CN116903451A - Method for efficiently and selectively oxidizing benzyl alcohol into benzaldehyde by photocatalysis - Google Patents
Method for efficiently and selectively oxidizing benzyl alcohol into benzaldehyde by photocatalysis Download PDFInfo
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 93
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 title claims description 19
- 230000001590 oxidative effect Effects 0.000 title claims description 5
- 238000007146 photocatalysis Methods 0.000 title description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000012456 homogeneous solution Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
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- 239000006227 byproduct Substances 0.000 abstract description 5
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- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
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- 230000001276 controlling effect Effects 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000002537 cosmetic Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000220304 Prunus dulcis Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 241000775848 Syringa oblata Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 235000013532 brandy Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229940089454 lauryl aldehyde Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- RVKCCVTVZORVGD-UHFFFAOYSA-N trinexapac-ethyl Chemical group O=C1CC(C(=O)OCC)CC(=O)C1=C(O)C1CC1 RVKCCVTVZORVGD-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Classifications
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- 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
-
- 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
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of high-efficiency selective benzyl alcohol oxide as benzaldehyde, which is an important chemical intermediate and has great application in the fields of pharmacy, medical treatment, cosmetics and the like. The current method for preparing benzyl alcohol has high cost, complex operation flow and easy generation of toxic byproducts, and we use inexhaustible solar energy as energy to synthesize BiOBr in situ 0.75 I 0.25 /Bi 24 O 31 Br 10 The composite material is used as a photocatalyst, acetonitrile is used as a solvent under the condition of not adding any sacrificial agent, and benzyl alcohol is efficiently and selectively oxidized into benzaldehyde. The reaction is carried out under the conditions of normal temperature and normal pressure and oxygen by regulating and controlling BiOBr x I 1‑x /Bi 24 O 31 Br 10 X ratio of (x)Regulating and controlling Br: the ratio I is thus such that the optimum catalytic activity is achieved. Experimental results show that BiOBr 0.75 I 0.25 /Bi 24 O 31 Br 10 The catalytic activity of the composite material is best, and the conversion rate of benzyl alcohol and the selectivity of generated benzaldehyde can reach 99% and 99% respectively within 1 h.
Description
Technical Field
The invention belongs to the field of energy materials, and particularly relates to a photocatalysis preparation method for selectively oxidizing benzyl alcohol into benzaldehyde.
Background
Benzaldehyde is an important chemical intermediate and chemical raw material and has great application in many fields. Not only can be used for preparing chemical raw materials such as laurylaldehyde, lauryl alcohol and the like, but also can be used as reagents for measuring ozone, phenol, alkaloid and methylene beside carboxyl. In addition, benzaldehyde can be used as special flavoring agent for head fragrance, and trace amount for flower fragrance formulation such as Syringa oblata, brandy, etc., and edible spice such as almond, berry, etc. In addition, benzaldehyde is an intermediate of the herbicide difenox, a plant growth regulator, trinexapac-ethyl. In addition, benzaldehyde can react with amide substances to produce medical intermediates.
Benzaldehyde is widely present in plants, especially rose plants, mainly in the leaves and stems of plants in the form of glycosides, but the cost of extracting benzaldehyde from plants is too high and the yield is low. The current industrial mass production method of benzaldehyde mainly comprises two main production methods respectively taking toluene and benzene as raw materials. The chlorination-recydrolysis method and the direct hydrolysis method of toluene are high in yield but high in cost, and toxic byproducts are generated. Benzene is used as a raw material, and under the actions of pressurization and aluminum trichloride, the benzene reacts with carbon monoxide and hydrogen chloride to obtain benzaldehyde, and the production process is complex and the energy consumption is high. Therefore, a benzaldehyde synthesis method which is low in cost, high in selectivity and environment-friendly is selected, and a method for preparing benzaldehyde by photocatalytic selective oxidation of benzyl alcohol is widely focused on green and efficient. In the course of research on photocatalytic selective oxidation of benzyl alcohol, a number of highly efficient catalysts have emerged, of which BiOBr x I 1-x Having a wider absorption sideband, a deeper valence band position has a stronger oxidizing ability, and in addition, the energy band structure thereof can be adjusted by adjusting x. But single BiOBr x I 1-x The carrier separation efficiency is low, and the catalytic activity of the heterojunction can be improved by a method for constructing the heterojunction.
