CN113845096A - Preparation method of cyano-rich carbon nitride, product and application thereof - Google Patents
Preparation method of cyano-rich carbon nitride, product and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of cyano-rich carbon nitride, a product thereof and application of the cyano-rich carbon nitride in the field of preparing aldehyde by photocatalytic oxidation of alcohol. The preparation method comprises the following steps: uniformly mixing a carbon nitride precursor with a pore-foaming agent, and then sintering at high temperature in the air to obtain the cyano-rich carbon nitride; the pore-foaming agent is selected from one or more of ammonium chloride, ammonium carbonate and ammonium sulfate. The carbon nitride rich in cyano group prepared by the specific process is used as a catalyst for the reaction of preparing aldehyde by photocatalytic oxidation of alcohol, and the oxidation with high conversion rate and high selectivity from alcohol to aldehyde under mild conditions (normal temperature and normal pressure) is realized. The catalyst has excellent catalytic activity on different substrates, and has wide application range; after being recycled for many times, the catalytic performance still keeps stable.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to a preparation method of cyano-rich carbon nitride, a product of the cyano-rich carbon nitride and application of the cyano-rich carbon nitride in the field of preparing aldehyde by photocatalytic oxidation of alcohol.
Background
The aldehyde is a common reagent and raw material in the chemical and medical field, has wide application in the fields of chemical industry, pharmacy, building and the like, and the demand for the aldehyde is increased year by year along with the acceleration of the industrialization process. The traditional method for industrially preparing aldehydes is that vaporized alcohol is blown and passed through the surface of silver, copper or silver-copper alloy as a catalyst at 300-480 ℃, and aldehydes are prepared by oxidative dehydrogenation of air. The method has high energy consumption, the catalyst is easy to inactivate, the conversion rate of the substrate is low, and the selectivity of the target product aldehyde needs to be improved. Therefore, the existing strategies and technologies for preparing aldehydes by oxidizing alcohols are in need of improvement and development.
Disclosure of Invention
The invention discloses a preparation method of carbon nitride rich in cyano group aiming at the problems in the prior art, the carbon nitride rich in cyano group prepared by the specific process is used as a catalyst for the reaction of preparing aldehyde by photocatalytic oxidation of alcohol, and the oxidation with high conversion rate and high selectivity from alcohol to aldehyde under mild conditions (normal temperature and normal pressure) is realized. The catalyst has excellent catalytic activity on different substrates, and has wide application range; after being recycled for many times, the catalytic performance still keeps stable.
The specific technical scheme is as follows:
a method for preparing cyano-rich carbon nitride, comprising:
uniformly mixing a carbon nitride precursor with a pore-foaming agent, and then sintering at high temperature in the air to obtain the cyano-rich carbon nitride;
the pore-foaming agent is selected from one or more of ammonium chloride, ammonium carbonate and ammonium sulfate.
The invention discloses a preparation method of cyano-rich carbon nitride, which is prepared by taking a carbon nitride precursor and a specific type of pore-foaming agent as raw materials and sintering at a high temperature in an air atmosphere.
The carbon nitride precursor is selected from one or more of cyanamide, dicyandiamide and urea.
The molar ratio of the carbon nitride precursor to the porogen is 6-50: 1.
and sintering at high temperature at 500-600 ℃ for 1-5 h.
The cyano-rich carbon nitride prepared by the process is used as a catalyst and can be used for the reaction of preparing aldehyde by photocatalytic oxidation of alcohol.
Tests show that the catalyst prepared by the specific process can realize high-conversion rate and high-selectivity oxidation of alcohol to aldehyde under mild conditions (normal temperature and normal pressure). The catalyst has excellent catalytic activity on different substrates, and has wide application range; after being recycled for many times, the catalytic performance still keeps stable.
Further comparative experiments show that if no pore-foaming agent is added, or the pore-foaming agent is replaced by potassium chloride, sodium borohydride and other raw materials commonly used in the field for preparing cyano-rich carbon nitride, the catalytic activity of the prepared product for catalyzing the reaction for preparing aldehyde by oxidizing alcohol is obviously reduced, and particularly the substrate conversion rate is greatly reduced. If the atmosphere of the high-temperature sintering is replaced by a protective atmosphere, such as nitrogen, the catalytic activity of the high-temperature sintering catalyst for catalyzing the reaction of oxidizing alcohol to prepare aldehyde is also obviously reduced.
