CN113813971A - 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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- CN113813971A CN113813971A CN202111199283.3A CN202111199283A CN113813971A CN 113813971 A CN113813971 A CN 113813971A CN 202111199283 A CN202111199283 A CN 202111199283A CN 113813971 A CN113813971 A CN 113813971A
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- sodium titanate
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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 85
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 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 33
- 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
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002071 nanotube Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001816 cooling 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 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- FOQHYNYNHYNUIN-UHFFFAOYSA-N [O].[Br] Chemical compound [O].[Br] FOQHYNYNHYNUIN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- -1 permanganates Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium 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
- 230000000694 effects Effects 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
- 239000011941 photocatalyst Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000012512 characterization method Methods 0.000 description 2
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- 238000001000 micrograph 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
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000028327 secretion Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid 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
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 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
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 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
- 238000001228 spectrum 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
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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
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- 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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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 necklaces formed by self-assembling and directionally arranging bismuth oxybromide and sodium titanate nano particles; the (101) and (020) crystal faces of the bismuth oxybromide and sodium titanate nanoparticles are in close contact to construct a heterogeneous interface. By utilizing the mutual cooperation of the oriented arrangement of bromine oxygen and sodium titanate nano particles and a heterogeneous interface, the separation and transfer of photoproduction electrons and holes are promoted, the high-efficiency conversion of the reaction for preparing benzaldehyde by photocatalysis 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 and most commonly used aromatic aldehyde in industry, and is widely applied to synthesis of chemical products such as various 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 not only use hazardous or corrosive agents, such as chromates, permanganates, hypochlorites and Br2And also releases considerable amounts of toxic by-products after production. With the continuous development of modern economic society, people are increasingly conscious of environmental protection. Therefore, the development of a green and environment-friendly benzaldehyde synthesis route is urgently needed.
The photocatalytic oxidation of benzyl alcohol to synthesize benzaldehyde is an important subject of chemical, especially catalytic research because of its characteristics of greenness, less pollution, less by-products and easy separation. BiOBr, a typical layered Bi-based semiconductor material, is considered 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 practical application of the photocatalyst is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst and a preparation method thereof, and the catalyst is used for the reaction of photocatalytic oxidation of benzyl alcohol to prepare benzaldehyde.
In order to realize the purpose, the invention adopts the following technical scheme:
the necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst is composed of a nano necklace formed by self-assembling and directionally arranging bismuth oxybromide and sodium titanate nano particles; the crystal face of the bismuth oxybromide (101) and the crystal face of the sodium titanate (020) are in close contact to construct a heterogeneous interface.
Furthermore, the nano necklace is a plurality of nano necklaces, and the plurality of nano necklaces are interwoven into a net structure.
Further, the size of the nano particles is 14-20 nm.
The preparation method of the necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst provided by the invention has the advantages that 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-assembling and directionally arranging the bismuth oxybromide and sodium titanate nanoparticles.
The preparation method of the necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst comprises the following steps:
(1) to the reaction solution of 10 mol. L-1Adding 1g of titanium dioxide (P25) into a sodium hydroxide solution, keeping the temperature at 120-150 ℃ for 24h, cooling to room temperature, centrifugally filtering and washing a 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 regulate pH to 10-12, adding Bi (NO) while stirring3)3·5H2O and KBr, sealing the reaction kettle at the constant temperature of 150-170 ℃ for 20h, cooling to room temperature, washing with water, centrifuging, and drying to obtain the chain-like bismuth oxybromide and sodium titanate nanotube heterojunction composite catalyst.
Further, Bi (NO)3)3·5H2The mass ratio of O to the sodium titanate nanotube is 1:1, wherein the mass of the sodium titanate nanotube is the mass of the wet sodium titanate nanotube after drying.
Further, said Bi (NO)3)3·5H2The molar ratio of O to KBr is 0.5:10-1: 10.
The invention provides a catalyst prepared by the preparation method.
The invention provides application of the catalyst prepared by the preparation method in preparation of benzaldehyde from benzyl alcohol.
