CN112275319B - Organic selenium catalyst loaded with carbon nano tubes and preparation method and application thereof - Google Patents
Organic selenium catalyst loaded with carbon nano tubes and preparation method and application thereof Download PDFInfo
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- CN112275319B CN112275319B CN202011208664.9A CN202011208664A CN112275319B CN 112275319 B CN112275319 B CN 112275319B CN 202011208664 A CN202011208664 A CN 202011208664A CN 112275319 B CN112275319 B CN 112275319B
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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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 scheme relates to an organic selenium catalyst for loading carbon nano tubes and a preparation method thereof, wherein selenium powder and alpha-halogenated carboxylic acid are firstly utilized to prepare carboxylic acid diselenide, and then the carboxylic acid diselenide is loaded on hydroxylated double-wall carbon nano tubes to prepare the organic selenium catalyst for loading carbon nano tubes. The organic selenium catalyst provided by the invention is loaded on the carbon nano tube, the preparation process is simple, and the conditions are mild; the method has the advantages that p-benzoquinone is synthesized by catalyzing the oxidation of phenol hydrogen peroxide, the selectivity in the synthesis process is high, and meanwhile, the conversion rate of phenol is nearly half; the reaction can be carried out for a short time at a milder temperature, so that higher conversion rate and selectivity can be obtained; the organic selenium catalyst loaded by the carbon nano tube can be recycled and reused for at least 10 times, and is economical and environment-friendly.
Description
Technical Field
The invention relates to the field of selenium catalysts, in particular to an organic selenium catalyst loaded with carbon nanotubes, and a preparation method and application thereof.
Background
Selenium element mainly has two existence modes of inorganic selenium and organic selenium in nature, and compared with the rapid development of inorganic selenium, the organic selenium compound has slow development process due to the limitations of large smell, high activity, instability, easy oxidation and the like. As an important reagent and an intermediate in organic synthesis, the organic selenium compound has diversified reaction performances, and meanwhile, the organic selenium compound as a catalyst has the advantages of being more stable, durable and low in price compared with a metal catalyst. However, little research has been done in the area of organoselenium catalysis, especially with respect to selectivity and conversion in the catalytic reaction of certain compounds.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a novel organic selenium catalyst which can be applied to the catalytic oxidation reaction of phenol and can remarkably improve the conversion rate and the selectivity.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of an organic selenium catalyst loaded with carbon nano tubes comprises the following steps:
1) Adding selenium powder into distilled water, introducing nitrogen, stirring uniformly, then adding aqueous solution of sodium borohydride, supplementing the same amount of selenium powder, and heating for reaction;
2) Dropwise adding a saturated sodium carbonate solution into an aqueous solution of alpha-halogenated carboxylic acid, and adjusting the pH to be alkaline;
3) Dropwise adding the alkaline solution obtained in the step 2) into the step 1), and stirring at room temperature for reaction for 24 hours;
4) Filtering after the reaction, regulating the pH value of the filtrate to be acidic by using dilute hydrochloric acid, carrying out suction filtration, washing and drying, and recrystallizing by using ethyl acetate to obtain the diselenide carboxylate;
5) Placing the modified carbon nano tube in an N, N-dimethylformamide solvent, adding the carboxylic acid diselenide, performing ultrasonic dispersion for 30min, stirring and refluxing for 12-24h at 70-80 ℃, filtering, washing and drying to obtain the organic selenium catalyst loaded with the carbon nano tube.
Further, the molar ratio of the selenium powder to the sodium borohydride to the halogenated carboxylic acid is 1:1:1.
Further, the temperature is raised to 50-60 ℃ in the step 1), and the reaction is carried out for 40-60min.
Further, the pH is adjusted to 9-10 in the step 2).
Further, the halogenated carboxylic acid is selected from one of 3-chloropropionic acid, 1-chloroacetic acid, o-chlorobenzoic acid, 4-bromomethylbenzoic acid, p-bromobenzoic acid or 4-bromo-2, 6-difluorobenzoic acid.
Further, the pH is adjusted to 3-4 in the step 4).
Further, the modified carbon nanotube is a hydroxylated double-wall carbon nanotube, and the mass ratio of the modified carbon nanotube to the carboxylic acid diselenide is 1:5-10.
A carbon nanotube-supported organic selenium catalyst prepared by the preparation method of any one of the above.