Disclosure of Invention
Aiming at the defects of the prior art and the needs of research and application in the field, the project aims at providing a method for preparing benzaldehyde by photocatalytic selective oxidation of benzyl alcohol, which is safe, environment-friendly, stable, efficient, green and economical.
The technical scheme for realizing the aim of the invention is as follows: synthesis of BiOBr by hydrothermal-calcination in situ synthesis x I 1-x /Bi 24 O 31 Br 10 Under the condition of not adding an organic sacrificial agent as an electron acceptor, acetonitrile is used as a solvent, and under the conditions of normal temperature, normal pressure and visible light irradiation, the heterojunction composite photocatalytic material realizes high-efficiency photocatalytic oxidation of benzyl alcohol into benzaldehyde.
The invention provides a preparation method of a catalyst for photocatalytic oxidation of benzyl alcohol into benzyl alcohol, which comprises the following specific steps:
3mmolBi (NO) 3 ) 3 ·5H 2 O was added to 20mL of ethylene glycol and was designated as solution A, 2.25 mmole KBr and 0.75 mmole KI were dissolved in another 20mL of ethylene glycol and designated as solution B, solution B was added to solution A, and after stirring for 3 hours, the mixed solution was charged into a 50mL stainless steel autoclave containing a polytetrafluoroethylene liner, placed in an oven, and heated at 160℃for 16 hours. Taking out, alternately washing with water and ethanol, and vacuum drying at 60deg.C for 8 hr to obtain BiOBr 0.75 I 0.25 。
BiOBr obtained as described above 0.75 I 0.25 Placing into a crucible, and maintaining at 550deg.C for 2 hr at a heating rate of 5deg.C/min under air condition to obtain BiOBr x I 1-x /Bi 24 O 31 Br 10 A composite material.
The description also provides a method for photocatalytic oxidation of benzyl alcohol, which comprises the following actual operations:
(1) BiOBr in different proportions x I 1-x /Bi 24 O 31 Br 10 The photocatalyst is dissolved in 50mL of acetonitrile, and the catalyst is uniformly dispersed in the solvent by ultrasonic treatment for 30 min; (2) o is led in under dark condition 2 Introducing for 1h to reach the adsorption-desorption balance of water-soluble oxygen; (3) then two balloons are tied up, an oxygen environment of 1atm is maintained, a 300W xenon lamp emits visible light into the reactor through top illumination, and the temperature of the reactor is controlled through water circulation condensationThe benzaldehyde is prepared after a certain reaction time at 25 ℃; (4) solutions of different reaction time periods were taken, filtered with a filter head, and analyzed for conversion and selectivity by variation of peak area of high performance liquid chromatography.
Preferably, in step (1), the total volume of acetonitrile solution after the sacrificial reagent is 50mL.
Preferably, in step (1), the concentration of benzyl alcohol added is 0.5mmol/L.
Preferably, in the step (2), the added catalysts are respectively BiOI and Bi 24 O 31 Br10、BiOBr 0.75 I 0.25 、BiOBr 0.75 I 0.25 /Bi 24 O 31 Br 10 。
Preferably, in the step (3), the visible light refers to light with a wavelength of more than or equal to 420 nm.
Preferably, in the step (4), the reaction time is 6 hours.
Preferably, in the step (4), the detection ultraviolet wavelength of the high performance liquid chromatography is set to 254nm, and the mobile phase is acetonitrile: water = 6:4, the detection time is 20min.
