CN113083341A - Hollow polymerization type carbon nitride catalyst and application thereof in photocatalytic reduction of CO2Use of synthetic acetaldehyde - Google Patents
Hollow polymerization type carbon nitride catalyst and application thereof in photocatalytic reduction of CO2Use of synthetic acetaldehyde Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 53
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 15
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- 238000006116 polymerization reaction Methods 0.000 title claims description 5
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims abstract description 35
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 33
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- 238000000034 method Methods 0.000 claims description 20
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- 239000000243 solution Substances 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 230000007246 mechanism Effects 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002101 nanobubble Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C07C45/44—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reduction and hydrolysis of nitriles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a hollow polymeric carbon nitride catalyst and application thereof in photocatalytic reduction of CO2Application of synthesizing acetaldehyde. A preparation method of a hollow polymeric carbon nitride catalyst comprises the following steps: adding dicyandiamide and N, N-diethylacetamide into water, mixing, heating and stirring uniformly to obtain a mixed aqueous solution of dicyandiamide and N, N-diethylacetamide, transferring the mixed aqueous solution of dicyandiamide and N, N-diethylacetamide into a hydrothermal reaction container to carry out hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, washing and drying the obtained product to obtain a supramolecular intermediate, and calcining the supramolecular intermediate at high temperature to obtain the hollow polymeric carbon nitride catalyst. The invention adopts N, N-diethyl acetamide as a reducing agent to modify dicyandiamide and utilizesThe N, N-diethyl acetamide regulates the self-assembly forming mechanism of dicyandiamide to obtain the polymeric carbon nitride catalyst with a hollow bubble shape, high crystallinity and an amorphous binary structure.
Description
The technical field is as follows:
the invention relates to the technical field of photocatalysis, in particular to a hollow polymeric carbon nitride catalyst and application thereof in photocatalytic reduction of CO2Application of synthesizing acetaldehyde.
Background art:
acetaldehyde is an important chemical raw material, and can be used for manufacturing acetic acid, acetic anhydride, synthetic resin, rubber, plastics and spices, and also can be used for preparing leather, pharmacy, papermaking and medicines, and can be used as a preservative, a poison preventer, a developer, a solvent, a reducing agent and the like.
The main synthesis methods of acetaldehyde include an ethylene direct oxidation method, an ethanol oxidation method, an acetylene direct hydration method, an ethanol deoxidation method and the like. The direct acetylene hydration method adopts mercury salt as a catalyst, so that the problem of mercury pollution exists, the raw material consumption of the ethanol oxidation method is high, the unit consumption of the raw material of the direct ethylene oxidation method is low, the synthesis process route is simple, and the method is the main method for industrially producing acetaldehyde at present, but the method mainly adopts hydrochloric acid solutions of palladium chloride and copper chloride as catalysts, so that the method has serious corrosion to equipment, and special materials such as noble metal titanium and the like are required to be used.
The invention content is as follows:
in order to solve the problems in the prior art, the invention provides a hollow polymeric carbon nitride catalyst and application thereof in photocatalytic reduction of CO2The invention discloses application of synthesized acetaldehyde, which is characterized in that N, N-diethyl acetamide is innovatively adopted as a reducing agent to modify dicyandiamide, and a self-assembly forming mechanism of dicyandiamide is regulated and controlled by the N, N-diethyl acetamide, so that a hollow bubble-shaped high-crystallinity/amorphous binary-structure polymeric carbon nitride catalyst is obtained.
One object of the present invention is to provide a method for preparing a hollow polymeric carbon nitride catalyst, comprising the steps of: adding dicyandiamide and N, N-diethylacetamide into water, mixing, heating and stirring uniformly to obtain a mixed aqueous solution of dicyandiamide and N, N-diethylacetamide, transferring the mixed aqueous solution of dicyandiamide and N, N-diethylacetamide into a hydrothermal reaction container to carry out hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, washing and drying the obtained product to obtain a supramolecular intermediate, and calcining the supramolecular intermediate at high temperature to obtain the hollow polymeric carbon nitride catalyst.
Preferably, the mass concentration of the dicyandiamide is 1-1000 g/L, the volume fraction of the N, N-diethyl acetamide is 0.05-10%, and the stirring time for uniformly stirring the dicyandiamide and the N, N-diethyl acetamide aqueous solution is 0.1-1 h.