Compared with the prior art, the invention has the beneficial effects that:
the invention synthesizes bismuth oxybromide and sodium titanate nano necklace heterojunction composite catalyst by using wet sodium titanate nano tube as precursor. The bismuth oxybromide and sodium titanate nanochain is formed by self-assembling and directionally arranging nanoparticles with the size of 14-20nm, and a plurality of the nanochain is interwoven into a net structure. The crystal faces of bismuth oxybromide (101) and sodium titanate (020) are in close contact, and a bromine-oxygen secretion and sodium titanate heterogeneous interface is effectively formed. By utilizing the mutual cooperation of the oriented arrangement of bromine oxygen and sodium titanate nano particles and a heterogeneous interface, the separation and transfer of photoproduction electrons and holes are promoted, the high-efficiency conversion of the reaction for preparing benzaldehyde by photocatalysis 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 and sodium titanate Na2Ti3O7BiOBr (bismuth oxybromide) and sodium titanate heterojunction composite catalyst
Na2Ti3O7XRD characterization of (1).
FIG. 2 shows a bismuth oxybromide and sodium titanate heterojunction composite catalyst BiOBr/Na2Ti3O7Characterizing an electron microscope; FIG. 2(a) is a scanning electron microscope picture of a bismuth oxybromide and sodium titanate heterojunction composite catalyst under a 500nm scale; FIG. 2(b) is a scanning electron microscope picture of a bismuth oxybromide and sodium titanate heterojunction composite catalyst on a 100nm scale; FIG. 2(c) is a transmission electron microscope image of a bismuth oxybromide and sodium titanate heterojunction composite catalyst on a 50nm scale; FIG. 2(d) is a high-resolution transmission electron microscope image of a bismuth oxybromide and sodium titanate heterojunction composite catalyst on a 2nm scale.
FIG. 3 shows bismuth oxybromide BiOBr and sodium titanate Na2Ti3O7BiOBr/Na catalyst for heterojunction composite of bismuth oxybromide and sodium titanate2Ti3O7Separation of photogenerated electrons and holes; FIG. 3(a) is a steady state fluorescence spectrum of a bismuth oxybromide and sodium titanate heterojunction composite catalyst; fig. 3(b) is the transient photocurrent intensity of the bismuth oxybromide and sodium titanate heterojunction composite catalyst.
FIG. 4 shows bismuth oxybromide BiOBr and sodium titanate Na2Ti3O7BiOBr/Na catalyst for heterojunction composite of bismuth oxybromide and sodium titanate2Ti3O7The reaction performance of preparing benzaldehyde by using the photocatalytic benzyl alcohol is good. FIG. 4(a) is the conversion of benzyl alcohol; FIG. 4(b) is the maximum production rate of benzaldehyde; FIG. 4(c) is the stability of the synthesized catalyst.
Detailed Description
The invention is further illustrated but is not in any way limited by the following specific examples.
Example 1
Preparation of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst
At room temperature, adding 30mL of deionized water into a 50mL polytetrafluoroethylene reaction kettle, adding 12g of sodium hydroxide while stirring, violently releasing heat, and cooling the solution to room temperature to obtain 0.1 mol.L-1And (2) adding 1g P25 into the sodium hydroxide solution under stirring, uniformly mixing, sealing the kettle, keeping the temperature at 120 ℃ for 24h, naturally cooling to room temperature, centrifugally filtering the obtained product, washing and precipitating until the pH value is about 8, and centrifuging to obtain a wet (non-dried) sodium titanate nanotube precursor.
