CN109665951B - ZnO/Se/SiO2Composite materials and their use as oxidizers - Google Patents

ZnO/Se/SiO2Composite materials and their use as oxidizers Download PDF

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CN109665951B
CN109665951B CN201910038447.0A CN201910038447A CN109665951B CN 109665951 B CN109665951 B CN 109665951B CN 201910038447 A CN201910038447 A CN 201910038447A CN 109665951 B CN109665951 B CN 109665951B
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zno
sio
composite material
room temperature
zinc nitrate
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CN109665951A (en
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徐洁
陈海燕
王元有
金党琴
龚爱琴
段汶君
许文静
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Yangzhou Polytechnic Institute
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Yangzhou Polytechnic Institute
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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
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Abstract

The invention relates to ZnO/Se/SiO2Composite material and application thereof as oxidant, ZnO/Se/SiO2The preparation method of the composite material comprises the following steps: adding hydrazine hydrate containing selenium into zinc nitrate solution at room temperature under stirring, continuously stirring for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2A composite material.

Description

ZnO/Se/SiO2Composite materials and their use as oxidizers
Technical Field
The invention belongs to the field of materials, and particularly relates to ZnO/Se/SiO2Composite materials and their use as oxidizers.
Background
The zinc oxide (ZnO) particles have the advantages of large specific surface area, stable chemical properties and the like, and are widely applied to the field of photocatalysts. Selenium (Se) has many excellent physicochemical properties as an intrinsic p-type semiconductor material. At present, no report on the aspect of using ZnO/Se composite materials as oxidants exists. The invention uses zinc nitrate as zinc source, SiO2As a carrier, preparing a novel ZnO/Se/SiO2Composite material which can be used as an oxidizing agent for oxidation reactions.
Disclosure of Invention
The invention provides ZnO/Se/SiO2Composite material, characterized in that the ZnO/Se/SiO2The preparation method of the composite material comprises the following steps:
adding hydrazine hydrate containing selenium into zinc nitrate solution at room temperature under stirring, continuously stirring for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2A composite material.
Wherein the concentration of the zinc nitrate solution is preferably 0.1-0.2mmol/mL, and each mmol of zinc nitrate is 1.0-1.5mL of selenium-containing hydrazine hydrate; the selenium-containing hydrazine hydrate contains 6-10mg of selenium per ml of hydrazine hydrate; 150-200 mu L of ethyl orthosilicate is used for each millimole of zinc nitrate; the above reaction is preferably carried out in an autoclave.
Another embodiment of the present invention provides a ZnO/Se/SiO solid2The preparation method of the composite material is characterized by comprising the following steps:
adding hydrazine hydrate containing selenium into zinc nitrate solution at room temperature under stirring, continuously stirring for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2A composite material.
Wherein the concentration of the zinc nitrate solution is preferably 0.1-0.2mmol/mL, and each mmol of zinc nitrate is 1.0-1.5mL of selenium-containing hydrazine hydrate; the selenium-containing hydrazine hydrate contains 6-10mg of selenium per ml of hydrazine hydrate; 150-200 mu L of ethyl orthosilicate is used for each millimole of zinc nitrate; the above reaction is preferably carried out in an autoclave.
Another embodiment of the present invention provides the above ZnO/Se/SiO2Use of a composite material as an oxidant.
Another embodiment of the present invention provides the above ZnO/Se/SiO2The application of the composite material in preparing cyclohexanedione by oxidizing cyclohexanediol. In particular to the application in preparing 1, 4-cyclohexanedione by oxidizing 1, 4-cyclohexanediol.
Another embodiment of the present invention provides a method for preparing 1, 4-cyclohexanedione, which is characterized by comprising the steps of:
dissolving 1, 4-cyclohexanediol in dichloromethane, and adding the ZnO/Se/SiO2The composite material is stirred and reacted for 10 to 12 hours at room temperature, and ZnO/Se/SiO is filtered and recovered2Concentrating the filtrate to remove dichloromethane to obtain 1, 4-cyclohexanedione; preference is given to using ZnO/Se/SiO per millimole of 1, 4-cyclohexanediol218-20mg of composite material.