Preferably, the temperature of the hydrothermal reaction is 100-200 ℃, and the reaction time is 5-15 h.
Preferably, the steps of washing and drying the obtained product to obtain the supramolecular intermediate are as follows: and washing the obtained product with ethanol and distilled water for three times respectively, and then placing the product in an oven for drying to obtain the supramolecular intermediate, wherein the drying temperature in the oven is 50-100 ℃, and the drying time is 6-10 h.
Preferably, the high-temperature calcination temperature is 400-600 ℃, and the calcination time is 2-10 h.
The invention also aims to provide the hollow polymeric carbon nitride catalyst prepared by the preparation method, wherein the wavelength of the response of the hollow polymeric carbon nitride catalyst to light is 450-600 nm. The hollow polymeric carbon nitride catalyst has a hollow nano bubble shape, a bubble edge structure high-crystallization/bubble inner amorphous binary crystal structure, and a wide-spectrum (450-600nm) optical activity response.
The invention also protects the hollow polymeric carbon nitride catalyst in the photocatalytic reduction of CO2Application of synthesizing acetaldehyde.
The invention uses the hollow polymerization type carbon nitride catalyst for photocatalytic reduction of CO2Synthesizing acetaldehyde. The catalyst has high acetaldehyde selectivity and stable catalytic activity, and can realize the photocatalytic high-efficiency synthesis of acetaldehyde at normal temperature and normal pressure.
Preferably, the method comprises the following steps: mixing hollow polymerization type carbon nitride catalyst with acetonitrile aqueous solution, and introducing CO under the irradiation of white light as a light source2The gas is subjected to a photocatalytic reaction to convert CO2Reducing to generate acetaldehyde, wherein the photocatalytic reaction time is 0.5-12 h.
More preferably, the mass fraction of acetonitrile in the acetonitrile aqueous solution is 5-99%, and the mass ratio of the hollow polymeric carbon nitride catalyst to acetonitrile is 0.01-0.2: 1, CO2The amount of the catalyst is 0.1 to 10 mL/min.
Preferably, the light source is 5W LED white light, and the irradiation intensity of the white light source is 1-1000 mW/cm2。
Compared with the prior art, the invention has the following advantages: the invention adopts N, N-diethyl acetamide as a reducing agent to modify dicyandiamide for the first time, and uses N, N-diethyl acetamide to regulate and control the formation mechanism of dicyandiamide during self-assembly, so that the prepared polymeric carbon nitride catalyst has a hollow bubble-shaped high-crystallinity/amorphous binary structure. Meanwhile, the invention realizes the photocatalytic reduction of CO at normal temperature and normal pressure for the first time2The synthesis reaction has stable catalytic activity and high selectivity of the product acetaldehyde.
Description of the drawings:
FIG. 1 is a Transmission Electron Micrograph (TEM) of a hollow polymeric carbon nitride catalyst prepared in example 1;
FIG. 2 is a Fourier Infrared Spectroscopy (FTIR) plot of hollow polymeric carbon nitride catalysts prepared in example 1, comparative example 1 and comparative example 2;
FIG. 3 is a graph showing UV diffuse reflection absorption spectra of hollow polymeric carbon nitride catalysts prepared in example 1, comparative example 1 and comparative example 2;
FIG. 4 is a mass spectrum of a product obtained by subjecting a hollow polymeric carbon nitride catalyst prepared in example 1 to a photocatalytic reaction;
FIG. 5 is a graph showing the photocatalytic reaction of different polymeric carbon nitride catalysts obtained in examples 1 to 4, comparative example 1 and comparative example 2;
FIG. 6 is a diagram showing a cycle of a photocatalytic reaction in the case of preparing a hollow polymeric carbon nitride catalyst according to example 1.
The specific implementation mode is as follows:
the technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art. The testing instrument of the mass spectrum is GC-MS Agilent 7890B-7250.