The invention has the beneficial effects that (1) the benzaldehyde is obtained by using a method which is green, pollution-free, stable, efficient and low in cost and does not add a sacrificial agent. (2) The catalyst used in the invention has the advantages of simple synthesis method, high yield, wide absorption side band and excellent carrier separation efficiency due to the unique structure, high catalytic activity of photocatalytic oxidation of benzyl alcohol into benzaldehyde, no generation of toxic byproducts, high catalytic efficiency of visible light and conversion rate and selectivity of 80% in 1 hour. The method not only avoids the generation of toxic byproducts, protects the environment, but also avoids the utilization of high cost such as high temperature, high pressure and the like, and has better practical application prospect.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a graph showing the conversion of photocatalytic oxidation benzyl alcohol as a function of time for example 1;
FIG. 2 is a 4-cycle stability test of photocatalytic oxidation of benzyl alcohol performed in example 1;
FIG. 3 is a BiOBr used in the photocatalytic reaction performed in example 1 0.75 I 0.25 /Bi 24 O 31 Br 10 Structural characterization of the composite material;
FIG. 4 is a graph of the conversion of benzyl alcohol over time and the selectivity of benzaldehyde over time for examples 1-6;
Detailed Description
Example 1;
(1) benzyl alcohol solution with concentration of 0.5mmol/L is prepared: to 50mL of acetonitrile solution was added 3mg of benzyl alcohol solution, and the mixture was sonicated to form a homogeneous solution; (2) 200mg of BiOBr was added to the solution of 0.5mmol/L in step (1) 0.75 I 0.25 /Bi 24 O 31 Br 10 Forming a uniform suspension by ultrasonic waves; (3) introducing oxygen for 1h under the dark condition, so as to reach the adsorption-analysis balance of the oxygen; (4) and (3) injecting visible light into a reactor through top illumination by using a 300W xenon lamp provided with a 420nm filter, controlling the temperature of the reactor to be 25 ℃ through water circulation condensation, and preparing the benzaldehyde product through a certain reaction time. (5) During the experiment, 1mL of the solution was centrifuged, and the supernatant was filtered with a 0.22 μm filter head, and the conversion of benzyl alcohol and the time-dependent benzaldehyde selectivity profile were determined by the variation of the peak area in high performance liquid chromatography.
Example 2;
steps (2), (3), (4), (5) of this example are the same as example 1, except step (1): preparation of 4g/L BiOBr 0.75 I 0.25 A solution; 200mg of photocatalyst is added into 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, the mixture is stirred for 1h by ultrasonic to form a homogeneous solution, samples are respectively taken at time nodes of 0h,1h,3h and 6h, and the conversion rate of the benzyl alcohol and the selectivity of the benzaldehyde are determined by high performance liquid chromatography.
Example 3;
steps (2), (3), (4), (5) of this example are the same as example 1, except step (1):preparing 4g/L Bi 24 O 31 Br 10 A solution; 200mg of photocatalyst is added into 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, the mixture is stirred for 1h by ultrasonic to form a homogeneous solution, samples are respectively taken at time nodes of 0h,1h,3h and 6h, and the conversion rate of the benzyl alcohol and the selectivity of the benzaldehyde are determined by high performance liquid chromatography.
Example 4;
steps (2), (3), (4), (5) of this example are the same as example 1, except step (1): preparing 4g/L BiOI solution; 200mg of photocatalyst is added into 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, the mixture is stirred for 1h by ultrasonic to form a homogeneous solution, samples are respectively taken at time nodes of 0h,1h,3h and 6h, and the conversion rate of the benzyl alcohol and the selectivity of the benzaldehyde are determined by high performance liquid chromatography.
Example 5;
steps (2), (3), (4), (5) of this example are the same as example 1, except step (1): preparation of 4g/LBiOBr 0.5 I 0.5 /Bi 24 O 31 Br 10 Is a solution of (a); 200mg of photocatalyst is added into 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, the mixture is stirred for 1h by ultrasonic to form a homogeneous solution, samples are respectively taken at time nodes of 0h,1h,3h and 6h, and the conversion rate of the benzyl alcohol and the selectivity of the benzaldehyde are determined by high performance liquid chromatography.
Example 6;
steps (2), (3), (4), (5) of this example are the same as example 1, except step (1): preparation of 4g/LBiOBr 0.25 I 0.75 /Bi 24 O 31 Br 10 Is a solution of (a); 200mg of photocatalyst is added into 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, the mixture is stirred for 1h by ultrasonic to form a homogeneous solution, samples are respectively taken at time nodes of 0h,1h,3h and 6h, and the conversion rate of the benzyl alcohol and the selectivity of the benzaldehyde are determined by high performance liquid chromatography.
Example 7;
steps (2), (3), (4), (5) of this example are the same as example 1, except step (1): to 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, no photocatalyst was added, and the solution was stirred with ultrasound for 1h to form a homogeneous solution, and samples were taken at time nodes of 0h,1h,3h and 6h, respectively, and analyzed by high performance liquid chromatography to determine the conversion rate of benzyl alcohol and the selectivity of benzaldehyde. As a result, it was found that the selectivity and the conversion were both 0, indicating the importance of the catalyst for the reaction.