Adding 30mL of deionized water into a 50mL polytetrafluoroethylene reaction kettle, adding 1g of wet sodium titanate nanotube precursor, stirring for 10min, adding a certain amount of ammonia water to adjust the pH value of the solution to be approximately equal to 11, and then adding 0.237mmol of Bi (NO) under stirring3)3·5H2O and 2.52mmol KBr, stirring for 10min, sealing the reaction kettle, keeping the temperature at 160 ℃ for 20h, cooling to room temperature, washing with water, centrifuging, and drying at 80 ℃ for 12h to obtain 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 for preparing benzaldehyde by photocatalytic oxidation of benzyl alcohol is carried out in a photocatalytic reaction kettle (Beijing Zhongzhijin source CEL-HPR + 100). The reaction takes acetonitrile as a solvent, o-xylene as an internal standard and benzyl alcohol as a reactant, and the reaction is carried out in an oxygen atmosphere. Accurately measuring 20mL of acetonitrile, 20 mu L of o-xylene and 20 mu L of benzyl alcohol, placing the materials in a reaction kettle, uniformly mixing the materials under a vortex oscillator, adding 50mg of catalyst, sealing the reactor, introducing 0.5Mpa of high-purity oxygen, placing the reactor under a xenon lamp light source, reacting at the temperature of 60 ℃ for 0-3h, centrifuging and filtering the reaction liquid. The stock solution and the reaction solution were measured by gas chromatography (Agilent GC7820A) equipped with FID and TCD dual detectors, respectively, and the conversion of benzyl alcohol and the selectivity of benzaldehyde were calculated. For the cycling stability experiment, the catalyst after the photocatalytic reaction was centrifuged, washed with ethanol and dried at 60 ℃ before the next experiment was performed.
Comparative example 1
Preparation of single-phase bismuth oxybromide catalyst
30mL of deionized water was added to a 50mL Teflon reactor, a defined amount of ammonia was added to adjust the pH of the solution to approximately 11, and then 0.237mmol of Bi (NO) was added with stirring3)3·5H2O and 2.52mmol KBr, stirring for 10min, sealing the reaction kettle, keeping the temperature at 160 ℃ for 20h, cooling to room temperature, washing with water, centrifuging, and drying at 80 ℃ for 12h to obtain the single-phase bismuth oxybromide catalyst.
Comparative example 2
Preparation of single-phase sodium titanate catalyst
Adding 30mL of deionized water into a 50mL polytetrafluoroethylene reaction kettle at room temperature, adding 12g of sodium hydroxide under stirring, violently releasing heat, cooling the solution to room temperature to obtain a 10M sodium hydroxide solution, then adding 1g P25 into the sodium hydroxide solution under stirring, uniformly mixing, sealing the kettle, keeping the temperature at 120 ℃ for 24h, naturally cooling to room temperature, centrifugally filtering the obtained product, washing and precipitating until the pH value is about 8, and drying the obtained sodium titanate nanotube in an oven at 80 ℃ for 12h after centrifugation to obtain the single-phase sodium titanate catalyst.
FIG. 1 shows XRD spectra of the catalysts synthesized in example 1 and comparative examples 1-2. The sodium titanate samples gave diffraction peaks at 24.88, 28.42 and 48.44 deg. corresponding to the (102), (111) and (410) crystal planes of monoclinic sodium titanate, respectively, indicating that the synthesized samples were single-phase sodium titanate. The diffraction peaks at 25.46, 31.97, 37.94, 48 and 55 ° in the bismuth oxybromide sample correspond to the crystal planes of bismuth oxybromide (011), (012), (112), (014) and (212), respectively, of the tetragonal crystal system, indicating that the synthesized sample is single-phase bismuth oxybromide. The peak of the bismuth oxybromide and sodium titanate composite catalyst only shows diffraction peaks corresponding to single-phase sodium titanate and single-phase bismuth oxybromide samples, and other diffraction peaks do not appear, which indicates that the bismuth oxybromide and sodium titanate composite catalyst is formed.
Figure 2 shows the morphology characterization of the bismuth oxybromide and sodium titanate heterojunction composite catalyst, and from figure 2b we can clearly see that the bismuth oxybromide and sodium titanate composite catalyst is composed of a nanochannel formed by a plurality of nanoparticles in an oriented arrangement. As can be seen from FIG. 2a, a necklace is randomly arranged and interlaced to form 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 0.40nm and 0.25nm 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 is shown that the bismuth oxybromide (101) and sodium titanate (020) crystal planes are in close contact with each other, and a bromine-oxygen secretion and sodium titanate heterogeneous interface is effectively formed.