A preparation method of a hollow polymeric carbon nitride catalyst comprises the following steps: adding a certain amount of dicyandiamide and N, N-diethylacetamide into water, mixing, heating and stirring uniformly to obtain a dicyandiamide and N, N-diethylacetamide mixed aqueous solution, transferring the dicyandiamide and N, N-diethylacetamide mixed aqueous solution into a hydrothermal reaction container, placing the hydrothermal reaction container in an oven for hydrothermal reaction, naturally cooling to room temperature, washing the obtained product with ethanol and distilled water for three times respectively, placing the washed product in the oven for drying to obtain a supramolecular intermediate, transferring the supramolecular intermediate into a ceramic crucible, placing the ceramic crucible in a muffle furnace for high-temperature calcination, and obtaining the hollow polymeric carbon nitride catalyst.
In the invention, N, N-diethyl acetamide is a reducing agent modified dicyandiamide. The source of N, N-diethylacetamide and dicyandiamide in the present invention is not particularly limited, and commercially available products or self-products known to those skilled in the art may be used. The mass concentration of dicyandiamide is 1-1000 g/L, the volume fraction of N, N-diethyl acetamide is 0.05-10%, and the stirring time for uniformly stirring dicyandiamide and the N, N-diethyl acetamide aqueous solution is 0.1-1 h.
In the invention, the temperature of the hydrothermal reaction is 100-200 ℃, and the reaction time is 5-15 h. The drying temperature in the oven is 50-100 ℃, and the drying time is 6-10 h. The high-temperature calcination temperature is 400-600 ℃, and the calcination time is 2-10 h.
Photocatalytic reduction of CO by hollow polymeric carbon nitride catalyst2The process for synthesizing acetaldehyde with high selectivity comprises the following steps: mixing hollow polymeric carbon nitride catalyst with acetonitrile water solution, and obtaining white light sourceIntroducing CO under irradiation of light2Gas of CO2Reduction produces acetaldehyde.
In the invention, the mass fraction of acetonitrile in the acetonitrile water solution is 5-99%, and the mass ratio of the hollow polymeric carbon nitride catalyst to the acetonitrile is 0.01-0.2: 1, the photocatalytic reaction time is 0.5-12 h, and CO2The amount of the catalyst is 0.1 to 10 mL/min. The light source is 5W LED white light, and the irradiation intensity of the white light source is 1-1000 mW/cm2。
Example 1
A preparation method of a hollow polymeric carbon nitride catalyst comprises the following steps:
adding dicyandiamide and N, N-diethylacetamide into water to prepare a mixed aqueous solution, wherein the mass concentration of dicyandiamide in the mixed aqueous solution is 1g/L, the volume fraction of N, N-diethylacetamide is 0.05%, transferring the mixed aqueous solution into a hydrothermal reaction kettle after heating and stirring for 0.1h, placing the hydrothermal reaction kettle in an oven, heating to 100 ℃, reacting for 5h, regulating and controlling the self-assembly formation mechanism of dicyandiamide by using N, N-diethylacetamide as an organic reducing agent in the hydrothermal reaction process, washing the obtained product with ethanol and distilled water for three times respectively after naturally cooling to room temperature, placing the product in the oven, drying at 50 ℃ for 6h to obtain a supramolecular intermediate, transferring the supramolecular intermediate into a crucible porcelain, placing the crucible porcelain in a 400 ℃ muffle furnace, and calcining at high temperature for 2h to obtain a polymeric carbon nitride catalyst PCN-N1。
Fig. 1 is a transmission electron microscope image of the polymeric carbon nitride catalyst obtained in this example, and it can be seen from fig. 1 that the catalyst has a hollow nano bubble-like morphology, thick edges, thin middle, highly ordered lattice stripes at the edges, and an amorphous crystal structure inside.
Example 2
Reference example 1 was repeated except that the volume fraction of N, N-diethylacetamide in the mixed aqueous solution was 0.1%, the mixture was heated to 180 ℃ in an oven, reacted for 10 hours, and the supramolecular intermediate was transferred to a ceramic crucible and calcined in a muffle furnace at 550 ℃ to obtain a polymeric carbon nitride catalyst PCN-N2。
Example 3
Reference example 1 was repeated except that the volume fraction of N, N-diethylacetamide in the mixed aqueous solution was 0.2%, to obtain a polymeric carbon nitride catalyst PCN-N3。
Example 4
Reference example 1 was conducted except that the volume fraction of N, N-diethylacetamide in the mixed aqueous solution was 0.4%, to obtain a polymeric carbon nitride catalyst PCN-N4。
Example 5
Reference example 1 was repeated, except that the mass concentration of dicyandiamide in the mixed aqueous solution was 1000g/L, the volume fraction of N, N-diethylacetamide was 10%, and the stirring time was 1 hour.
