CN113813971B - Preparation method and application of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst - Google Patents
Preparation method and application of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst Download PDFInfo
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- CN113813971B CN113813971B CN202111199283.3A CN202111199283A CN113813971B CN 113813971 B CN113813971 B CN 113813971B CN 202111199283 A CN202111199283 A CN 202111199283A CN 113813971 B CN113813971 B CN 113813971B
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- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 54
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002071 nanotube Substances 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005489 Bromoxynil Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- -1 permanganates Chemical class 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of nano composite materials and photocatalysis, and particularly relates to a preparation method and application of a necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst. The catalyst consists of nano necklace formed by self-assembly directional arrangement of bismuth oxybromide and sodium titanate nano particles; the (101) crystal face and the (020) crystal face of the bismuth oxybromide and the sodium titanate nanometer particle are closely contacted to construct a heterogeneous interface. By utilizing the mutual coordination of directional arrangement of bromoxynil and sodium titanate nano particles and a heterogeneous interface, the separation and transmission of photo-generated electrons and holes are promoted, the efficient conversion of the reaction of preparing benzaldehyde by photocatalytic benzyl alcohol is realized, the conversion rate of the benzyl alcohol is 100%, and the selectivity of the benzaldehyde can reach 100%.
Description
Technical Field
The invention belongs to the technical field of nano composite materials and photocatalysis, and particularly relates to a preparation method and application of a necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst.
Background
Benzaldehyde is an important chemical intermediate, is the simplest aromatic aldehyde which is the most commonly used in industry, and is widely applied to the synthesis of various chemical products such as medicines, foods, living goods and the like. The traditional benzaldehyde preparation method mainly adopts a toluene oxidation or benzyl chloride hydrolysis method. Both of the above processes use not only dangerous or corrosive agents such as chromates, permanganates, hypochlorites and Br 2 And also release a considerable amount of toxic by-products after production. With the sustainable development of modern economic society, people's awareness of environmental protection is also continuously increasing. Therefore, there is an urgent need to develop a green and environment-friendly benzaldehyde synthesis route.
The photocatalytic oxidation of benzyl alcohol to benzaldehyde is an important subject for chemical, particularly catalytic, research due to its green, less pollution, less byproducts, easy separation and other characteristics. BiOBr, a typical layered Bi-based semiconductor material, is considered to be an excellent semiconductor photocatalyst due to its chemical stability and unique chemical properties. However, the conventional BiOBr photocatalyst has low separation efficiency of photo-generated electrons and holes, and limits practical application of photocatalysis.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst and a preparation method thereof, and the catalyst is used for preparing benzaldehyde by photocatalytic oxidation of benzyl alcohol.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst provided by the invention is composed of nano necklaces formed by self-assembly directional arrangement of bismuth oxybromide and sodium titanate nano particles; the bismuth oxybromide (101) crystal face and the sodium titanate (020) crystal face are closely contacted to form a heterogeneous interface.
Further, the nano necklaces are a plurality of, and the plurality of nano necklaces are interwoven into a net structure.
Further, the nanoparticle has a size of 14-20 nm.
According to the preparation method of the necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst, wet sodium titanate nanotubes are used as precursors, and a one-step hydrothermal method is adopted to controllably synthesize the nano necklace formed by self-assembly and directional arrangement of bismuth oxybromide and sodium titanate nanoparticles.
The invention relates to a preparation method of a necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst, which comprises the following steps:
(1) To the direction of10 mol·L -1 1g of titanium dioxide (P25) is added into the sodium hydroxide solution, the temperature is kept constant at 120-150 ℃ for 24-h,
cooling to room temperature, centrifugally filtering and washing the product to pH 7-9, and centrifuging to obtain wet sodium titanate nanotube precursor;
(2) Adding wet sodium titanate nanotube precursor into deionized water, adding ammonia water to adjust pH to 10-12, adding Bi (NO) under stirring 3 ) 3 ·5H 2 O and KBr, sealing the reaction kettle at the constant temperature of 150-170 ℃ for 20 h, cooling to room temperature, washing with water, centrifuging and drying to obtain the necklace-shaped bismuth oxybromide and sodium titanate nanotube heterojunction composite catalyst.
