the microspheres in a 60 ℃ oven to obtain TiO 2 Hollow microspheres for standby.
(6) The TiO obtained in the step (5) is treated 2 The hollow microspheres are subjected to surface treatment, soaked in 2mol/L dilute sulfuric acid solution for 2 hours, respectively washed with absolute ethyl alcohol and deionized water for 3-5 times, and then placed in a 60 ℃ oven for drying for standby.
(7) Weighing the TiO obtained in step (6) 2 Dissolving hollow microspheres, bismuth nitrate pentahydrate, cetyl trimethyl ammonium bromide and PVP in glycol, stirring for half an hour, transferring to a 50mL reaction kettle, hydrothermal for 1 hour at 160 ℃, cooling to room temperature along with a furnace, and centrifuging to obtain TiO 2 Crude product of heterojunction material with BiOBr core-shell structure; wherein, the concentration of bismuth nitrate pentahydrate in glycol is 0.02mol/L, the concentration of PVP in glycol is 0.2g/L, and TiO is used for preparing the aqueous solution 2 The molar ratio of the hollow microspheres to bismuth nitrate pentahydrate and cetyltrimethylammonium bromide is 5:4:4.
(8) The TiO obtained in the step (7) is treated 2 The crude product of the heterojunction material with the BiOBr core-shell structure is respectively washed by absolute ethyl alcohol and deionized water for 3 to 5 times, and then is dried in a baking oven at 60 ℃ to obtain flower-spherical TiO 2 A BiOBr core-shell structure heterojunction material.
As can be seen from FIG. 1, the flower-shaped spherical TiO prepared in this example 2 The heterojunction material with the/BiOBr core-shell structure has single TiO 2 Diffraction peaks with BiOBr. The peak positions in the figure are respectively positioned on the standard PDF card TiO 2 (JCPLDS: 84-1286) corresponds to BiOBr (JCPLDS: 78-0348). Wherein 2θ=25.3° corresponds to this TiO 2 Due to the (101) crystal face of TiO 2 The mass of the TiO is relatively low in the sample 2 The diffraction peak is smaller; other 2θ=25.2 °, 31.7 °, 32.2 °, 46.2 °, 57.2 °, 67.5 ° and 76.8 ° correspond to the (101), (102), (110), (200), (212), (220) and (310) crystal planes of the BiOBr, respectively. From XRD patterns, it can be seen that TiO is synthesized 2 BiOBr composite.
As can be seen from FIG. 2, the hollow TiO prepared in this example 2 The diameter of the microsphere is basically in the range of 400-600 nm, some microspheres with smaller wall thickness are broken, and a hollow structure can be seen.
As can be seen from FIG. 3, the TiO prepared in this example 2 The heterojunction material with the/BiOBr core-shell structure is in a flower sphere shape independently, and the BiOBr nano-sheet is wrapped in the hollow TiO 2 Flower-sphere-shaped TiO formed on microsphere surface 2 The overall size of each independent flower ball is basically in the range of 400-800 nm.
FIG. 4 shows the TiO composition prepared in this example 2 High-angle annular dark field image (HAADF-STEM) of BiOBr core-shell structure heterojunction material, and the result shows that the heterojunction material is a hollow core-shell heterostructure and is formed by stacking BiOBr nano sheets on TiO 2 Forming flower ball-shaped TiO on the surface of the hollow microsphere 2 A BiOBr core-shell structure heterojunction material.
In the form of CO 2 Reduction to model reaction to investigate the flower-spherical TiO prepared in example 1 2 The photo-catalytic performance of the BiOBr core-shell structure heterojunction material comprises the following specific processes:
0.05g of TiO prepared in this example is weighed 2 loading/BiOBr catalyst into a reaction tank, introducing CO into the reaction tank 2 And H is 2 The volume ratio is 1:4, continuously ventilating for 30min to ensure that the air in the reaction tank is discharged, and sealing the reaction tank after ventilation is finished; turning on lightThe source was irradiated with a full spectrum light source, and 1mL of the gas in the reaction vessel was extracted every half an hour, and the gas species and the contents of the respective substances were detected by chromatography. After 3h illumination, CO was measured 2 Converted into CO with a CO production rate of 15.84 mu mol h -1 ·g -1 Has better CO conversion performance. Compared with comparative example 1 in which SiO was not added 2 Bulk TiO of microsphere 2 The catalytic performance of example 1 was 2.2 times that of comparative example 1. Thus, the TiO prepared by the invention 2 The BiOBr core-shell structure heterojunction material can enhance the repeated reflection of light in the spherical material, improve the absorption capacity of the heterojunction material to visible light, enlarge the specific surface area, and increase the contact area with reactants, thereby improving the CO absorption capacity of the heterojunction material 2 High-efficiency stable reduction performance of the catalyst.