Compared with the prior art, the invention has the advantages that: (1) the invention takes zinc nitrate as a zinc source and SiO2As a carrier, preparing a novel ZnO/Se/SiO2The composite material can be used as an oxidant for oxidizing cyclohexanediol to prepare cyclohexanedione; (2) ZnO/Se/SiO prepared by the invention2The composite material oxidant can be recycled for secondary use.
Drawings
FIG. 1 is an SEM image (right) of product A and a TEM image (left) of product A;
figure 2 is the XRD pattern of product a.
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
Adding hydrazine hydrate containing selenium (10mL, 100mg containing selenium) into zinc nitrate solution (0.1mmol/mL, 100mL) at room temperature under stirring, continuously stirring for 20min, heating to 170 ℃ (high-pressure reaction kettle), reacting for 12h, naturally cooling to 90 ℃, adding tetraethoxysilane (1.5mL), continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and vacuum drying to obtain the ZnO/Se/SiO2Composite material (hereinafter referred to as product a, fig. 1, 2).
Example 2
Adding hydrazine hydrate containing selenium (30mL, 180mg containing selenium) into zinc nitrate solution (0.2mmol/mL, 100mL) at room temperature under stirring, stirring for 30min, heating to 180 deg.C (high pressure reaction kettle), reacting for 8h, naturally cooling to 90 deg.C, and adding n-siliconEthyl acetate (4.0mL), stirring continuously until the mixture is naturally cooled to room temperature, filtering, washing precipitates with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2Composite material (hereinafter referred to as product B, SEM image is consistent with product A).
Example 3
Adding hydrazine hydrate containing selenium (10mL, 100mg containing selenium) into zinc nitrate solution (0.1mmol/mL, 100mL) at room temperature under stirring, continuously stirring for 20min, heating to 170 ℃ (high-pressure reaction kettle), reacting for 12h, naturally cooling to room temperature, filtering, precipitating, washing with deionized water and absolute ethyl alcohol in sequence, and vacuum drying to obtain the ZnO/Se composite material (hereinafter referred to as product C).
Example 4
Adding hydrazine hydrate (10mL) into zinc nitrate solution (0.1mmol/mL, 100mL) at room temperature under stirring, continuously stirring for 20min, heating to 170 ℃ (high-pressure reaction kettle), reacting for 12h, naturally cooling to 90 ℃, adding tetraethoxysilane (1.5mL), continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and vacuum drying to obtain ZnO/SiO2Composite material (hereinafter referred to as product D).
Example 5
1, 4-cyclohexanediol (10mmol) was dissolved in dichloromethane (40mL), product A (200mg) was added, the reaction was stirred at room temperature for 10 hours, product A was recovered by filtration, the filtrate was concentrated to remove dichloromethane to give 1, 4-cyclohexanedione (1.03g, yield about 91.9%, HPLC purity 90.8%,1H、13c NMR data consistent with the report).
Example 6
1, 4-cyclohexanediol (10mmol) was dissolved in dichloromethane (40mL), product B (180mg) was added, the reaction stirred at room temperature for 12 hours, product B was recovered by filtration and the dichloromethane was removed by concentration to give 1, 4-cyclohexanedione (1.06g, yield about 92.3%, HPLC purity 90.5%,1H、13c NMR data consistent with the report).
Example 7
1, 4-cyclohexanediol (10mmol) was dissolved in dichloromethane (40mL), product C (200mg) was added and after stirring at room temperature for 10 hours, product C was recovered by filtration and the filtrate was concentrated to remove dichloromethane to give a solid (1.10g, 89.5% 1, 4-cyclohexanediol by HPLC).
Example 8
1, 4-cyclohexanediol (10mmol) was dissolved in dichloromethane (40mL), product D (200mg) was added and after stirring at room temperature for 10 hours, product D was recovered by filtration and the filtrate was concentrated to remove dichloromethane to give a solid (1.16g, 98.2% 1, 4-cyclohexanediol by HPLC).
Example 9
1, 4-cyclohexanediol (10mmol) was dissolved in methylene chloride (40mL), and the product A recovered in example 1 was added, and after stirring and reacting at room temperature for 10 hours, the product A was recovered by filtration, and the filtrate was concentrated to remove methylene chloride, to give 1, 4-cyclohexanedione (1.08g, yield about 96.3%, HPLC purity 84.8%).

