CN108525655B - Preparation method and application of novel composite catalyst for oxidizing hydroxyl into carbonyl - Google Patents

Preparation method and application of novel composite catalyst for oxidizing hydroxyl into carbonyl Download PDF

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CN108525655B
CN108525655B CN201810418475.0A CN201810418475A CN108525655B CN 108525655 B CN108525655 B CN 108525655B CN 201810418475 A CN201810418475 A CN 201810418475A CN 108525655 B CN108525655 B CN 108525655B
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王芳
黄德奇
王雪源
仇实
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Abstract

The invention relates to a preparation method and application of a novel composite catalyst for oxidizing hydroxyl into carbonyl, which specifically comprises the following steps: (1) after uniformly mixing single-walled carbon nanohorns SWCNHs and ionic liquid, adding trifluoromethanesulfonic acid (TfOH), heating to 110-120 ℃, reacting for 5-6 hours, and performing post-treatment to obtain modified SWCNHs; (2) and (2) uniformly mixing the modified SWCNHs obtained in the step (1), a zinc salt solution and ammonia water in a high-pressure kettle, heating to 120-130 ℃, reacting for 10-12h, naturally cooling to room temperature, and performing post-treatment to obtain the micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material.

Description

Preparation method and application of novel composite catalyst for oxidizing hydroxyl into carbonyl
Technical Field
The invention belongs to the field of materials and catalysis, and particularly relates to a preparation method and application of a novel composite catalyst for oxidizing hydroxyl into carbonyl.
Background
The single-walled carbon nanohorns (SWNHs) are novel nano materials similar to single-walled carbon nanotubes (SWNTs), and have become research hotspots due to unique structures, one end of each single SWNHs is a closed conical structure, the diameter is 2-5 nm, the length is 20-50nm, the cone angle is about 20 degrees, and about 2000 single-walled carbon nanohorns are aggregated to form a spherical aggregate with the diameter of 80-100 nm under a normal state. The ZnO nanoparticles are considered to be photocatalyst materials with the most application prospect due to the advantages of no toxicity, low price, larger specific surface area, excellent chemical stability and light stability, photocatalytic activity for a plurality of chemical reactions and the like. The invention utilizes ionic liquid and acid to modify single-walled nanohorns, and then zinc oxide is loaded to obtain a micro flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material which can be used for catalyzing various oxidation reactions. The patent obtains the subsidy of the professional construction project subsidy project (PPZY2015B180) of the brand of Jiangsu colleges and universities.
Disclosure of Invention
The invention provides a micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material, which is characterized in that the preparation method of the micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material comprises the following steps:
(1) after uniformly mixing single-walled carbon nanohorns SWCNHs and ionic liquid, adding trifluoromethanesulfonic acid (TfOH), heating to 110-120 ℃, reacting for 5-6 hours, and performing post-treatment to obtain modified SWCNHs;
(2) and (2) uniformly mixing the modified SWCNHs obtained in the step (1), a zinc salt solution and ammonia water in a high-pressure kettle, heating to 120-130 ℃, reacting for 10-12h, naturally cooling to room temperature, and performing post-treatment to obtain the micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material.
The mass ratio of the single-wall carbon nanohorn SWCNHs to the ionic liquid to the trifluoromethanesulfonic acid (TfOH) is 1: 1: 4-5, 40-50mmol of zinc salt is used for each gram of modified SWCNHs, the molar ratio of the zinc salt to ammonia water is 1: 1.2-1.5, the concentration of a zinc salt solution is 1-2 mol/L, and the concentration of the ammonia water is 1 mol/L;
the ionic liquid is selected from carboxyl functionalized ionic liquid, and further preferably selected from 1-carboxyethyl-3-methylimidazole nitrate, 1-carboxyethyl-3-methylimidazole hydrogen sulfate, 1-carboxyethyl-3-methylimidazole bromide and 1-carboxyethyl-3-methylimidazole chloride; the zinc salt is selected from one or more of zinc chloride, zinc nitrate, zinc sulfate or hydrates thereof;
the post-treatment comprises filtering, washing the precipitate with deionized water and ethanol, and vacuum drying at 60-80 deg.C for 6-10 h.
Another embodiment of the present invention provides a method for preparing the above micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material, which is characterized by comprising the steps of:
