CN115337954A - Composite photocatalyst based on carbon nitride and preparation method and application thereof - Google Patents

Composite photocatalyst based on carbon nitride and preparation method and application thereof Download PDF

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CN115337954A
CN115337954A CN202211267134.0A CN202211267134A CN115337954A CN 115337954 A CN115337954 A CN 115337954A CN 202211267134 A CN202211267134 A CN 202211267134A CN 115337954 A CN115337954 A CN 115337954A
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carbon nitride
composite photocatalyst
nds
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CN115337954B (en
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郝彦海
张超
王艳
郝敬瑞
牛忠华
秋淑娟
郭旭光
张宝仲
王世杰
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Shandong Huantou Environment Engineering Co ltd
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Abstract

The invention belongs to the technical field of photocatalysis, relates to hydrogen production by photocatalytic decomposition of water, and particularly relates to a composite photocatalyst based on carbon nitride and a preparation method and application thereof. The preparation method comprises the following steps: HKH and BPTA were added to methanol andcarrying out solvent thermal reaction in the mixed solution of N-methyl pyrrolidone to obtain Bulk-C 4 N, hydrothermal method is adopted for Bulk-C 4 N is treated to obtain C 4 N quantum dot solution; pyrolysis of melamine to give Bulk-C 3 N 4 Under the air atmosphere, bulk-C is added 3 N 4 Heating the mixture to 510 to 550 ℃ by a program to obtain C 3 N 4 Nanosheets; c is to be 3 N 4 Nanosheet addition to C 4 And stirring and mixing the N quantum dot solution, and standing to obtain the nano-composite material. The photocatalyst provided by the invention can improve C 3 N 4 The bandwidth is reduced, so that the separation efficiency of photo-generated electrons and holes of the photocatalyst is effectively improved, and the photocatalytic hydrogen production performance of the material is improved.

Description

Composite photocatalyst based on carbon nitride and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalysis, relates to hydrogen production by photocatalytic water decomposition, and particularly relates to a composite photocatalyst based on carbon nitride as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
C 3 N 4 The graphene-like two-dimensional lamellar structure is a polymer semiconductor, 6 lone-pair nitrogen exists in the structure, and the forbidden band width is about 2.7 ev. The band structure of the solar cell is easy to generate photon-generated carriers, so that the utilization of renewable solar energy is improved, and photocatalysis is realized. C of a layer structure 3 N 4 Is an effective carrier, can increase the contact area between active sites and reactants, improve the dispersibility of materials, and avoid the aggregation of substances. However, the wide forbidden band makes the absorptivity to full spectrum visible light relatively low, and the carrier recombination rate is too high, resulting in C 3 N 4 The photocatalytic effect as a photocatalyst is poor.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a composite photocatalyst based on carbon nitride and a preparation method and application thereof 3 N 4 The method has the advantages of reducing bandwidth and inhibiting charge recombination, thereby effectively improving the separation efficiency of photo-generated electrons and holes of the photocatalyst and improving the photocatalytic hydrogen production performance of the material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the preparation method of the composite photocatalyst based on the carbon nitride comprises the following steps:
adding cyclohexadecanone (HKH) and 3,3' -diaminobenzidine (BPTA) into a mixed solution of methanol and N-methylpyrrolidone for solvothermal reaction to obtain Bulk-C 4 N, hydrothermal method is adopted for Bulk-C 4 N is processed to obtain C 4 N quantum dots (C) 4 NDs) solution;
pyrolyzing melamine to obtain Bulk-C 3 N 4 Under the air atmosphere, bulk-C is added 3 N 4 Heating to 510-550 ℃ by a program and carrying out heat treatment to obtain C 3 N 4 Nanosheet (C) 3 N 4 NSs）；
C is to be 3 N 4 Nanosheet addition to C 4 And stirring and mixing the N quantum dot solution, and standing to obtain the product.
The invention is through C 4 N quantum dots and C 3 N 4 The nano sheets are compounded to form a heterogeneous composite material, the interface of the heterogeneous composite material can promote charge separation, inhibit the compounding rate, and enable the material to have a smaller band gap under the action of van der Waals force, thereby being beneficial to enhancing the light absorption capacity and light stability of the composite material to visible lightAnd (5) performing qualitative determination. In addition, the heterogeneous composite material has large specific surface area and can provide a large number of reaction active sites.