FIG. 3 shows the separation performance of photo-generated electrons and holes of the catalyst synthesized in 1-2. In the steady state fluorescence spectrum of fig. 3a, it can be seen that the peak intensities of the spectra of bismuth oxybromide and sodium titanate are much higher than those of the heterojunction composite catalyst of bismuth oxybromide and sodium titanate; the transient photocurrent intensity of fig. 3b, bismuth oxybromide and sodium titanate heterojunction composite catalyst gave the strongest photocurrent intensity. These results indicate that the construction of the heterojunction of bismuth oxybromide and sodium titanate effectively facilitates the separation of the photogenerated electrons and holes.
FIG. 4 shows the reaction performance of the catalyst synthesized in 1-2 in photocatalytic preparation of benzaldehyde. As can be seen from fig. 4a, the conversion of benzyl alcohol of the synthesized catalyst gradually increased with the increase of the reaction time. Compared with single-phase bismuth oxybromide and single-phase sodium titanate, the nano necklace heterojunction composite catalyst has the advantages that the reaction activity is enhanced, the conversion rate of benzyl alcohol can reach 100% after the reaction is carried out for 3 hours, and the selectivity of benzaldehyde can reach 100%. As can be seen from FIG. 4b, the maximum benzaldehyde formation rate was 7.52mmol after 2hreacted benzyl alcohol·g-1·h-1The single-phase bismuth oxybromide and the single-phase sodium titanate respectively catalyze the benzyl alcohol to prepare the benzaldehyde at a high reaction speed16 and 22 times the rate. Fig. 4c shows that the bismuth oxybromide and sodium titanate heterojunction composite catalyst has excellent reaction stability, the activity of the composite catalyst is not obviously reduced after 4 times of reaction cycles, and the activity of the composite catalyst is only reduced from 87.4% to 84.5%.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (9)
1. A necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst is characterized in that the catalyst is composed of nano necklaces formed by self-assembly and directional arrangement of bismuth oxybromide and sodium titanate nano particles; the crystal face of the bismuth oxybromide (101) and the crystal face of the sodium titanate (020) are in close contact to construct a heterogeneous interface.
2. A necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst as in claim 1, wherein the nanochain is a plurality of nanochains, and a plurality of nanochains are interwoven into a net structure.
3. A necklace-like bismuth oxybromide and sodium titanate heterojunction composite catalyst as in claim 1, wherein the size of the nano-particles is 14-20 nm.
4. A preparation method of a necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst is characterized in that a wet sodium titanate nanotube is used as a precursor, and a one-step hydrothermal method is adopted to controllably synthesize a nano necklace formed by self-assembling and directionally arranging bismuth oxybromide and sodium titanate nano particles.
5. The preparation method of the necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst as claimed in claim 4, is characterized by comprising the following steps:
(1) to the reaction solution of 10 mol. L-1Adding 1g of titanium dioxide (P25) into a sodium hydroxide solution, keeping the temperature at 120-150 ℃ for 24h, cooling to room temperature, centrifugally filtering and washing a 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 regulate pH to 10-12, adding Bi (NO) while stirring3)3·5H2O and KBr, sealing the reaction kettle at the constant temperature of 150-170 ℃ for 20h, cooling to room temperature, washing with water, centrifuging, and drying to obtain the chain-like bismuth oxybromide and sodium titanate nanotube heterojunction composite catalyst.
6. The preparation method of the catenated bismuth oxybromide and sodium titanate heterojunction composite catalyst according to claim 4, wherein Bi (NO) is used3)3·5H2The mass ratio of O to the sodium titanate nanotube is 1:1, wherein the mass of the sodium titanate nanotube is the mass of the wet sodium titanate nanotube after drying.
7. The preparation method of the catenated bismuth oxybromide and sodium titanate heterojunction composite catalyst according to claim 4, wherein the Bi (NO) is3)3·5H2The molar ratio of O to KBr is 0.5:10-1: 10.
8. The catalyst prepared by the preparation method of any one of claims 4 to 7.
9. The use of the catalyst of claim 8 in the preparation of benzaldehyde from benzyl alcohol.
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