(1) after uniformly mixing single-walled carbon nanohorns SWCNHs and ionic liquid, adding trifluoromethanesulfonic acid (TfOH), heating to 110-120 ℃, reacting for 5-6 hours, and performing post-treatment to obtain modified SWCNHs;
(2) and (2) uniformly mixing the modified SWCNHs obtained in the step (1), a zinc salt solution and ammonia water in a high-pressure kettle, heating to 120-130 ℃, reacting for 10-12h, naturally cooling to room temperature, and performing post-treatment to obtain the micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material.
The mass ratio of the single-wall carbon nanohorn SWCNHs to the ionic liquid to the trifluoromethanesulfonic acid (TfOH) is 1: 1: 4-5, 40-50mmol of zinc salt is used for each gram of modified SWCNHs, the molar ratio of the zinc salt to ammonia water is 1: 1.2-1.5, the concentration of a zinc salt solution is 1-2 mol/L, and the concentration of the ammonia water is 1 mol/L;
the ionic liquid is selected from carboxyl functionalized ionic liquid, and further preferably selected from 1-carboxyethyl-3-methylimidazole nitrate, 1-carboxyethyl-3-methylimidazole hydrogen sulfate, 1-carboxyethyl-3-methylimidazole bromide and 1-carboxyethyl-3-methylimidazole chloride; the zinc salt is selected from one or more of zinc chloride, zinc nitrate, zinc sulfate or hydrates thereof;
the post-treatment comprises filtering, washing the precipitate with deionized water and ethanol, and vacuum drying at 60-80 deg.C for 6-10 h.
Another embodiment of the present invention provides the use of the above micro flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material as a catalyst.
Another embodiment of the present invention provides the use of the above micro flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material as an oxidation reaction catalyst.
Another embodiment of the present invention provides the use of the above micro flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material in the oxidation of hydroxyl groups to carbonyl groups.
Another embodiment of the present invention provides the use of the above micro flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material in the preparation of p-benzoquinone from phenol.
Another embodiment of the present invention provides the use of the above micro flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material in the conversion of a compound of formula I to a compound of formula II;
Figure BDA0001649269960000031
r is selected from optionally substituted alkyl, preferably methyl, benzyl, etc.
Compared with the prior art, the invention has the advantages that: the invention utilizes carboxyl functionalized ionic liquid and trifluoromethanesulfonic acid to modify single-walled nanohorns, and then loads zinc oxide to obtain a micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material which can be used for catalyzing various oxidation reactions and can achieve good effects.
Drawings
SEM image of product A in FIG. 1
SEM image of product C in FIG. 2
SEM image of product D in FIG. 3
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
(1) Uniformly mixing single-walled carbon nanohorns SWCNHs (10g) and 1-carboxyethyl-3-methylimidazole nitrate (10g), adding trifluoromethanesulfonic acid (40g), heating to 110-115 ℃, reacting for 5 hours, filtering, washing precipitates with deionized water and ethanol, and drying in vacuum at 60 ℃ for 10 hours to obtain modified SWCNHs;
(2) and (2) uniformly mixing the modified SWCNHs (1.0g) obtained in the step (1), 1 mol/L zinc nitrate solution (40m L) and 1 mol/L ammonia water (48m L) in an autoclave, heating to 120-125 ℃ for reaction for 12 hours, naturally cooling to room temperature, filtering, washing precipitates with deionized water and ethanol, and performing vacuum drying at 80 ℃ for 6 hours to obtain the micron single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material (hereinafter referred to as a product A).
Example 2
(1) Uniformly mixing single-walled carbon nanohorns SWCNHs (10g) and 1-carboxyethyl-3-methylimidazole hydrogen sulfate (10g), adding trifluoromethanesulfonic acid (50g), heating to 115-120 ℃, reacting for 6 hours, filtering, washing precipitates with deionized water and ethanol, and drying in vacuum at 70 ℃ for 8 hours to obtain modified SWCNHs;
(2) and (2) uniformly mixing the modified SWCNHs (1.0g) obtained in the step (1), 2 mol/L zinc chloride solution (25m L) and 1 mol/L ammonia water (75m L) in an autoclave, heating to 125-130 ℃, reacting for 10 hours, naturally cooling to room temperature, filtering, washing precipitates with deionized water and ethanol, and vacuum-drying at 60 ℃ for 10 hours to obtain the micron single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material (hereinafter referred to as a product B).
Example 3
(1) Uniformly mixing single-walled carbon nanohorns SWCNHs (10g) and 1-ethyl-3-methylimidazole nitrate (10g), adding trifluoromethanesulfonic acid (40g), heating to 110-115 ℃, reacting for 5 hours, filtering, washing precipitates with deionized water and ethanol, and drying in vacuum at 60 ℃ for 10 hours to obtain modified SWCNHs;