The research shows that C 3 N 4 Nanosheet to C 4 In the process of stirring and mixing the N quantum dot solution, C 3 N 4 Nanosheets and C 4 The quality of the N quantum dots has higher influence on the catalytic activity of the composite photocatalyst based on carbon nitride in the photocatalytic decomposition of water to prepare hydrogen, and when C is used 3 N 4 Nanosheets and C 4 The mass ratio of the N quantum dots to the C is 25.1-0.4 3 N 4 The hydrogen activity of the water produced by photocatalytic decomposition of the nanosheets is higher. When C is present 3 N 4 Nanosheets and C 4 When the mass ratio of the N quantum dots is 25 to 0.18 to 0.22, the activity of photocatalytic decomposition of water to produce hydrogen is remarkably improved.
In another aspect, a composite photocatalyst based on carbon nitride is obtained by the preparation method.
In a third aspect, the composite photocatalyst based on carbon nitride is applied to photocatalytic decomposition of water to prepare hydrogen.
The invention has the beneficial effects that:
1. the invention can be realized by controlling C 4 Content regulation of NDs (Newcastle disease virus) in composite photocatalyst based on carbon nitride 4 The doping amount of N is adjusted, so that the catalytic performance of the photocatalyst is adjusted.
2. The preparation method can prepare C with different particle sizes by adjusting the hydrothermal reaction time 4 NDs, thereby enabling regulation of C 4 Size adjustment of NDs particle diameter C 4 N electron point and C 3 N 4 And (4) composite effect of the nano sheet.
3. The invention improves C by constructing a heterojunction composite structure 4 N/C 3 N 4 The energy band structure enhances the charge separation efficiency, so that the composite photocatalyst based on carbon nitride has the performance of high-efficiency photocatalytic hydrogen production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows C prepared in examples 4 and 7 4 NDs and Bulk-C 4 An XRD spectrum of N;
FIG. 2 is C, prepared according to example 4 4 Atomic force microscopy of NDs;
FIG. 3 is C, prepared according to example 4 4 Particle size distribution profiles of NDs;
FIG. 4 is C, prepared according to example 13 4 Atomic force microscopy of NDs;
FIG. 5 is C, prepared according to example 13 4 The particle size distribution profile of NDs;
FIG. 6 is C, prepared according to example 14 4 Atomic force microscopy of NDs;
FIG. 7 is C prepared in example 14 4 Particle size distribution profiles of NDs;
FIG. 8 is C, prepared according to example 4 4 Transmission electron micrographs of NDs;
FIG. 9 is C, prepared according to example 6 3 N 4 Transmission electron micrographs of NSs;
FIG. 10 is C prepared in example 4 4 FTIR spectra of NDs;
FIG. 11 is C, prepared according to example 6 3 N 4 FTIR spectra of NSs;
FIG. 12 shows UV spectra of materials prepared in examples 4 and 6;
FIG. 13 is a graph showing the hydrogen production of each of the photocatalysts prepared in example 5;
in the figure, 4, 6,7, 13, 14 represent samples produced in examples 4, 6,7, 13, 14, respectively.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the prior art C 3 N 4 The wide forbidden band width has relatively low full-spectrum visible light absorptivity, and the carrier recombination rate is too high, which causes C 3 N 4 The photocatalyst has poor photocatalytic effect, and the invention provides a composite photocatalyst based on carbon nitride and a preparation method and application thereof.
The invention provides a preparation method of a composite photocatalyst based on carbon nitride, which comprises the following steps:
adding cyclohexadecanone (HKH) and 3,3' -diaminobenzidine (BPTA) into a mixed solution of methanol and N-methylpyrrolidone for solvothermal reaction to obtain Bulk-C 4 N, hydrothermal method is adopted to react Bulk-C 4 N is treated to obtain C 4 N quantum dots (C) 4 NDs) solution;
pyrolyzing melamine to obtain Bulk-C 3 N 4 Under the air atmosphere, bulk-C is added 3 N 4 Heating to 510 to 550 ℃ by program, and carrying out heat treatment to obtain C 3 N 4 Nanosheet (C) 3 N 4 NSs）；
C is to be 3 N 4 Nanosheet addition to C 4 And stirring and mixing the N quantum dot solution, and standing to obtain the nano-composite material.