Further, bi (NO 3 ) 3 ·5H 2 The mass ratio of O to the sodium titanate nanotubes is 1:1, wherein the mass of the sodium titanate nanotubes is the mass of the wet sodium titanate nanotubes after drying.
Further, the Bi (NO 3 ) 3 ·5H 2 The molar ratio of O to KBr is 0.5:10-1:10.
The invention provides the catalyst prepared by the preparation method.
The invention provides an application of the catalyst prepared by the preparation method in preparing benzaldehyde from benzyl alcohol.
Compared with the prior art, the invention has the beneficial effects that:
the wet sodium titanate nanotube is used as a precursor to synthesize the bismuth oxybromide and sodium titanate nano necklace heterojunction composite catalyst. The bismuth oxybromide and sodium titanate nanometer necklace is formed by self-assembly and directional arrangement of nanometer particles with the size of 14-20 nm, and a plurality of necklaces are mutually interwoven into a net structure. The bismuth oxybromide (101) crystal face and the sodium titanate (020) crystal face are closely contacted, so that a bromoxynil and sodium titanate heterogeneous interface is effectively formed. By utilizing the mutual coordination of directional arrangement of bromoxynil and sodium titanate nano particles and a heterogeneous interface, the separation and transmission of photo-generated electrons and holes are promoted, the efficient conversion of the reaction of preparing benzaldehyde by photocatalytic benzyl alcohol is realized, the conversion rate of the benzyl alcohol is 100%, and the selectivity of the benzaldehyde can reach 100%.
Drawings
FIG. 1 shows bismuth oxybromide BiOBr, sodium titanate Na 2 Ti 3 O 7 Bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na 2 Ti 3 O 7 XRD characterization of (b);
FIG. 2 is a bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na 2 Ti 3 O 7 2a is bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na 2 Ti 3 O 7 The formed net structure diagram, 2b is bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na 2 Ti 3 O 7 Nanometer necklace graph formed by directional arrangement of nanometer particles, 2c is bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na 2 Ti 3 O 7 A size map of the nanoparticles;
FIG. 3 shows bismuth oxybromide BiOBr, sodium titanate Na 2 Ti 3 O 7 Bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na 2 Ti 3 O 7 The separation performance of the photo-generated electrons and the holes, 3a is the steady-state fluorescence spectrum of the bismuth oxybromide and sodium titanate heterojunction composite catalyst, and 3b is the transient photocurrent intensity of the bismuth oxybromide and sodium titanate heterojunction composite catalyst;
FIG. 4 shows bismuth oxybromide BiOBr, sodium titanate Na 2 Ti 3 O 7 Bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na 2 Ti 3 O 7 The photocatalytic reaction performance of benzyl alcohol to prepare benzaldehyde, 4a is the conversion rate of benzyl alcohol, 4b is the maximum generation rate of benzaldehyde, and 4c is the activity of the synthesized catalyst.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited in any way.
Example 1
Preparation of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst
Adding 30 mL deionized water into a 50 mL polytetrafluoroethylene reaction kettle at room temperature, adding 12 g sodium hydroxide under stirring, and strongly releasing heat, and cooling the solution to room temperature to obtain 0.1 molL -1 Sodium hydroxide solution, then adding 1g of P25 into the sodium hydroxide solution under stirring, uniformly mixing, sealing the kettle, naturally cooling to room temperature at constant temperature of 24-h at 120 ℃, centrifugally filtering the obtained product, washing the precipitate to pH of about 8, and centrifuging to obtain a wet (non-dried) sodium titanate nanotube precursor.