The invention further provides application of the organic selenium catalyst loaded with the carbon nano tube, and preferably, the catalyst is used for catalyzing phenol hydrogen peroxide to oxidize and synthesize p-benzoquinone.
The beneficial effects of the invention are as follows: the organic selenium catalyst provided by the invention is loaded on the carbon nano tube, the preparation process is simple, and the conditions are mild; the method has the advantages that p-benzoquinone is synthesized by catalyzing the oxidation of phenol hydrogen peroxide, the selectivity in the synthesis process is high, and meanwhile, the conversion rate of phenol is nearly half; the reaction can be carried out for a short time at a milder temperature, so that higher conversion rate and selectivity can be obtained; the organic selenium catalyst loaded by the carbon nano tube can be recycled and reused for at least 10 times, and is economical and environment-friendly.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a preparation method of an organic selenium catalyst loaded with carbon nano tubes, which comprises the following steps:
1) Adding 0.8g (0.01 mol) of selenium powder into distilled water, introducing nitrogen gas, stirring uniformly, then adding 0.75g (0.02 mol) of sodium borohydride aqueous solution, adding 0.8g (0.01 mol) of selenium powder, heating to 50-60 ℃, and reacting for 40-60min;
2) Dropwise adding a saturated sodium carbonate solution into 10ml of an aqueous solution of 0.02mol of alpha-halogenated carboxylic acid, and adjusting the pH to 9-10;
3) Dropwise adding the alkaline solution obtained in the step 2) into the step 1), and stirring at room temperature for reaction for 24 hours;
4) Filtering after the reaction, regulating the pH of the filtrate to 3-4 by using dilute hydrochloric acid, carrying out suction filtration, washing and drying, and recrystallizing by using ethyl acetate to obtain the diselenide carboxylate;
5) Placing the modified carbon nano tube in an N, N-Dimethylformamide (DMF) solvent, adding the carboxylic acid diselenide, performing ultrasonic dispersion for 30min, stirring and refluxing for 12-24h at 70-80 ℃, filtering, washing and drying to obtain the organic selenium catalyst loaded with the carbon nano tube.
Wherein the halogenated carboxylic acid is selected from one of 3-chloropropionic acid, 1-chloroacetic acid, o-chlorobenzoic acid, 4-bromomethylbenzoic acid, p-bromobenzoic acid or 4-bromo-2, 6-difluorobenzoic acid, and steps 1) to 4) can be represented by the following equations.
Further, the modified carbon nanotube is a hydroxylated double-walled carbon nanotube CNTs-OH, and the mass ratio of the modified carbon nanotube to the carboxylic acid diselenide is 1:5-10. The surface of the hydroxylated double-wall carbon nanotube CNTs-OH is hydroxylated and can be subjected to esterification reaction with carboxyl of carboxylic diselenide, so that selenium element is loaded on the surface of the carbon nanotube. The carbon nano tube has larger specific surface area, stable nano structure and heat resistance stability, and can improve the catalytic activity of selenium when being used as a supported catalyst.
The organic selenium catalyst loaded with the carbon nano tube can be used for carrying out catalytic oxidation of phenol and hydrogen peroxide, and the preparation process can comprise the following steps:
adding an organic selenium catalyst loaded with carbon nano tubes, phenol and 30% hydrogen peroxide into a reaction bottle, adding DMF, uniformly stirring, charging nitrogen, and reacting for 1-2h at 60 ℃ after sealing. Wherein the organic selenium catalyst loading the carbon nano tube is 0.5-5wt% of phenol, and the molar ratio of hydrogen peroxide to phenol is 1-3:1.
Example 1: the preparation method comprises the steps of preparing the organic selenium catalyst loaded with the carbon nano tube according to the process, wherein the halogenated carboxylic acid is 3-chloropropionic acid, and the mass ratio of the modified carbon nano tube to the carboxylic acid diselenide ether is 3-10. To the reaction flask were added 0.47mg of the carbon nanotube-supported organic selenium catalyst, 0.47g (. Apprxeq.5 mmol) of phenol and 0.56g of 30% hydrogen peroxide, 10ml of DMF was added, and the mixture was stirred uniformly, nitrogen was introduced, and the mixture was sealed and reacted at 60℃for 2 hours.