(2) and (2) uniformly mixing the modified SWCNHs (1.0g) obtained in the step (1), 1 mol/L zinc nitrate solution (40m L) and 1 mol/L ammonia water (48m L) in an autoclave, heating to 120-125 ℃ for reaction for 12 hours, naturally cooling to room temperature, filtering, washing precipitates with deionized water and ethanol, and vacuum-drying at 80 ℃ for 6 hours to obtain the single-walled carbon nanohorn/zinc oxide material (hereinafter referred to as product C).
Example 4
Taking single-walled carbon nanohorns SWCNHs (1.0g), 1 mol/L zinc nitrate solution (40m L) and 1 mol/L ammonia water (48m L) to mix uniformly in a high-pressure kettle, heating to 120 ℃ and 125 ℃ for reaction for 12h, naturally cooling to room temperature, filtering, washing precipitates with deionized water and ethanol, and vacuum-drying at 80 ℃ for 6h to obtain the single-walled carbon nanohorn/zinc oxide material (hereinafter referred to as product D).
Example 5
Dissolving phenol (1.0g) in chloroform (50g), adding a product A (10mg) at room temperature, heating to 50 ℃ for reaction for 3 hours, cooling to room temperature to obtain 49.8g of reaction liquid, and sampling to analyze the composition of the reaction liquid, wherein the phenol content is 0.36%, the p-benzoquinone content is 1.81%, the phenol conversion rate is 82.0%, and the p-benzoquinone selectivity is 95.7%.
Example 6
Dissolving phenol (10g) in chloroform (300 g), adding the product B (100mg) at room temperature, heating to 50 ℃ for reaction for 3 hours, cooling to room temperature to obtain 307.2g of reaction liquid, and sampling to analyze the composition of the reaction liquid, wherein the phenol content is 0.43 percent, the p-benzoquinone content is 2.93 percent, the phenol conversion rate is 86.8 percent, and the p-benzoquinone selectivity is 90.3 percent.
Example 7
Phenol (1.0g) was dissolved in 50g of chloroform, product C (10mg) was added at room temperature, the temperature was raised to 50 ℃ to react for 3 hours, and then the temperature was lowered to room temperature to obtain 49.6g of a reaction solution, and the composition of the reaction solution was analyzed by sampling, wherein 1.97% of phenol was not detected.
Example 8
Phenol (1.0g) was dissolved in 50g of chloroform, and product D (10mg) was added at room temperature, and after heating to 50 ℃ and reacting for 3 hours, the temperature was lowered to room temperature to obtain 49.9g of a reaction solution, and the composition of the reaction solution was analyzed by sampling, wherein 1.98% of phenol was not detected.
Example 9
Figure BDA0001649269960000051
Compound 1(1.0mmol) was dissolved in dichloromethane (10m L), product a (5mg) was added at room temperature, the reaction was stirred until compound 1 was completely disappeared by T L C detection (about 24 hours), the solvent was removed by concentration, and compound 2(173mg, 90.0%) was obtained by silica gel column chromatography (petroleum ether: ethyl acetate ═ 2: 1), structure-confirmed compound 21H、13The C NMR data are consistent with the report.
Example 10
Dissolving compound 1(1.0mmol) in dichloromethane (10m L), adding product B (5mg) at room temperature, stirring for reaction until compound 1 disappears completely (about 24 hr) under detection of T L C, concentrating to remove solvent, and performing silica gel column chromatography (petroleum ether: ethyl acetate: 2: 1) to obtain compound 2(169mg, 87.9%), and detecting compound 2 with T L C and detecting compound 21The H NMR data agree with those of example 9.
Example 11
Compound 1(1.0mmol) was dissolved in dichloromethane (10m L), product C (5mg) was added at room temperature, and the reaction was stirred for 24 hours, after which time T L C showed only one spot of compound 1, and after reaction continued for 24 hours with product C (5mg), no compound 2 was detected by T L C.
In the same manner, when product D was used instead of product C, compound 2 was not detected by T L C, indicating that product C, D did not convert compound 1 to compound 2.
Example 12
Figure BDA0001649269960000052
Compound 3(1.0mmol) was dissolved in dichloromethane (15m L), product a (5mg) was added at room temperature, the reaction was stirred until compound 3 was completely disappeared by T L C detection (about 24 hours), the solvent was removed by concentration, and compound 4(231mg, 86.1%) was obtained by silica gel column chromatography (petroleum ether: ethyl acetate ═ 2: 1), structure-confirmed compound 41H、13The C NMR data are consistent with the report.
The product B, C, D was used instead of the product A in the above reaction, and only the product B gave the compound 4 in a yield of 85.3%, and no compound 4 was detected in the reaction solution T L C of the product C, D.