Preferably:
the carbon nitride precursor is selected from cyanamide;
the pore-forming agent is selected from ammonium sulfate;
the molar ratio of the carbon nitride precursor to the porogen is 10-50: 1, more preferably 10 to 15: 1, more preferably 12: 1.
preferably:
sintering at high temperature, wherein the temperature is 550-600 ℃, and the heating rate is 2-3 ℃/min; more preferably, the temperature is 550 ℃.
Experiments show that the prepared cyano-rich carbon nitride can more efficiently catalyze the reaction of preparing aldehyde by oxidizing alcohol through further optimizing the types of the raw materials and the process parameters, and the conversion rate of a substrate can be greatly improved.
The invention also discloses a reaction for preparing aldehyde by photocatalytic oxidation of alcohol, wherein an alcohol compound is used as a raw material, and the cyano-rich carbon nitride is used as a catalyst.
The structural formula of the alcohol compound is shown as the following formula (I):
in the formula, R1Is selected from H or CH3，R2Selected from pyridyl, thienyl, cyclohexyl, n-hexyl, phenethyl, phenyl or substituted phenyl;
the substituted phenyl is selected from phenyl substituted by methoxy, methyl, acetyl, fluorine, chlorine, bromine or nitro.
When the substituent is methoxy, the ortho-position, meta-position or para-position of the phenyl can be selected for substitution;
when the substituent is methyl, acetyl, fluoro, chloro, bromo or nitro, the phenyl group may be optionally substituted in the para position.
Specifically, the alcohol compound is selected from benzyl alcohol, p-methoxybenzyl alcohol, m-methoxybenzyl alcohol, o-methoxybenzyl alcohol, 3, 5-dimethoxybenzyl alcohol, p-fluorobenzyl alcohol, p-chlorobenzyl alcohol, p-bromobenzyl alcohol, p-acetylbenzyl alcohol, p-nitrobenzyl alcohol, p-methylbenzyl alcohol, DL-1-phenylethyl alcohol, phenylpropyl alcohol, 2-pyridinylcarbinol, 2-thiophenemethanol, cyclohexylmethanol or n-heptanol.
Experiments show that the cyano-rich carbon nitride prepared by the invention has stronger substrate adaptability and excellent catalytic activity on the alcohol compounds.
Further preferably, the alcohol compound is selected from benzyl alcohol, p-methoxybenzyl alcohol, m-methoxybenzyl alcohol, o-methoxybenzyl alcohol, 3, 5-dimethoxybenzyl alcohol, p-chlorobenzyl alcohol, p-bromobenzyl alcohol, p-acetoxybenzyl alcohol, p-methylbenzyl alcohol or 2-thiophenyl alcohol.
The reaction for preparing aldehyde by photocatalytic oxidation of alcohol specifically comprises the following steps:
blending an alcohol compound, a catalyst and a solvent in a reaction device, introducing oxygen into the reaction device, and then placing the reaction device under a light source for irradiating for 4-12 hours;
the solvent is selected from one or more of water, acetonitrile, ethyl acetate, acetone and dichloromethane; further preferred is acetonitrile.
The concentration of the alcohol compound in the solvent is 0.5-5 mg/mL.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of cyano-rich carbon nitride, which is prepared by taking a carbon nitride precursor and a specific type of pore-foaming agent as raw materials and sintering the raw materials at a high temperature in an air atmosphere, and has simple and controllable preparation process.
The cyano-rich carbon nitride prepared by the process can be used as a catalyst for the reaction of preparing aldehyde by photocatalytic oxidation of alcohol, and the alcohol is converted into the aldehyde by the photocatalytic technology at normal temperature and normal pressure. The application of the catalyst realizes the oxidation of alcohol to aldehyde with high conversion rate and high selectivity under mild conditions. The catalyst has stronger substrate adaptability and excellent catalytic activity on various different alcohol compounds; after being recycled for many times, the catalytic performance still keeps stable. Solves the problems of high energy consumption, unstable catalytic activity, low conversion rate and selectivity and the like in the existing aldehyde preparation process.
Drawings
FIG. 1 is an XRD spectrum of cyano-rich carbon nitride prepared in examples 1-3 respectively, and an XRD spectrum of a product prepared in comparative example 1 is given for comparison;
FIG. 2 is an IR spectrum of the cyano-rich carbon nitride prepared in each of examples 1-3, and an IR spectrum of the product prepared in comparative example 1 is shown for comparison.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to embodiments and drawings. It should be understood, however, that the description herein of specific embodiments is only for the purpose of illustration and not for the purpose of limitation.