Example 2: the preparation method comprises the steps of preparing the organic selenium catalyst loaded with the carbon nano tube according to the process, wherein the halogenated carboxylic acid is 1-chloroacetic acid, and the mass ratio of the modified carbon nano tube to the carboxylic acid diselenide ether is 4-10. To the reaction flask were added 0.47mg of the carbon nanotube-supported organic selenium catalyst, 0.47g (. Apprxeq.5 mmol) of phenol and 0.56g of 30% hydrogen peroxide, 10ml of DMF was added, and the mixture was stirred uniformly, nitrogen was introduced, and the mixture was sealed and reacted at 60℃for 2 hours.
Example 3: the preparation method comprises the steps of preparing the organic selenium catalyst loaded with the carbon nano tube according to the process, wherein the halogenated carboxylic acid is o-chlorobenzoic acid, and the mass ratio of the modified carbon nano tube to the carboxylic acid diselenide is 3-10. To the reaction flask were added 0.47mg of the carbon nanotube-supported organic selenium catalyst, 0.47g (. Apprxeq.5 mmol) of phenol and 0.56g of 30% hydrogen peroxide, 10ml of DMF was added, and the mixture was stirred uniformly, nitrogen was introduced, and the mixture was sealed and reacted at 60℃for 2 hours.
Example 4: the preparation method comprises the steps of preparing the organic selenium catalyst loaded with the carbon nano tube according to the process, wherein the halogenated carboxylic acid is 4-bromomethylbenzoic acid, and the mass ratio of the modified carbon nano tube to the carboxylic acid diselenide is 2-10. To the reaction flask were added 0.47mg of the carbon nanotube-supported organic selenium catalyst, 0.47g (. Apprxeq.5 mmol) of phenol and 0.56g of 30% hydrogen peroxide, 10ml of DMF was added, and the mixture was stirred uniformly, nitrogen was introduced, and the mixture was sealed and reacted at 60℃for 2 hours.
Example 5: the preparation method comprises the steps of preparing the organic selenium catalyst loaded with the carbon nano tube according to the process, wherein the halogenated carboxylic acid is 4-bromo-2, 6-difluorobenzoic acid, and the mass ratio of the modified carbon nano tube to the carboxylic acid diselenide is 1-10. To the reaction flask were added 0.47mg of the carbon nanotube-supported organic selenium catalyst, 0.47g (. Apprxeq.5 mmol) of phenol and 0.56g of 30% hydrogen peroxide, 10ml of DMF was added, and the mixture was stirred uniformly, nitrogen was introduced, and the mixture was sealed and reacted at 60℃for 2 hours.
The filtrates of examples 1-5 were analyzed for composition and the results are recorded in Table 1.
TABLE 1
Phenol conversion | P-benzoquinone selectivity | Cycle times | |
Example 1 | 40.12% | 87.15% | Not less than 10 times |
Example 2 | 36.66% | 86.12% | Not less than 10 times |
Example 3 | 43.01% | 85.94% | Not less than 10 times |
Example 4 | 39.56% | 90.21% | Not less than 10 times |
Example 5 | 41.21% | 91.03% | Not less than 10 times |
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (7)
1. The preparation method of the organic selenium catalyst loaded with the carbon nano tubes is characterized by comprising the following steps of:
1) Adding selenium powder into distilled water, introducing nitrogen, stirring uniformly, then adding aqueous solution of sodium borohydride, supplementing the same amount of selenium powder, and heating for reaction;
2) Dropwise adding a saturated sodium carbonate solution into an aqueous solution of 4-bromo-2, 6-difluorobenzoic acid, and adjusting the pH to be alkaline;
3) Dropwise adding the alkaline solution obtained in the step 2) into the step 1), and stirring at room temperature to react 24-h;
4) Filtering after the reaction, regulating the pH value of the filtrate to be acidic by using dilute hydrochloric acid, carrying out suction filtration, washing and drying, and recrystallizing by using ethyl acetate to obtain the diselenide carboxylate;
5) Placing the modified carbon nano tube in an N, N-dimethylformamide solvent, adding the carboxylic acid diselenide, stirring and refluxing at 70-80 ℃ for 12-24h, filtering, washing and drying to obtain the organic selenium catalyst loaded with the carbon nano tube;
the modified carbon nano tube is a hydroxylated double-wall carbon nano tube, and the mass ratio of the modified carbon nano tube to the carboxylic acid diselenide ether is 1:5-10.
2. The method for preparing the carbon nanotube-supported organic selenium catalyst according to claim 1, wherein the molar ratio of the selenium powder to sodium borohydride to 4-bromo-2, 6-difluorobenzoic acid is 1:1:1.