Example 8;
steps (1), (2), (3), (5) of this example are the same as example 1 except for step (4): preparing 4g/LBiOBr without 300W visible light source 0.75 I 0.25 /Bi 24 O 31 Br 10 Is a solution of (a); 200mg of photocatalyst is added into 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, the mixture is stirred for 1h by ultrasonic to form a homogeneous solution, samples are taken at time nodes of 0h,1h,3h and 6h respectively, the conversion rate of the benzyl alcohol and the selectivity of the benzaldehyde are determined by high performance liquid chromatography, the conversion rate of the benzyl alcohol and the selectivity of the benzaldehyde after 6h are found to be 0, and the importance of a light source to the reaction is demonstrated.
Example 9;
steps (1), (2), (3), (4) of this example are the same as example 1 except for step (5): preparation of 4g/LBiOBr 0.75 I 0.25 /Bi 24 O 31 Br 10 Is a solution of (a); 200mg of photocatalyst is added into 50mL of acetonitrile solution containing 0.5mmol/L benzyl alcohol, ultrasonic stirring is carried out for 1h to form homogeneous solution, sampling is carried out at time nodes of 0h,1h,3h and 6h respectively, after the reaction is finished, the catalyst is centrifugally collected by the residual solution, the cyclic reaction is carried out, four times of operation are repeated, the experimental results of each cycle are respectively tested by high performance liquid chromatography, and the results of each cycle are almost consistent, thus the photocatalyst has good stability.
The above examples demonstrate that: by adopting the method provided by the invention, benzaldehyde with high selectivity and higher reaction rate can be obtained under visible light, in addition, the reaction process is carried out at normal temperature and normal pressure, no noble metal doping exists, no toxic byproducts are generated, and the method is environment-friendly and has certain application potential.
The above-described embodiments 1-7 are merely representative examples of the present invention, and are not intended to limit the present invention in any way, so that those skilled in the art can smoothly practice the present invention as described in the specification, drawings and the above. However, those skilled in the art should not depart from the scope of the invention, and make various changes, modifications and adaptations of the invention using the teachings disclosed in the foregoing embodiments; meanwhile, any equivalent changes, modifications and evolution made by the implementation technique according to the present invention to the above embodiment 2 are all within the scope of the present invention.
Claims (7)
1. A preparation method of a photocatalyst for efficiently and photo-catalytically oxidizing benzyl alcohol into benzaldehyde is characterized by comprising the following steps of: acetonitrile is taken as a solvent, no sacrificial agent is added, and under the irradiation of visible light (lambda is more than or equal to 420 nm), biOBr is carried out 0.75 I 0.25 /Bi 24 O 31 Br 10 Under the action of a catalyst, benzyl alcohol is oxidized into benzaldehyde, and the specific steps are as follows:
1 adding BiOBr in different proportions to acetonitrile solution containing benzyl alcohol x I 1-x /Bi 24 O 31 Br 10 Photocatalyst, and stirring for 30min by ultrasonic to form homogeneous solution;
2, introducing oxygen for 1h under the dark condition so as to reach the adsorption-analysis balance of the oxygen, and then adding two balloons on the reactor to keep the reaction in the oxygen environment;
the 3300W xenon lamp irradiates visible light to a reactor through top irradiation, the temperature of the reactor is controlled to be 25 ℃ through a water circulation condensing device, and the reactor is continuously stirred and reacts for a period of time to obtain a reaction product benzaldehyde;
4, taking solutions in different reaction stages, centrifugally separating the catalyst, taking supernatant, filtering by using a filter head, and then putting the supernatant into a high performance liquid chromatograph for analysis.
2. The method for photocatalytic preparation of benzaldehyde according to claim 1, wherein: the total volume of the solution after adding benzyl alcohol described in step (1) was 50mL.
3. The method for photocatalytic production of benzaldehyde according to claim 1, wherein: the ratio of the photocatalyst in the step (1) is BiOBr x I 1-x /Bi 24 O 31 Br 10 (x＝0,0.25,0.5,0.75,1)。
4. The method for photocatalytic production of benzaldehyde according to claim 1, wherein: the mass of the photocatalyst in the step (1) was 200mg.
5. The method for photocatalytic production of benzaldehyde according to claim 1, wherein: the concentration of benzyl alcohol in step (1) was 0.5mmol/L.
6. The method for photocatalytic production of benzaldehyde according to claim 1, wherein: in the step (3), the xenon lamp is provided with a 420nm filter (lambda is more than or equal to 420 nm).
7. The method for photocatalytic production of benzaldehyde according to claim 1, wherein: the liquid chromatography mobile phase in the step (4) is acetonitrile: water=6:4, the detection uv wavelength was 254nm.
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