Comparative example 1
Comparative example 1 Bulk-TiO was used 2 The preparation process of the BiOBr material is as follows:
(1) Measuring 1mL of ammonia water, 2mL of tetrabutyl titanate and ethanol by using a measuring cylinder, heating to 45 ℃, stirring for 24 hours, cooling to room temperature, respectively cleaning with absolute ethanol and deionized water for 3-5 times, and then placing in a 60 ℃ oven for drying to obtain amorphous massive TiO 2 Particles for standby; wherein, the volume ratio of ammonia water, tetrabutyl titanate and ethanol is controlled to be 1:2:150.
(2) The amorphous bulk TiO obtained in the step (1) is treated 2 Transferring to a muffle furnace, heating at 550 ℃ for 2 hours, and cooling to room temperature along with the furnace to obtain massive TiO 2 ；
(3) The bulk TiO obtained in the step (2) is treated 2 Surface treatment is carried out, the surface treatment is soaked in dilute sulfuric acid solution with the concentration of 2mol/L for 2 hours, absolute ethyl alcohol and deionized water are respectively used for cleaning for 3 to 5 times, and then the surface treatment is put into a baking oven with the temperature of 60 ℃ for standby.
(4) Weighing the bulk TiO obtained in the step (3) 2 Dissolving the particles, bismuth nitrate pentahydrate, cetyl trimethyl ammonium bromide and PVP in 25mL of glycol, stirring for 30min, transferring into a 50mL reaction kettle, hydrothermal treating at 160deg.C for 1 hr, and cooling to room temperature with a furnace to obtain Bulk-TiO 2 crude/BiOBr; wherein the bismuth nitrate pentahydrate is prepared by mixing ethylene glycol with waterThe concentration of the solution is 0.02mol/L, the concentration of PVP is 0.2g/L, and Bulk-TiO is controlled 2 The molar ratio of bismuth nitrate pentahydrate to cetyltrimethylammonium bromide is 5:4:4.
(5) Bulk-TiO obtained in the step (4) is subjected to 2 Washing the BiOBr coarse product with absolute ethanol and deionized water for 3-5 times, and oven drying at 60deg.C to obtain Bulk-TiO 2 BiOBr composite.
Likewise, for comparison with example 1, CO 2 Reduction to model reaction to investigate Bulk-TiO prepared in comparative example 1 2 The photo-catalytic performance of the BiOBr composite material is as follows:
weighing 0.05g of Bulk-TiO prepared in this comparative example 2 Loading the/BiOBr composite material into a reaction tank, and introducing CO into the reaction tank 2 And H is 2 The volume ratio is 1:4, continuously ventilating for 30min to ensure that the air in the reaction tank is discharged, sealing the reaction tank after ventilation is finished, turning on a light source, irradiating by using a full spectrum light source, extracting 1mL of gas in the reaction tank every half an hour, and detecting the gas types and the content of each substance by using a chromatograph. After 3h illumination, the rate of CO production was determined to be 7.24. Mu. Mol.h by product detection -1 ·g -1 There is a significant decrease in catalytic performance compared to example 1.