Preparation C 4 N can be prepared from BPTA and HKH, or triphenylene-2,3,6,7,10,11-Hexamine (HATP) and HKH, but C is obtained due to the different structures of BPTA and HATP 4 The unit structures in N are different, and the C prepared by BPTA and HKH is adopted in the invention 4 N is easier to realize industrialized mass production, and the generated unit structure is more beneficial to C 3 N 4 The nano-sheets are compounded, thereby improving C 3 N 4 The bandwidth is reduced, and the photoproduction electrons and holes of the photocatalyst are effectively improvedThe separation efficiency.
In some embodiments, C 3 N 4 Nanosheets and C 4 The mass ratio of the N quantum dots is 25.1-0.4. The photocatalyst prepared under the condition has higher photocatalytic activity. When C is present 3 N 4 Nanosheets and C 4 When the mass ratio of the N quantum dots is 25.18-0.22, the activity of the photocatalyst for photocatalytic decomposition of water to produce hydrogen can be remarkably improved.
The solvent thermal reaction takes non-aqueous organic matters as a solvent, and the non-aqueous organic matters are heated in a closed system to form a high-pressure reaction system, so that the solvent is selected to have a larger forming relationship with the solvent thermal reaction system 4 And N is added. In some embodiments, bulk-C is prepared 4 In the process of N, the volume of the methanol and the N-methylpyrrolidone is 1 to 3 to 5. The photocatalyst prepared under the condition has better effect.
In some embodiments, the temperature of the solvothermal reaction is 150 to 200 ℃ and the reaction time is 24h. Under the reaction condition, especially at the temperature of 170 to 180 ℃, the prepared photocatalyst has better effect.
In some embodiments, the temperature for hydrothermal treatment is 170 to 210 ℃ and the reaction time is 7 to 11 hours.
In some embodiments, C 4 The concentration of the N quantum dot solution is 0.05-0.15 mg/mL.
In some embodiments, melamine pyrolysis yields Bulk-C 3 N 4 The temperature of (a) is 500 to 550 ℃. The pyrolysis time is 4 to 5 hours. Studies have shown that this temperature allows the melamine to be pyrolyzed completely, thus avoiding C 3 N 4 Impurities are doped to affect the performance of the photocatalyst. The pyrolysis adopts temperature programming, and can avoid the influence of too fast heating on C 3 N 4 The morphology of (2). The rate of temperature rise was 1~3 ℃/min.
In some embodiments, the heat treatment time is 4 to 8 hours.
In some embodiments, the ramp rate of the heat treatment is 1~3 ℃/min.
In some embodiments, C 3 N 4 Nano meterAdding to C 4 The stirring speed of stirring and mixing the N quantum dot solution is 500 to 700 rad/min.
In some embodiments, C 3 N 4 Nanosheet addition to C 4 The stirring and mixing time of the N quantum dot solution is 3 to 5 hours.
In another embodiment of the invention, a composite photocatalyst based on carbon nitride is provided, which is obtained by the preparation method.