Claims (9)

1. A preparation method of a micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material is characterized by comprising the following steps:
(1) after uniformly mixing single-walled carbon nanohorns SWCNHs and ionic liquid, adding trifluoromethanesulfonic acid (TfOH), heating to 110-120 ℃, reacting for 5-6 hours, and performing post-treatment to obtain modified SWCNHs;
(2) uniformly mixing the modified SWCNHs, the zinc salt solution and ammonia water in a high-pressure kettle, heating to 120-130 ℃, reacting for 10-12h, naturally cooling to room temperature, and performing post-treatment to obtain the micrometer flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material.
2. The preparation method of claim 1, wherein the mass ratio of the single-walled carbon nanohorns SWCNHs, the ionic liquid and the trifluoromethanesulfonic acid (TfOH) in step (1) is 1: 1: 4-5.
3. The process of claim 1, wherein in step (2) 40-50mmol of zinc salt is used per gram of modified SWCNHs, the molar ratio of zinc salt to ammonia water is 1: 1.2-1.5, the concentration of zinc salt solution is 1-2 mol/L, and the concentration of ammonia water is 1 mol/L.
4. The method according to claim 1, wherein the ionic liquid in step (1) is selected from carboxyl-functionalized ionic liquids.
5. The method of claim 4, wherein the carboxyl-functionalized ionic liquid is selected from the group consisting of 1-carboxyethyl-3-methylimidazole nitrate, 1-carboxyethyl-3-methylimidazole hydrogensulfate, 1-carboxyethyl-3-methylimidazole bromide, and 1-carboxyethyl-3-methylimidazole chloride.
6. The method according to claim 1, wherein the zinc salt in step (2) is selected from one or more of zinc chloride, zinc nitrate, zinc sulfate and hydrates thereof.
7. The preparation method according to claim 1, wherein the post-treatment in steps (1) and (2) is filtration, washing the precipitate with deionized water and ethanol, and vacuum drying at 60-80 ℃ for 6-10 h.
8. Use of a micro flower-shaped single-walled carbon nanohorn/zinc oxide (SWCNHs/ZnO) material prepared by the preparation method of any one of claims 1 to 7 for converting a compound of formula I into a compound of formula II;
Figure FDA0002521392440000011
r is selected from optionally substituted alkyl.
9. The use according to claim 8, wherein R is selected from the group consisting of methyl and benzyl.
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JP2008074666A (en) * 2006-09-21 2008-04-03 Tohoku Univ Zinc oxide fiber exhibiting visible light responsive photocatalytic function and preparation method
WO2012178071A2 (en) * 2011-06-23 2012-12-27 Brown University Device and methods for temperature and humidity measurements using a nanocomposite film sensor
CN102872867A (en) * 2012-10-19 2013-01-16 厦门大学 Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst
CN103316683A (en) * 2013-07-05 2013-09-25 昆明理工大学 Preparation method of carbon nanotube loaded copper-based catalyst applied to methanol synthesis
EP2647430A1 (en) * 2012-04-05 2013-10-09 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof

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KR101409421B1 (en) * 2012-09-20 2014-06-18 한국과학기술연구원 Fiber-based filter with nanonet layer and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074666A (en) * 2006-09-21 2008-04-03 Tohoku Univ Zinc oxide fiber exhibiting visible light responsive photocatalytic function and preparation method
WO2012178071A2 (en) * 2011-06-23 2012-12-27 Brown University Device and methods for temperature and humidity measurements using a nanocomposite film sensor
EP2647430A1 (en) * 2012-04-05 2013-10-09 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof
CN102872867A (en) * 2012-10-19 2013-01-16 厦门大学 Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst
CN103316683A (en) * 2013-07-05 2013-09-25 昆明理工大学 Preparation method of carbon nanotube loaded copper-based catalyst applied to methanol synthesis

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