Example 2
Flower ball-shaped TiO 2 The preparation method of the BiOBr core-shell structure heterojunction material mainly comprises the following steps:
(1) Measuring tetraethyl silicate, ammonia water, deionized water and ethanol by a measuring cylinder, mixing in a beaker, stirring for 3 hours at room temperature, cleaning for 3-5 times by the deionized water, and drying to obtain SiO 2 Microspheres for standby; wherein, the volume ratio of tetraethyl silicate, ammonia water, deionized water and ethanol is 1:1:2:15;
(2) Weighing 0.2g of SiO synthesized in step (1) with an electronic balance 2 Dispersing the microspheres in 150mL of ethanol to obtain a suspension;
(3) Measuring 1mL of ammonia water and 2mL of tetrabutyl titanate by using a measuring cylinder, adding the ammonia water and the tetrabutyl titanate into the suspension in the step (2), heating the mixture to 45 ℃ and stirring the mixture for 2After 4 hours, the obtained solution is cooled to room temperature, centrifugally dried, washed for 3 to 5 times by absolute ethyl alcohol and deionized water, and then dried in a baking oven at 60 ℃ to obtain amorphous SiO 2 @TiO 2 Standby; wherein, the volume ratio of the ammonia water, the tetrabutyl titanate and the ethanol in the suspension is controlled to be 1:2:150.
(4) The amorphous SiO obtained in the step (3) is treated 2 @TiO 2 Transferring to a muffle furnace, heating at 550 ℃ for 2 hours, cooling to room temperature along with the furnace to obtain SiO 2 @TiO 2 A microsphere;
(5) The SiO obtained in the step (4) is reacted with 2 @TiO 2 Etching the microspheres in hydrofluoric acid solution with volume concentration of 5%, respectively washing the microspheres with absolute ethyl alcohol and deionized water for 3-5 times, and then drying the microspheres in a 60 ℃ oven to obtain TiO 2 Hollow microspheres for standby.
(6) The TiO obtained in the step (5) is treated 2 The hollow microspheres are subjected to surface treatment, soaked in 2mol/L dilute sulfuric acid solution for 2 hours, respectively washed with absolute ethyl alcohol and deionized water for 3-5 times, and then placed in a 60 ℃ oven for drying for standby.
(7) Weighing the TiO obtained in step (6) 2 Dissolving hollow microspheres, bismuth nitrate pentahydrate, cetyl trimethyl ammonium bromide and PVP in glycol, stirring for half an hour, transferring to a 50mL reaction kettle, hydrothermal for 1 hour at 160 ℃, cooling to room temperature along with a furnace, and centrifuging to obtain TiO 2 Crude product of heterojunction material with BiOBr core-shell structure; wherein, the concentration of bismuth nitrate pentahydrate in glycol is 0.02mol/L, PVP is 0.2g/L, tiO 2 The molar ratio of the hollow microspheres, the bismuth nitrate pentahydrate and the cetyltrimethylammonium bromide is 7:4:4.
(8) The TiO obtained in the step (7) is treated 2 The crude product of the heterojunction material with the BiOBr core-shell structure is respectively washed by absolute ethyl alcohol and deionized water for 3 to 5 times, and then is dried in a baking oven at 60 ℃ to obtain flower-spherical TiO 2 A BiOBr core-shell structure heterojunction material.
In the form of CO 2 Reduction to model reaction to investigate the flower-like TiO prepared in example 2 2 Photo-catalytic performance of/BiOBr core-shell structure heterojunction material withThe body process is as follows:
0.05g of TiO prepared in this example is weighed 2 loading/BiOBr catalyst into a reaction tank, introducing CO into the reaction tank 2 And H is 2 The volume ratio is 1:4, continuously ventilating for 30min to ensure that the air in the reaction tank is discharged, and sealing the reaction tank after ventilation is finished; the light source was turned on, irradiation was performed using a full spectrum light source, and 1mL of the gas in the reaction tank was extracted every half an hour, and the gas species and the contents of the respective substances were detected by chromatography. After 3h of illumination, the conversion of CO2 into CO can be determined by product detection, and the CO generation rate is 15.11 mu mol.h -1 ·g -1 The catalytic performance of the catalyst is Bulk-TiO synthesized in comparative example 1 2 2.1 times per BiOBr.