3. The method for preparing the carbon nanotube-supported organic selenium catalyst according to claim 1, wherein the temperature is raised to 50-60 ℃ in the step 1), and the reaction is performed for 40-60min.
4. The method for preparing the carbon nanotube-supported organic selenium catalyst according to claim 1, wherein the pH is adjusted to 9 to 10 in the step 2).
5. The method for preparing the carbon nanotube-supported organic selenium catalyst according to claim 1, wherein the pH is adjusted to 3 to 4 in the step 4).
6. A carbon nanotube-supported organic selenium catalyst prepared by the preparation method of any one of claims 1 to 5.
7. The use of the carbon nanotube-supported organic selenium catalyst according to claim 6, wherein the p-benzoquinone is synthesized by catalyzing the oxidation of phenol hydrogen peroxide.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102039121A (en) * | 2009-10-21 | 2011-05-04 | 中国科学院大连化学物理研究所 | Platinum/carbon nanotube catalyst and preparation method and application thereof |
CN102421743A (en) * | 2009-05-07 | 2012-04-18 | 塞拉尼斯国际公司 | Vinyl ester production from acetylene and carboxylic acid utilizing heterogeneous catalyst |
CN102553528A (en) * | 2011-12-20 | 2012-07-11 | 华北电力大学(保定) | Modified carbon nano tube material, method for removing mercury ions in water and method for regenerating modified carbon nano tube material |
CN105921168A (en) * | 2016-04-28 | 2016-09-07 | 南开大学 | Preparation method of hydrodeoxidation isocatalyst, hydrodeoxidation isocatalyst and application thereof |
CN108452805A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院福建物质结构研究所 | A kind of NiTiO for photodissociation aquatic products hydrogen3/TiO2Catalyst and its preparation method and application |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4601860A (en) * | 1982-09-23 | 1986-07-22 | Ppg Industries, Inc. | Method for producing selenoethers from selenoalcohols or their salts, and carbonates |
KR101038750B1 (en) * | 2009-05-20 | 2011-06-03 | 한국에너지기술연구원 | Carbon nanotubes catalysts having metal nano-particle catalyst supported on inner channel of carbon nanotube and preparation method thereof |
TWI535654B (en) * | 2014-09-12 | 2016-06-01 | 國立清華大學 | Method for modifying surface of carbon nanotube with thiol group |
CN105130864B (en) * | 2015-07-27 | 2016-09-21 | 扬州大学 | A kind of method synthesizing diselenide |
CN105251488A (en) * | 2015-10-21 | 2016-01-20 | 扬州大学 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
CN106588618B (en) * | 2016-10-28 | 2019-07-02 | 江苏扬农化工集团有限公司 | A method of the Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone of catalyst containing selenium |
CN107814376A (en) * | 2017-09-30 | 2018-03-20 | 无锡厚发自动化设备有限公司 | A kind of titania-doped coated carbon nano-tube composite material of selenium |
-
2020
- 2020-11-03 CN CN202011208664.9A patent/CN112275319B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102421743A (en) * | 2009-05-07 | 2012-04-18 | 塞拉尼斯国际公司 | Vinyl ester production from acetylene and carboxylic acid utilizing heterogeneous catalyst |
CN102039121A (en) * | 2009-10-21 | 2011-05-04 | 中国科学院大连化学物理研究所 | Platinum/carbon nanotube catalyst and preparation method and application thereof |
CN102553528A (en) * | 2011-12-20 | 2012-07-11 | 华北电力大学(保定) | Modified carbon nano tube material, method for removing mercury ions in water and method for regenerating modified carbon nano tube material |
CN105921168A (en) * | 2016-04-28 | 2016-09-07 | 南开大学 | Preparation method of hydrodeoxidation isocatalyst, hydrodeoxidation isocatalyst and application thereof |
CN108452805A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院福建物质结构研究所 | A kind of NiTiO for photodissociation aquatic products hydrogen3/TiO2Catalyst and its preparation method and application |
Non-Patent Citations (2)
Title |
---|
Design and preparation of a polymer resinsupported organoselenium catalyst with industrial potential;Yuguang Wang等;《J. Mater. Chem. A》;第4卷;全文 * |
有机硒催化苯酚选择性氧化制对苯醌的研究;王芳等;《有机化学》;第37卷;全文 * |
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