Example 1
Selecting cyanamide as a carbon nitride precursor, mixing the cyanamide with ammonium chloride according to a molar ratio of 12:1, calcining the mixture in a muffle furnace in an air atmosphere, heating the mixture to 550 ℃ from 25 ℃ at a heating rate of 2.2 ℃/min, and keeping the temperature for 4 hours to prepare the cyano-rich carbon nitride (CN-Cl).
20mg of the cyano-rich carbon nitride prepared in this example, 0.1mmol of benzyl alcohol, and 5mL of acetonitrile were placed in a 20mL quartz glass reaction flask, and oxygen gas at one atmospheric pressure was introduced into the reaction flask to react for 4 hours under irradiation of visible light at 30 ℃.
Example 2
The preparation procedure was essentially the same as in example 1, except that the porogen was replaced with ammonium carbonate and the resulting cyano-rich carbon nitride was identified as CN-C.
The conditions for the catalytic activity test were also exactly the same as in example 1.
Example 3
The preparation process was essentially the same as in example 1, except that the porogen was replaced with ammonium sulfate and the resulting cyano-rich carbon nitride was designated CN-S.
The conditions for the catalytic activity test were also exactly the same as in example 1.
Fig. 1 is an XRD spectrogram of cyano-rich carbon nitride prepared in each of examples 1 to 3, and the XRD spectrogram of the product prepared in comparative example 1 is shown for comparison, and it can be found that all samples have significant XRD diffraction peaks at 27.3 ° and 13.1 ° corresponding to characteristic peaks of carbon nitride substances, and the intrinsic crystal structure of carbon nitride is not changed by introducing a porogen.
FIG. 2 is an infrared spectrum of cyano-rich carbon nitride prepared in each of examples 1 to 3, and an infrared spectrum of a product prepared in comparative example 1 is shown for comparison, and the comparison shows that a carbon nitride sample prepared by using a porogen is 2180cm-1The peak is obvious in carbon-nitrogen triple bond, namely cyano peak, and the peak is most obvious in cyano peak of the sample prepared by taking ammonium sulfate as a pore-foaming agent.
Examples 4 to 5
The cyano-rich carbon nitride prepared in example 3 was used, except that the visible light irradiation time in the catalytic activity test was replaced with 8h and 10h, respectively.
The catalytic activity results of photocatalytic benzyl alcohol preparation of benzaldehyde by cyanocarbon nitride prepared in the above examples 1 to 5 are shown in table 1 below.
TABLE 1
Example 6
The procedure was essentially the same as in example 3 except that the molar ratio of cyanamide to ammonium sulfate was replaced by 6:1 and the resulting cyano-rich carbon nitride was identified as CN-S6.
20mg of the cyanocarbon nitride, 0.1mmol of benzyl alcohol and 5mL of acetonitrile prepared in this example were placed in a 20mL quartz glass reaction flask, and oxygen gas under one atmospheric pressure was introduced into the reaction flask to react for 8 hours under irradiation of visible light at 30 ℃.
Example 7
The procedure was essentially the same as in example 3 except that the molar ratio of cyanamide to ammonium sulfate was replaced by 50:1 and the resulting cyano-rich carbon nitride was designated CN-S50.
The conditions for the catalytic activity test were also exactly the same as in example 6.
Example 8
The preparation procedure was essentially the same as in example 3, except that the calcination temperature was replaced by 500 ℃ and the resulting cyano-rich carbon nitride was designated as CN-S-500.
The conditions for the catalytic activity test were exactly the same as in example 6.
Example 9
The preparation procedure was essentially the same as in example 3, except that the calcination temperature was replaced by 600 ℃ and the resulting cyano-rich carbon nitride was designated as CN-S-600.
The conditions for the catalytic activity test were exactly the same as in example 6.
Example 10
The preparation process was essentially the same as in example 3, except that the calcination time was replaced with 2 h.
The conditions for the catalytic activity test were exactly the same as in example 6.
Example 11
20mg of the CN-S catalyst prepared in example 3, 0.1mmol of benzyl alcohol and 5mL of deionized water were placed in a 20mL quartz glass reaction flask, and oxygen gas under one atmospheric pressure was introduced into the reaction flask to react for 8 hours under irradiation of visible light at 30 ℃.
Example 12
20mg of the CN-S catalyst prepared in example 3, 0.1mmol of benzyl alcohol, and 5mL of ethyl acetate were placed in a 20mL quartz glass reaction flask, and oxygen gas was introduced into the reaction flask under one atmospheric pressure to perform a reaction under irradiation of visible light at 30 ℃ for 8 hours.