Adding 30 mL deionized water into 50 mL polytetrafluoroethylene reaction kettle, adding 1g wet sodium titanate nanotube precursor, stirring for 10 min, adding a certain amount of ammonia water to adjust pH of the solution to about 11, and adding 0.237 mmol Bi (NO 3 ) 3 5H2O and 2.52 mmol KBr, stirring for 10 min, sealing the reaction kettle, keeping the constant temperature at 160 ℃ for 20H, cooling to room temperature, washing with water, centrifuging, and drying at 80 ℃ for 12H to prepare the necklace-shaped bismuth oxybromide and sodium titanate nanotube heterojunction composite catalyst.
Example 2
Reaction for preparing benzaldehyde by photocatalytic oxidation of benzyl alcohol
The reaction of preparing benzaldehyde by photocatalytic oxidation of benzyl alcohol is carried out in a photocatalytic reaction kettle (Beijing Zhongjinyuan CEL-HPR+100). The reaction takes acetonitrile as a solvent, o-xylene as an internal standard and benzyl alcohol as a reactant, and is carried out under the oxygen atmosphere. Accurately measuring 20 mL acetonitrile, 20 mu L o-xylene and 20 mu L benzyl alcohol, placing the materials in a reaction kettle, uniformly mixing the materials under a vortex oscillator, adding 50 mg catalyst, sealing the reactor, introducing 0.5 Mpa high-purity oxygen, placing the materials under a xenon lamp light source, reacting at 60 ℃ at 0-3 h, centrifuging the reaction solution, and filtering. The stock solution and the reaction solution were detected by gas chromatography (Agilent GC 7820A) equipped with both FID and TCD detectors, respectively, and the conversion rate of benzyl alcohol and the selectivity of benzaldehyde were calculated. For the circulation stabilization experiment, the catalyst after the photocatalytic reaction was centrifuged, washed with ethanol and dried at 60 ℃ and then subjected to the next experiment.
Comparative example 1
Preparation of single-phase bismuth oxybromide catalyst
Adding 30 mL deionized water into a 50 mL polytetrafluoroethylene reaction kettle, adding a certain amount of ammonia water to adjust the pH of the solution to be approximately equal to 11, and thenAfter that, 0.237 mmol Bi (NO) was added with stirring 3 ) 3 ·5H 2 O and 2.52 mmol KBr, stirring for 10 min, sealing the reaction kettle, keeping the constant temperature at 160 ℃ for 20 h, cooling to room temperature, washing with water, centrifuging, and drying at 80 ℃ for 12 h to prepare the single-phase bismuth oxybromide catalyst.
Comparative example 2
Preparation of single-phase sodium titanate catalyst
Adding 30 mL deionized water into 50 mL polytetrafluoroethylene reaction kettle at room temperature, adding 12 g sodium hydroxide under stirring, violently releasing heat, cooling to room temperature to obtain 10M sodium hydroxide solution, adding 1g P25 into sodium hydroxide solution under stirring, mixing, sealing, maintaining constant temperature at 120deg.C for 24 h, and naturally cooling to room temperature
And (3) centrifuging the obtained product, filtering, washing the precipitate to pH of about 8, and drying the obtained sodium titanate nanotube in an oven at 80 ℃ for 12 h after centrifuging to obtain the single-phase sodium titanate catalyst.
FIG. 1 shows XRD spectra of catalysts synthesized in example 1 and comparative examples 1 to 2. Sodium titanate samples gave diffraction peaks at 24.88, 28.42 and 48.44 ° corresponding to monoclinic sodium titanate (102), (111) and (410) crystal planes, respectively, indicating that the synthesized samples were single-phase sodium titanate. Diffraction peaks at 25.46, 31.97, 37.94, 48 and 55 degrees in the bismuth oxybromide sample correspond to the (011), (012), (112), (014) and (212) crystal planes of the tetragonal bismuth oxybromide, respectively, indicating that the synthesized sample is single-phase bismuth oxybromide. Only diffraction peaks corresponding to the single-phase sodium titanate and the single-phase bismuth oxybromide sample appear in the spectrum peaks of the bismuth oxybromide and sodium titanate composite catalyst, and other diffraction peaks do not appear, which indicates that the bismuth oxybromide and sodium titanate composite catalyst is formed.