Example 6
Reference example 1 was repeated, except that the hydrothermal reaction was carried out at 200 ℃ for 15 hours.
Example 7
Reference example 1 was repeated, except that the drying temperature was 100 ℃ and the drying time was 10 hours.
Example 8
Reference example 1 was repeated, except that the high-temperature calcination temperature was 600 ℃ and the calcination time was 10 hours.
Comparative example 1
And (3) placing 1g of dicyandiamide in a muffle furnace at 550 ℃ for high-temperature calcination for 2h to obtain the polymeric carbon nitride catalyst PCN.
Comparative example 2
Preparing 1g/L dicyandiamide aqueous solution, heating and stirring for 0.1H, transferring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, heating to 100 ℃, reacting for 5H, naturally cooling to room temperature, washing the obtained product with ethanol and distilled water for three times respectively, placing the product in the oven, drying the product at 50 ℃ for 6H, transferring the dried product into a ceramic crucible, placing the ceramic crucible in a muffle furnace at 550 ℃ for high-temperature calcination for 2H, and obtaining the polymeric carbon nitride catalyst PCN-H.
FIG. 2 is a Fourier Infrared Spectroscopy (FTIR) plot of the polymeric carbon nitride catalysts prepared in example 1, comparative example 1 and comparative example 2, and it can be seen in FIG. 2 that three catalysts are comparedAgent PCN-N1PCN and PCN-H, the Fourier Infrared Spectroscopy (FTIR) plots of the three catalysts remained essentially consistent, containing surface-NH2Containing a C-N conjugated heterocyclic ring and a triazine ring; can be seen at 805cm-1After hydrothermal treatment, the triazine ring is low in cost towards high wave number, and the structure of the triazine ring is slightly changed.
FIG. 3 shows the UV-diffuse reflection absorption spectra of the polymeric carbon nitride catalysts prepared in example 1, comparative example 1 and comparative example 2. in FIG. 3, it can be seen that PCN-H has a distinct blue shift compared with PCN band edge, and the band is increased, but after the addition of N, N-diethylacetamide, the light absorption range is increased, and the absorption is distinct in the region around 450-600 nm.
Application example 1
20mg of the polymeric carbon nitride catalyst obtained in example 2 was mixed with 40g of an aqueous acetonitrile solution (5% by mass) and irradiated with 100mW/cm of radiation intensity under white light irradiation from a 5W LED2Under the condition of introducing CO2Carrying out a photocatalytic reaction for 1h, CO2The flow rate of (2) was 0.5 mL/min. The resulting product was examined by GC-MS Agilent 7890B-7250 and, as shown in FIG. 4, no gas phase product was produced, only liquid phase product.
Application example 2
20mg of each of the polymeric carbon nitride catalysts obtained in examples 1 to 4, comparative example 1 and comparative example 2 was mixed with 40g of a 5% aqueous acetonitrile solution, and the mixture was irradiated with 100mW/cm white light from a 5W LED2Under the condition of introducing CO2Carrying out a photocatalytic reaction for 1h, CO2The flow rate of (2) was 0.5 mL/min. And detecting the output rate of the catalytic reaction. As a result, as shown in FIG. 5, it can be seen from the reactivity that PCN-N was observed under light irradiation2Can convert CO into2Reduction to give 610umolg-1h-1About acetaldehyde, and has high selectivity of 94.1 percent of acetaldehyde.
Application example 3
60mg of the polymeric carbon nitride catalyst obtained in example 1 was mixed with 6g of a 5% aqueous acetonitrile solution and irradiated with 5W LED white lightThe illumination intensity is 100mW/cm2Under the condition of introducing CO2Carrying out a photocatalytic reaction for 1h, CO2The flow rate of (2) was 0.5 mL/min. The catalytic reaction rate was measured. After the catalyst whose catalytic reaction rate was detected was filtered out and dried, the above steps were repeated five times. As a result, as shown in FIG. 6, the catalytic activity was substantially unchanged after six cycles, and the stability of the catalytic activity was high.