In a third embodiment of the invention, an application of the composite photocatalyst based on carbon nitride in hydrogen production through photocatalytic decomposition of water is provided.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 20 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring to a 100mL reaction kettle liner, assembling the reaction kettle, and reacting in an oven at 175 ℃ for 24h. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reaction kettle, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, water to 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 2:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 30 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and oven drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Putting the powder in a boat, heating to 520 ℃ in a muffle furnace at a heating rate of 2 ℃/min, and then keeping the constant temperature of 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 3:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 50 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 4:
this example is the synthesis of C 4 NDs：
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
Example 5:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 10 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2. Get 5mg Bulk-C 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 6:
this example is the synthesis of C according to the following procedure 3 N 4 NSs：
5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
Example 7:
this example is the synthesis of Bulk-C according to the following procedure 4 N：
1. HKH (cyclohexadedone) 41.6 mg and BPTA (3,3' -diaminobenzidine) 42.7 mg were added to 10 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and oven drying to obtain Bulk-C 4 N。
Example 8:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HK of 41.6 mgH (cyclohexadecanone) and 42.7 mg BPTA (3,3' -diaminobenzidine) were added to 20 mL (V) Methanol :V NMP = 1:4), transferring to the inner lining of a 100mL reaction kettle, and reacting in an oven for 12 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 9:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 30 mL (V Methanol :V NMP = 1:4), transferring to the inner lining of a 100mL reaction kettle, assembling the reaction kettle, and reacting in an oven at 175 ℃ for 24 hours. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h.Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solution 25mg of C each was added 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 10:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, assembling the reaction kettle, and reacting in an oven for 24 hours at 150 ℃. Cooling to room temperature, washing with ethanol and deionized water twice, and oven drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 11:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (ring) of 41.6 mg was addedHexaketone) and 42.7 mg (3,3' -diaminobenzidine) were added to 25 mL (V) Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, assembling the reaction kettle, and reacting in an oven for 24 hours at 200 ℃. Cooling to room temperature, washing with ethanol and deionized water twice, and oven drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 12:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2. 10 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooling downAfter cooling to room temperature, grinding into powder. 1 g of Bulk-C was taken 3 N 4 Putting the powder in a boat, heating to 520 ℃ in a muffle furnace at a heating rate of 2 ℃/min, and then keeping the constant temperature of 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 13:
this example is the synthesis of C according to the following procedure 4 NDs：
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 8 h to obtain C 4 NDs solution.
Example 14:
this example is the synthesis of C 4 NDs：
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring to the inner lining of a 100mL reaction kettle, assembling the reaction kettle, and reacting in an oven at 175 ℃ for 24 hours. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 12h to obtain C 4 NDs solution.
Example 15:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring to the inner lining of a 100mL reaction kettle, assembling the reaction kettle, and reacting in an oven at 175 ℃ for 24 hours. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 10 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solution 25mg of C each was added 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring with a speed of 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on the carbon nitride.
Example 16:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into 100mL reactor, reacting in oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. Taking 5 g melamine, transferring the melamine into an alumina crucible, and heating the melamine to 600 ℃ in a muffle furnace at a heating rate of 2 ℃/minThen the temperature is constant for 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solution 25mg of C each was added 3 N 4 NSs, water to 50 mL,600 rad/min stirring 4h, standing overnight.
Example 17:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into a reaction kettle, reacting in an oven at 170 ℃ for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 600 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Putting the powder in a boat, heating to 520 ℃ in a muffle furnace at a heating rate of 2 ℃/min, and then keeping the constant temperature of 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solution 25mg of C each was added 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring with a speed of 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on the carbon nitride.
Example 18:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and 42.7 were mixedmg of BPTA (3,3' -diaminobenzidine) was added to 25 mL (V) Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into a reaction kettle, reacting in an oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 4h. Cooled to room temperature and ground into a powder. 1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 4h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
Example 19:
in this example, a composite photocatalyst based on carbon nitride was synthesized according to the following steps:
1. HKH (cyclohexadecanone) of 41.6 mg and BPTA (3,3' -diaminobenzidine) of 42.7 mg were added to 25 mL (V Methanol :V NMP = 1:4), transferring the mixed solvent to the inner lining of a 100mL reaction kettle, and reacting in an oven for 24 hours at 175 ℃ after the reaction kettle is assembled. Cooling to room temperature, washing with ethanol and deionized water twice, and oven drying to obtain Bulk-C 4 N。
2.5 mg of Bulk-C was taken 4 Dispersing N into 50 mL water, transferring into a reaction kettle, reacting in an oven at 200 deg.C for 10 h to obtain C 4 NDs solution.