Claims (7)

1. ZnO/Se/SiO2Composite material, characterized in that the ZnO/Se/SiO2The preparation method of the composite material comprises the following steps:
adding hydrazine hydrate containing selenium into zinc nitrate solution at room temperature under stirring, continuously stirring for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2A composite material.
2. The ZnO/Se/SiO of claim 12The composite material is characterized in that the concentration of zinc nitrate solution is 0.1-0.2mmol/mL, and each mmol of zinc nitrate uses 1.0-1.5mL of selenium-containing hydrazine hydrate; the selenium-containing hydrazine hydrate contains 6-10mg of selenium per ml of hydrazine hydrate.
3. The ZnO/Se/SiO of any one of claims 1 to 22Composite material, characterized in that it uses 150-200 μ L of ethyl orthosilicate per millimole of zinc nitrate.
4. The method of any one of claims 1 to 3ZnO/Se/SiO2Use of a composite material as an oxidant.
5. The ZnO/Se/SiO of any one of claims 1 to 32The application of the composite material in preparing cyclohexanedione by oxidizing cyclohexanediol.
6. The ZnO/Se/SiO of any one of claims 1 to 32Application of the composite material in preparing 1, 4-cyclohexanedione by oxidizing 1, 4-cyclohexanediol.
7. A preparation method of 1, 4-cyclohexanedione is characterized by comprising the following steps:
dissolving 1, 4-cyclohexanediol in dichloromethane, adding the ZnO/Se/SiO as claimed in claim 12The composite material is stirred and reacted for 10 to 12 hours at room temperature, and ZnO/Se/SiO is filtered and recovered2Concentrating the filtrate to remove dichloromethane to obtain 1, 4-cyclohexanedione; ZnO/Se/SiO used per millimole of 1, 4-cyclohexanediol218-20mg of composite material.
CN201910038447.0A 2019-01-15 2019-01-15 ZnO/Se/SiO2Composite materials and their use as oxidizers Active CN109665951B (en)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
CN101020627A (en) * 2007-01-22 2007-08-22 河北大学 Process of synthesizing 1,4-cyclohexyl dione
CN102447064A (en) * 2010-10-06 2012-05-09 曾永斌 Polymer solar cell and preparation method thereof
JP2015142882A (en) * 2014-01-31 2015-08-06 博 久保田 Hydrogen formation catalyst
CN106588618A (en) * 2016-10-28 2017-04-26 江苏扬农化工集团有限公司 Method for catalyzing oxidation of phenol and hydrogen peroxide with selenium-containing catalyst for synthesis of p-benzoquinone
CN107321375A (en) * 2017-07-13 2017-11-07 扬州工业职业技术学院 A kind of SiO2/ZnO/g‑C3N4Nano material and its application in reduction of hexavalent chromium
WO2018109247A1 (en) * 2016-12-15 2018-06-21 Consejo Superior De Investigaciones Científicas (Csic) Regioselective, stereoselective and catalytic hydrochlorination of alkynes
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Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020627A (en) * 2007-01-22 2007-08-22 河北大学 Process of synthesizing 1,4-cyclohexyl dione
CN102447064A (en) * 2010-10-06 2012-05-09 曾永斌 Polymer solar cell and preparation method thereof
JP2015142882A (en) * 2014-01-31 2015-08-06 博 久保田 Hydrogen formation catalyst
CN106588618A (en) * 2016-10-28 2017-04-26 江苏扬农化工集团有限公司 Method for catalyzing oxidation of phenol and hydrogen peroxide with selenium-containing catalyst for synthesis of p-benzoquinone
WO2018109247A1 (en) * 2016-12-15 2018-06-21 Consejo Superior De Investigaciones Científicas (Csic) Regioselective, stereoselective and catalytic hydrochlorination of alkynes
CN107321375A (en) * 2017-07-13 2017-11-07 扬州工业职业技术学院 A kind of SiO2/ZnO/g‑C3N4Nano material and its application in reduction of hexavalent chromium
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