Example 3
Flower ball-shaped TiO 2 The preparation method of the BiOBr core-shell structure heterojunction material mainly comprises the following steps:
(1) Measuring tetraethyl silicate, ammonia water, deionized water and ethanol by a measuring cylinder, mixing in a beaker, stirring for 3 hours at room temperature, cleaning for 3-5 times by the deionized water, and drying to obtain SiO 2 Microspheres for standby; wherein, the volume ratio of tetraethyl silicate, ammonia water, deionized water and ethanol is 1:1:2:15;
(2) Weighing 0.2g of SiO synthesized in step (1) with an electronic balance 2 Dispersing the microspheres in 150mL of ethanol to obtain a suspension;
(3) Measuring 1mL of ammonia water and 2mL of tetrabutyl titanate by using a measuring cylinder, adding the 1mL of ammonia water and 2mL of tetrabutyl titanate into the suspension in the step (2), heating to 45 ℃, stirring for 24 hours, cooling the obtained solution to room temperature, centrifugally drying, washing with absolute ethyl alcohol and deionized water for 3-5 times, and then drying in a 60 ℃ oven to obtain amorphous SiO 2 @TiO 2 Standby; wherein, the volume ratio of the ammonia water, the tetrabutyl titanate and the ethanol in the suspension is controlled to be 1:2:150.
(4) The amorphous SiO obtained in the step (3) is treated 2 @TiO 2 Transferring to a muffle furnace, heating at 550 ℃ for 2 hours, cooling to room temperature along with the furnace to obtain SiO 2 @TiO 2 A microsphere;
(5) The step (4) is followed bySiO 2 @TiO 2 Etching the microspheres in hydrofluoric acid solution with volume concentration of 5%, respectively washing the microspheres with absolute ethyl alcohol and deionized water for 3-5 times, and then drying the microspheres in a 60 ℃ oven to obtain TiO 2 Hollow microspheres for standby.
(6) The TiO obtained in the step (5) is treated 2 The hollow microspheres are subjected to surface treatment, soaked in 2mol/L dilute sulfuric acid solution for 2 hours, respectively washed with absolute ethyl alcohol and deionized water for 3-5 times, and then placed in a 60 ℃ oven for drying for standby.
(7) Weighing the TiO obtained in step (6) 2 Dissolving hollow microspheres, bismuth nitrate pentahydrate, cetyl trimethyl ammonium bromide and PVP in glycol, stirring for half an hour, transferring to a 50mL reaction kettle, hydrothermal for 1 hour at 160 ℃, cooling to room temperature along with a furnace, and centrifuging to obtain TiO 2 Crude product of heterojunction material with BiOBr core-shell structure; wherein, the concentration of bismuth nitrate pentahydrate in glycol is 0.02mol/L, PVP is 0.2g/L, tiO 2 The mole ratio of the hollow microsphere, the bismuth nitrate pentahydrate and the cetyltrimethylammonium bromide is 3:4:4.
(8) The TiO obtained in the step (7) is treated 2 The crude product of the heterojunction material with the BiOBr core-shell structure is respectively washed by absolute ethyl alcohol and deionized water for 3 to 5 times, and then is dried in a baking oven at 60 ℃ to obtain flower-spherical TiO 2 A BiOBr core-shell structure heterojunction material.
In the form of CO 2 Reduction to model reaction to investigate the flower-like TiO prepared in example 2 2 The photo-catalytic performance of the BiOBr core-shell structure heterojunction material comprises the following specific processes:
0.05g of TiO prepared in this example is weighed 2 loading/BiOBr catalyst into a reaction tank, introducing CO into the reaction tank 2 And H is 2 The volume ratio is 1:4, continuously ventilating for 30min to ensure that the air in the reaction tank is discharged, and sealing the reaction tank after ventilation is finished; the light source was turned on, irradiation was performed using a full spectrum light source, and 1mL of the gas in the reaction tank was extracted every half an hour, and the gas species and the contents of the respective substances were detected by chromatography. After 3h of illumination, the rate of CO production was determined to be 13.5. Mu. Mol.h by product detection -1 ·g -1 The catalytic performance of the catalyst is Bulk-TiO synthesized in comparative example 1 2 1.86 times per BiOBr.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.