Application example 4
The same as in application example 1, except that: the mass fraction of the acetonitrile aqueous solution is 99%, and the mass ratio of the hollow polymeric carbon nitride catalyst to the acetonitrile is 0.2: 1, the irradiation intensity is 1000mW/cm2，CO2The flow rate of (2) is 10 mL/min. The photocatalytic reaction time is 0.5 h.
Application example 5
The same as in application example 1, except that: the mass fraction of the acetonitrile aqueous solution is 5%, and the mass ratio of the hollow polymeric carbon nitride catalyst to the acetonitrile is 0.01: 1, the irradiation intensity is 1000mW/cm2，CO2The flow rate of (2) was 0.1 mL/min. The photocatalytic reaction time is 12 h.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a hollow polymeric carbon nitride catalyst is characterized by comprising the following steps: adding dicyandiamide and N, N-diethylacetamide into water, mixing, heating and stirring uniformly to obtain a mixed aqueous solution of dicyandiamide and N, N-diethylacetamide, transferring the mixed aqueous solution of dicyandiamide and N, N-diethylacetamide into a hydrothermal reaction container to carry out hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, washing and drying the obtained product to obtain a supramolecular intermediate, and calcining the supramolecular intermediate at high temperature to obtain the hollow polymeric carbon nitride catalyst.
2. The method for preparing a hollow polymeric carbon nitride catalyst according to claim 1, wherein the mass concentration of dicyandiamide in the mixed aqueous solution of dicyandiamide and N, N-diethylacetamide is 1 to 1000g/L, the volume fraction of N, N-diethylacetamide is 0.05 to 10%, and the stirring time for uniformly stirring the mixed aqueous solution of dicyandiamide and N, N-diethylacetamide is 0.1 to 1 hour.
3. The method for preparing a hollow polymeric carbon nitride catalyst according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 100 ℃ to 200 ℃ for 5 to 15 hours.
4. The preparation method of the hollow polymeric carbon nitride catalyst according to claim 1, wherein the step of washing and drying the obtained product to obtain the supramolecular intermediate comprises: and washing the obtained product with ethanol and distilled water for three times respectively, and then placing the product in an oven for drying to obtain the supramolecular intermediate, wherein the drying temperature in the oven is 50-100 ℃, and the drying time is 6-10 h.
5. The method for preparing a hollow polymeric carbon nitride catalyst according to claim 1, wherein the high-temperature calcination temperature is 400 ℃ to 600 ℃ and the calcination time is 2 to 10 hours.
6. The hollow polymeric carbon nitride catalyst prepared by the method of claim 1, wherein the wavelength of the response of the hollow polymeric carbon nitride catalyst to light is 450-600 nm.
7. The hollow polymeric carbon nitride catalyst of claim 6 for photocatalytic reduction of CO2Application of synthesizing acetaldehyde.
8. The hollow polymeric carbon nitride catalyst of claim 7 in photocatalytic reductionCO2The application of the synthesized acetaldehyde is characterized by comprising the following steps: mixing hollow polymerization type carbon nitride catalyst with acetonitrile aqueous solution, and introducing CO under the irradiation of white light as a light source2The gas is subjected to a photocatalytic reaction to convert CO2Reduction produces acetaldehyde.
9. The hollow polymeric carbon nitride catalyst of claim 8 for photocatalytic reduction of CO2The application of the synthesized acetaldehyde is characterized in that the mass fraction of acetonitrile in the acetonitrile water solution is 5-99%, and the mass ratio of the hollow polymeric carbon nitride catalyst to the acetonitrile is 0.01-0.2: 1, CO2The introduction amount of (A) is 0.1-10 mL/min, and the photocatalytic reaction time is 0.5-12 h.
10. The hollow polymeric carbon nitride catalyst of claim 7 for photocatalytic reduction of CO2The application of the synthesized acetaldehyde is characterized in that the light source is 5W LED white light, and the irradiation intensity of the white light source is 1-1000 mW/cm2。
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