The morphology characterization of the bismuth oxybromide and sodium titanate heterojunction composite catalyst is shown in fig. 2, and from fig. 2b, it can be clearly seen that the bismuth oxybromide and sodium titanate composite catalyst is composed of a nano necklace formed by directional arrangement of a plurality of nano particles. From fig. 2a it can be seen that a necklace is randomly arranged, interwoven into a net structure. As can be seen from fig. 2c, the size of the nanoparticles is 14-20 nm. As shown in fig. 2d, lattice fringes with interplanar spacings of 0.40 nm and 0.25 nm can be clearly seen on the nanoparticles, corresponding to bismuth oxybromide (101) crystal planes and sodium titanate (020) crystal planes, respectively, and based on the above analysis, it was shown that close contact between bismuth oxybromide (101) and sodium titanate (020) crystal planes effectively formed a bromoxynil and sodium titanate heterogeneous interface.
FIG. 3 compares the separation performance of photo-generated electrons and holes of the synthesized catalyst of 1-2. The steady state fluorescence spectrum of fig. 3a shows that the spectral peak intensities of bismuth oxybromide and sodium titanate are much higher than those of bismuth oxybromide and sodium titanate heterojunction composite catalyst; the transient photocurrent intensity of fig. 3b, bismuth oxybromide and sodium titanate heterojunction composite catalyst gives the strongest photocurrent intensity. These results indicate that the construction of the heterojunction of bismuth oxybromide and sodium titanate effectively promotes the separation of photogenerated electrons and holes.
FIG. 4 shows the reaction performance of the catalyst synthesized by 1-2 in preparing benzaldehyde by photocatalysis of benzyl alcohol. As can be seen from fig. 4a, the conversion of benzyl alcohol of the synthesized catalyst gradually increases with the increase of the reaction time. Compared with single-phase bismuth oxybromide and single-phase sodium titanate, the nano necklace heterojunction composite catalyst of bismuth oxybromide and sodium titanate shows enhanced reaction activity, reaction 3 h, the conversion rate of benzyl alcohol can reach 100%, and the selectivity of the benzaldehyde can reach 100%. As can be seen from FIG. 4b, reaction 2 h, the maximum rate of benzaldehyde formation was 7.52 mmol reacted benzyl alcohol ·g -1 ·h -1 The reaction rates of the single-phase bismuth oxybromide and the single-phase sodium titanate catalytic benzyl alcohol for preparing benzaldehyde are 16 times and 22 times respectively. Fig. 4c shows that the bismuth oxybromide and sodium titanate heterojunction composite catalyst has excellent reaction stability, the reaction cycle is 4 times, the activity of the composite catalyst is not obviously reduced, and the activity is only reduced from 87.4% to 84.5%.
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (5)
1. The necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst is characterized by comprising nano necklace formed by self-assembling and directional arrangement of bismuth oxybromide and sodium titanate nano particles; the nanometer necklaces are mutually interwoven into a net structure; the bismuth oxybromide (101) crystal face and the sodium titanate (020) crystal face are tightly contacted to form a heterogeneous interface; the bismuth oxybromide is BiOBr; the sodium titanate is Na 2 Ti 3 O 7 ；
The preparation method of the catalyst comprises the following steps:
(1) To 10 mol.L -1 Adding 1g of titanium dioxide P25 into a sodium hydroxide solution, keeping the temperature at 120-150 ℃ for 24-h, cooling to room temperature, centrifugally filtering and washing the product until the pH value is 7-9, and centrifuging to obtain a wet sodium titanate nanotube precursor;
(2) Adding wet sodium titanate nanotube precursor into deionized water, adding ammonia water to adjust pH to 10-12, adding Bi (NO) under stirring 3 ) 3 ·5H 2 O and KBr, sealing the reaction kettle at the constant temperature of 150-170 ℃ for 20 h, cooling to room temperature, washing with water, centrifuging and drying to obtain the necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst.