Example 13
20mg of the CN-S catalyst prepared in example 3, 0.1mmol of p-methoxybenzyl alcohol and 5mL of acetonitrile were placed in a 20mL quartz glass reaction flask, and oxygen gas at one atmospheric pressure was introduced into the reaction flask to react for 8 hours under irradiation of visible light at 30 ℃.
Examples 14 to 28
The CN-S catalyst prepared in example 3 was used, except that in the case of the catalytic activity test, p-methoxybenzyl alcohol in example 13 was replaced with m-methoxybenzyl alcohol, o-methoxybenzyl alcohol, 3, 5-dimethoxybenzyl alcohol, p-fluorobenzyl alcohol, p-chlorobenzyl alcohol, p-bromobenzyl alcohol, p-acetylbenzyl alcohol, p-nitrobenzyl alcohol, p-methylbenzyl alcohol, DL-1-phenylethyl alcohol, phenylpropyl alcohol, 2-pyridinemethanol, 2-thiophenyl alcohol, cyclohexylmethanol or n-heptanol, respectively.
Example 29
The preparation process is basically the same as that in example 3, except that dicyandiamide is selected as the carbon nitride precursor.
Example 30
The preparation process is basically the same as that in example 3, except that urea is selected as the carbon nitride precursor.
The catalytic activity results of photocatalytic alcohol preparation using cyanocarbon nitride prepared in example 4 and examples 6 to 30 are shown in table 2 below.
TABLE 2
Test for catalytic stability
The cyano-rich carbon nitride and the catalytic activity test conditions of example 4 were selected, and the catalyst was repeatedly collected and reacted 5 times, and the catalytic stability results are shown in table 3 below.
TABLE 3
Comparative example 1
The preparation process was essentially the same as in example 3, except that no porogen was added and the resulting product was Bulk-based carbon nitride (Bulk).
20mg of bulk phase-based carbon nitride prepared in this comparative example, 0.1mmol of benzyl alcohol, and 5mL of acetonitrile were placed in a 20mL quartz glass reaction flask, and oxygen gas at one atmospheric pressure was introduced into the reaction flask to react for 8 hours under irradiation of visible light at 30 ℃.
Comparative example 2
The preparation process was essentially the same as in example 3, except that ammonium sulfate was replaced with potassium chloride.
The conditions of the catalytic activity test were exactly the same as in comparative example 1.
Comparative example 3
The preparation process was substantially the same as in example 3 except that the calcination atmosphere was replaced with nitrogen gas from air.
The conditions for the catalytic activity test were exactly the same as in example 6.
Comparative example 4
The method reported in the reference (ChemCatChem 2019,11,6275) selects melamine as a carbon nitride precursor, puts the precursor into a muffle furnace to be calcined in an air atmosphere, heats the precursor to 550 ℃ from 25 ℃ at a heating rate of 2 ℃/min, keeps the temperature for 3h, takes the prepared carbon nitride, grinds the carbon nitride and sodium borohydride according to a mass ratio of 1: 1, mixing, calcining for 0.5h in a muffle furnace nitrogen atmosphere, cleaning with deionized water, and drying to prepare the cyano-rich carbon nitride obtained by sodium borohydride auxiliary etching.
20mg of the cyanocarbon nitride compound prepared in this comparative example, 0.1mmol of benzyl alcohol, and 5mL of acetonitrile were placed in a 20mL quartz glass reaction flask, and oxygen gas at one atmospheric pressure was introduced into the reaction flask to react for 8 hours under irradiation of visible light at 30 ℃.
Comparative example 5
The reference (ChemCatChem 2016,8,3441) reports a method of selecting cyanamide as a precursor of carbon nitride, and mixing the cyanamide with ammonium sulfate according to a mass ratio of 1: 2.2, placing the mixture in a muffle furnace in a nitrogen atmosphere for calcining, heating the mixture to 600 ℃ from 25 ℃ at the heating rate of 2.5 ℃/min, and preserving the heat for 1h to prepare the carbon nitride.
20mg of the carbon nitride prepared in this comparative example, 0.1mmol of benzyl alcohol, and 5mL of acetonitrile were placed in a 20mL quartz glass reaction flask, and oxygen gas at one atmospheric pressure was introduced into the reaction flask to react for 8 hours under irradiation of visible light at 30 ℃.
Comparative example 6
According to the method reported in the reference (Chemical Engineering Journal 409(2021)128030), melamine is selected as a carbon nitride precursor, the carbon nitride precursor is mixed with potassium chloride according to the mass ratio of 8:1, then the mixture is placed in a muffle furnace nitrogen atmosphere for calcination, the temperature is increased from 25 ℃ at the heating rate of 5 ℃/min to 550 ℃, and the temperature is kept for 3 hours, so that the carbon nitride is prepared.