3. 5 g melamine is taken and transferred into an alumina crucible, the temperature is raised to 500 ℃ in a muffle furnace at the temperature rise rate of 2 ℃/min, and then the melamine is processed at constant temperature of 6 h. Cooled to room temperature and ground into a powder.1 g of Bulk-C was taken 3 N 4 Placing the powder in a boat, heating to 520 deg.C in a muffle furnace at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 6 h to obtain C 3 N 4 NSs。
4. Respectively taking 0.5, 1, 2, 4 and 6 mL of C 4 NDs solutions were each charged with 25mg of C 3 N 4 NSs, adding water to a constant volume of 50 mL, stirring at 600 rad/min for 4h, and standing overnight to obtain the composite photocatalyst based on carbon nitride.
As can be seen from FIG. 1, C appears in the XRD results of the samples prepared in examples 4 and 7 4 And N, no other characteristic diffraction peak is found, which shows that the components of the material are not obviously changed after the quantum dot synthesis is realized.
As can be seen from FIGS. 2 and 3, C prepared in example 4 4 NDs size is mainly focused on 2.8 nm.
As can be seen from FIGS. 4 and 5, C prepared in example 13 4 The size of NDs is mainly focused on 2.5 nm.
As can be seen from FIGS. 6 and 7, C prepared in example 14 4 The size of NDs is mainly focused on 2.3 nm.
Combination of the graphs 2~3 show that hydrothermal reaction time affects C under the same hydrothermal reaction temperature 4 The size of NDs, which increased and then decreased with hydrothermal reaction time, indicates that C can be adjusted by hydrothermal reaction time 4 Size of NDs.
As can be seen from the TEM results in fig. 8, the sample prepared in example 4 exhibited uniform nanoparticulate morphology.
As can be seen from the TEM results in fig. 9, the sample prepared in example 6 exhibited two-dimensional nanoplatelets and a wrinkle phenomenon occurred.
As can be seen from FIG. 10, the infrared characteristic peak and C of the sample prepared in example 4 4 The N quantum dots are identical.
As can be seen from FIG. 11, the infrared characteristic peak and C of the sample prepared in example 6 3 N 4 The quantum dots are uniform.
As can be seen from fig. 12, the absorption light range of the sample prepared in example 6 is mainly concentrated in the ultraviolet region, which is about 200 nm to 400 nm.
Xenon lamp is selected as light source (lambda)>420 nm), adding 100mL aqueous solution of Triethanolamine (TEOA) with the volume ratio of 10% into a 500 mL photoreactor, sampling once every 1h, and detecting the yield of hydrogen by using a gas chromatograph. As can be seen from FIG. 13, when C is 1 to 4mL 4 NDs solution (0.1 mg/mL) with 25mg C 3 N 4 NSs mixed C 4 N/ C 3 N 4 Can improve the amount of photocatalytic hydrogen evolution when the carbon concentration is 2 mL C 4 NDs solution (0.1 mg/mL) with 25mg C 3 N 4 NSs mixed C 4 N/ C 3 N 4 Has the best photocatalytic hydrogen evolution amount. Thus, it is shown that when C 4 NDs and C 3 N 4 When NSs is mixed according to the mass ratio of 0.1 to 0.4 4 NDs and C 3 N 4 When NSs is mixed according to the mass ratio of 0.2.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a composite photocatalyst based on carbon nitride is characterized by comprising the following steps:
adding cyclohexanone and 3,3' -diaminobenzidine into a mixed solution of methanol and N-methylpyrrolidone for solvothermal reaction to obtain Bulk-C 4 N, hydrothermal method is adopted to react Bulk-C 4 N is processed to obtain C 4 N quantum dot solution;
pyrolyzing melamine to obtain Bulk-C 3 N 4 Under the air atmosphere, bulk-C is added 3 N 4 Heating to 510-550 ℃ by a program and carrying out heat treatment to obtain C 3 N 4 Nanosheets;
c is to be 3 N 4 Nanosheet plusInto C 4 And stirring and mixing the N quantum dot solution, and standing to obtain the product.
2. The method for preparing a composite photocatalyst based on carbon nitride as claimed in claim 1, wherein C is 3 N 4 Nanosheets and C 4 The mass ratio of the N quantum dots is 25.1-0.4.
3. The method for preparing a composite photocatalyst based on carbon nitride as claimed in claim 1, wherein Bulk-C is prepared 4 In the process of N, the volume of the methanol and the N-methylpyrrolidone is 1 to 3 to 5.