2. The necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst according to claim 1, characterized in that the size of the sodium titanate nano-particles is 14-20 nm.
3. The necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst according to claim 1, characterized in that Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to the sodium titanate nanotubes is 1:1, wherein the mass of the sodium titanate nanotubes is the mass of the wet sodium titanate nanotubes after drying.
4. According to claim 1The necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst is characterized in that the Bi (NO 3 ) 3 ·5H 2 The molar ratio of O to KBr is 0.5:10-1:10.
5. Use of the catalyst of any one of claims 1-4 in the preparation of benzaldehyde from benzyl alcohol.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789141A (en) * | 2004-12-15 | 2006-06-21 | 河南大学 | Method for preparing nano-tubular sodium titanate/titanci acid |
| CN103599772A (en) * | 2013-11-22 | 2014-02-26 | 福州大学 | Titanate nanotube composite type photocatalyst as well as preparation method and application thereof |
| DE102014212900A1 (en) * | 2014-07-03 | 2016-01-07 | RUHR-UNIVERSITäT BOCHUM | Photocatalytic preparation of 1,3-dihydroxyacetone |
| CN107572585A (en) * | 2017-09-08 | 2018-01-12 | 华南师范大学 | A kind of bismuth oxybromide visible light catalyst and preparation method thereof |
| CN109134228A (en) * | 2018-06-22 | 2019-01-04 | 杭州电子科技大学 | A kind of method that room temperature catalytic phenylmethanol generates benzaldehyde |
| CN109550513A (en) * | 2017-09-27 | 2019-04-02 | 天津大学 | A kind of preparation method and application of the titania nanotube heterojunction material of compound bismuth oxygen bromine |
| CN111939949A (en) * | 2020-07-17 | 2020-11-17 | 杭州师范大学 | Bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst and preparation method thereof |
| CN112808283A (en) * | 2020-12-31 | 2021-05-18 | 西安理工大学 | SrTiO3Microwave rapid preparation method of-BiOBr composite catalyst |
-
2021
- 2021-10-14 CN CN202111199283.3A patent/CN113813971B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789141A (en) * | 2004-12-15 | 2006-06-21 | 河南大学 | Method for preparing nano-tubular sodium titanate/titanci acid |
| CN103599772A (en) * | 2013-11-22 | 2014-02-26 | 福州大学 | Titanate nanotube composite type photocatalyst as well as preparation method and application thereof |
| DE102014212900A1 (en) * | 2014-07-03 | 2016-01-07 | RUHR-UNIVERSITäT BOCHUM | Photocatalytic preparation of 1,3-dihydroxyacetone |
| CN107572585A (en) * | 2017-09-08 | 2018-01-12 | 华南师范大学 | A kind of bismuth oxybromide visible light catalyst and preparation method thereof |
| CN109550513A (en) * | 2017-09-27 | 2019-04-02 | 天津大学 | A kind of preparation method and application of the titania nanotube heterojunction material of compound bismuth oxygen bromine |
| CN109134228A (en) * | 2018-06-22 | 2019-01-04 | 杭州电子科技大学 | A kind of method that room temperature catalytic phenylmethanol generates benzaldehyde |
| CN111939949A (en) * | 2020-07-17 | 2020-11-17 | 杭州师范大学 | Bismuth oxybromide/titanium dioxide nanotube composite material photocatalyst and preparation method thereof |
| CN112808283A (en) * | 2020-12-31 | 2021-05-18 | 西安理工大学 | SrTiO3Microwave rapid preparation method of-BiOBr composite catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 钛酸钠纳米管光催化降解有机磷农药敌敌畏;丁绮等;《分析科学学报》;第36卷(第2期);第255-259页 * |
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