20mg of the carbon nitride prepared in this comparative example, 0.1mmol of benzyl alcohol, and 5mL of acetonitrile were placed in a 20mL quartz glass reaction flask, and oxygen gas at one atmospheric pressure was introduced into the reaction flask to react for 8 hours under irradiation of visible light at 30 ℃.
The catalytic activity results of photocatalytic benzyl alcohol prepared from the products prepared in example 4 and comparative examples 1 to 6 are shown in table 4 below.
TABLE 4
Claims (10)
1. A method for preparing cyano-rich carbon nitride, which is characterized by comprising the following steps:
uniformly mixing a carbon nitride precursor with a pore-foaming agent, and then sintering at high temperature in the air to obtain the cyano-rich carbon nitride;
the pore-foaming agent is selected from one or more of ammonium chloride, ammonium carbonate and ammonium sulfate.
2. The method of claim 1, wherein the carbon nitride precursor is selected from one or more of cyanamide, dicyandiamide, and urea.
3. The method for preparing cyano-rich carbon nitride according to claim 1, wherein the molar ratio of the carbon nitride precursor to the porogen is 6-50: 1.
4. the method for preparing cyano-rich carbon nitride according to claim 1, wherein the high-temperature sintering is performed at 500-600 ℃ for 1-5 hours.
5. The method for producing cyano-rich carbon nitride according to any one of claims 1 to 4, characterized in that:
the carbon nitride precursor is selected from cyanamide;
the pore-forming agent is selected from ammonium sulfate;
the molar ratio of the carbon nitride precursor to the porogen is 10-15: 1.
6. the method for preparing cyano-rich carbon nitride according to claim 5, wherein the high temperature sintering is performed at 550-600 ℃.
7. A cyano-rich carbon nitride prepared according to the method of any one of claims 1 to 6.
8. A reaction for preparing aldehyde by photocatalytic oxidation of alcohol, characterized in that an alcohol compound is used as a raw material, and the cyano-rich carbon nitride according to claim 7 is used as a catalyst.
9. The photocatalytic oxidation of an alcohol to aldehydes as set forth in claim 8, wherein the alcohol compound has the formula (i):
in the formula, R1Is selected from H or CH3，R2Selected from pyridyl, thienyl, cyclohexyl, n-hexyl, phenethyl, phenyl or substituted phenyl;
the substituted phenyl is selected from phenyl substituted by methoxy, methyl, acetyl, fluorine, chlorine, bromine or nitro.
10. The photocatalytic oxidation reaction of an alcohol to aldehydes according to claim 8, characterized by specifically comprising:
blending an alcohol compound, a catalyst and a solvent in a reaction device, introducing oxygen into the reaction device, and then placing the reaction device under a light source for irradiating for 4-12 hours;
the solvent is selected from one or more of water, acetonitrile, ethyl acetate, acetone and dichloromethane;
the concentration of the alcohol compound in the solvent is 0.5-5 mg/mL.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114453001A (en) * | 2022-03-10 | 2022-05-10 | 江苏理工学院 | Carbon nitride nanosheets co-doped with aromatic ring and cyano group, and preparation method and application thereof |
| CN115025803A (en) * | 2022-06-29 | 2022-09-09 | 安徽大学 | Cyano-modified carbon nitride and preparation method and application thereof |
| CN116273122A (en) * | 2023-03-17 | 2023-06-23 | 江苏理工学院 | A preparation method of carbon nitride supported catalyst and its application in plasma-catalytic oxidation denitrification |
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| CN114453001A (en) * | 2022-03-10 | 2022-05-10 | 江苏理工学院 | Carbon nitride nanosheets co-doped with aromatic ring and cyano group, and preparation method and application thereof |
| CN115025803A (en) * | 2022-06-29 | 2022-09-09 | 安徽大学 | Cyano-modified carbon nitride and preparation method and application thereof |
| CN115025803B (en) * | 2022-06-29 | 2024-01-09 | 安徽大学 | Cyano modified carbon nitride and preparation method and application thereof |
| CN116273122A (en) * | 2023-03-17 | 2023-06-23 | 江苏理工学院 | A preparation method of carbon nitride supported catalyst and its application in plasma-catalytic oxidation denitrification |
| CN116273122B (en) * | 2023-03-17 | 2024-06-11 | 江苏理工学院 | Preparation method of carbon nitride supported catalyst and application of carbon nitride supported catalyst in plasma-catalytic oxidation denitration |
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