4. The method for preparing the carbon nitride-based composite photocatalyst as claimed in claim 1, wherein the temperature of the solvothermal reaction is 150 to 200 ℃ and the reaction time is as follows.
5. The method for preparing the carbon nitride-based composite photocatalyst as claimed in claim 1, wherein the temperature of hydrothermal treatment is 170-210 ℃, and the reaction time is 7-11 h.
6. The method for preparing a composite photocatalyst based on carbon nitride as claimed in claim 1, wherein melamine is pyrolyzed to obtain Bulk-C 3 N 4 The temperature of (a) is 500 to 550 ℃.
7. The method for preparing the composite photocatalyst based on carbon nitride as claimed in claim 1, wherein the time of the heat treatment is 4 to 8 hours.
8. The method for preparing a composite photocatalyst based on carbon nitride as claimed in claim 1, wherein the temperature rise rate of the heat treatment is 1~3 ℃/min.
9. A composite photocatalyst based on carbon nitride, obtainable by the process of any one of claims 1~8.
10. Use of the composite photocatalyst based on carbon nitride as claimed in claim 9 in the photocatalytic decomposition of water to produce hydrogen.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106732719A (en) * 2016-12-05 2017-05-31 厦门大学 A kind of preparation method of carbonitride/stannic disulfide quantum dot composite photo-catalyst
WO2019229255A1 (en) * 2018-05-31 2019-12-05 Cambridge Enterprise Limited Photocatalyst and photocatalytic methods for producing hydrogen
CN111790432A (en) * 2020-08-10 2020-10-20 泰州市海创新能源研究院有限公司 Nickel carbide/carbon nitride nanosheet photocatalytic material and preparation method and application thereof
CN112142021A (en) * 2020-09-11 2020-12-29 江苏理工学院 Preparation method and application of carbon-nitrogen polymer two-dimensional material
CN112495421A (en) * 2020-12-09 2021-03-16 北华大学 Preparation method of nitrogen-doped carbon quantum dot modified nitrogen-rich graphite type carbon nitride photocatalyst
CN113851696A (en) * 2021-09-14 2021-12-28 中山大学 C4N quantum dot material, preparation method thereof and lithium-sulfur battery diaphragm
CN115090313A (en) * 2022-05-26 2022-09-23 南京林业大学 0D/3D biochar quantum dot/g-C 3 N 4 Preparation method and application of heterojunction photocatalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106732719A (en) * 2016-12-05 2017-05-31 厦门大学 A kind of preparation method of carbonitride/stannic disulfide quantum dot composite photo-catalyst
WO2019229255A1 (en) * 2018-05-31 2019-12-05 Cambridge Enterprise Limited Photocatalyst and photocatalytic methods for producing hydrogen
CN111790432A (en) * 2020-08-10 2020-10-20 泰州市海创新能源研究院有限公司 Nickel carbide/carbon nitride nanosheet photocatalytic material and preparation method and application thereof
CN112142021A (en) * 2020-09-11 2020-12-29 江苏理工学院 Preparation method and application of carbon-nitrogen polymer two-dimensional material
CN112495421A (en) * 2020-12-09 2021-03-16 北华大学 Preparation method of nitrogen-doped carbon quantum dot modified nitrogen-rich graphite type carbon nitride photocatalyst
CN113851696A (en) * 2021-09-14 2021-12-28 中山大学 C4N quantum dot material, preparation method thereof and lithium-sulfur battery diaphragm
CN115090313A (en) * 2022-05-26 2022-09-23 南京林业大学 0D/3D biochar quantum dot/g-C 3 N 4 Preparation method and application of heterojunction photocatalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENHAO SHU等: ""Cutting COF-like C4N to Give Colloidal Quantum Dots: Towards Optical Encryption and Bidirectional Sulfur Chemistry via Functional Group and Edge Effects"", 《ANGEW. CHEM.》 *
SHU-WEN SUN等: ""High-Performance Ru@C4N Electrocatalyst for Hydrogen Evolution Reaction in Both Acidic and Alkaline Solutions"", 《ACS APPL. MATER. INTERFACES》 *

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