Claims (9)
1. Flower ball-shaped TiO 2 A heterojunction material with a BiOBr core-shell structure is characterized in that the heterojunction material adopts TiO 2 The hollow microsphere is taken as a main body, a plurality of BiOBr nano-sheets are grown on each TiO 2 The surface of the hollow microsphere forms a heterostructure of an independent flower-ball-shaped core-shell structure.
2. The TiO according to claim 1 2 The BiOBr core-shell structure heterojunction material is characterized in that the TiO 2 The size of the hollow microsphere is 300-600 nm, and the flower-sphere-shaped TiO 2 The overall size of the heterojunction material with the BiOBr core-shell structure is 400-800 nm; the TiO 2 The mol ratio of Ti/Bi in the BiOBr core-shell structure heterojunction material is (0.7-3): 1.
3. the TiO according to any one of claims 1 to 2 2 A preparation method of a heterojunction material with a BiOBr core-shell structure is characterized in that silicon dioxide is used as a template to synthesize TiO 2 The hollow microsphere is used for carrying the BiOBr nano sheet on TiO by an in-situ hydrothermal method 2 The surfaces of the hollow microspheres form flower-sphere-shaped TiO 2 A BiOBr core-shell structure heterojunction material.
4. Flower ball-shaped TiO 2 The preparation method of the BiOBr core-shell structure heterojunction material is characterized by comprising the following steps:
(1) Dissolving tetraethyl silicate in ethanol, deionized water and ammonia water, stirring and reacting to obtain SiO 2 A microsphere;
(2) SiO is made of 2 Dispersing the microspheres in ethanol, adding ammonia water, and stirring to obtainA dispersion; adding tetrabutyl titanate into the dispersion liquid, and performing heating treatment; the solution obtained after the heating treatment is separated to obtain a solid product and calcined to obtain SiO 2 @TiO 2 A microsphere; siO is made of 2 @TiO 2 Etching the microspheres by using hydrofluoric acid solution to obtain TiO 2 Hollow microspheres;
(3) Hollow TiO 2 Soaking the microspheres in dilute sulfuric acid, washing, drying, dispersing into ethylene glycol, adding bismuth nitrate pentahydrate, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone, and performing hydrothermal reaction to obtain TiO 2 A BiOBr core-shell structure heterojunction material.
5. The TiO according to claim 4 2 The preparation method of the BiOBr core-shell structure heterojunction material is characterized in that in the step (1), the volume ratio of the tetraethyl silicate to ethanol, deionized water and ammonia water is 1: (10-15): (1-2): 1, a step of; the stirring time is 2-5 h.
6. The TiO according to claim 4 2 The preparation method of the BiOBr core-shell structure heterojunction material is characterized in that in the step (2), the SiO 2 The dispersion concentration of the microspheres in the ethanol is 0.5-2 g/L, and the volume ratio of ammonia water to ethanol is 1: (100-200), the volume ratio of butyl titanate to ethanol is 1: (50-100); the heating temperature is 40-50 ℃ and the heating time is 20-30 hours; the calcination temperature is 500-600 ℃, and the calcination time is 1-4 h; the volume concentration of the hydrofluoric acid solution is 2-5%.
7. The TiO according to claim 4 2 The preparation method of the BiOBr core-shell structure heterojunction material is characterized in that in the step (3), the concentration of dilute sulfuric acid is 1.5-2.5 mol/L, and the soaking time is 2-3 h; hollow TiO 2 The dispersion concentration of the microsphere in the glycol solution is 0.015-0.05 mol/L, and the mole ratio of bismuth nitrate pentahydrate to cetyltrimethylammonium bromide is (0.7-3) according to Ti/Bi: 1, bi/Br molar ratio of 1: (1-1.5) feeding; PVP concentration in glycol is 0.1-5 g/L; the hydrothermal reaction temperature is 120-180 ℃ and the hydrothermal time is 0.5-to-ultra2h。
8. The TiO according to claim 1 2 Application of the/BiOBr core-shell structure heterojunction material in photocatalytic degradation.
9. The TiO according to claim 1 2 Application of the/BiOBr core-shell structure heterojunction material in photocatalytic carbon dioxide reduction.
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