CN110813345A - Method for preparing novel carbon-nitrogen nonmetal photocatalyst by utilizing p/n junction principle - Google Patents
Method for preparing novel carbon-nitrogen nonmetal photocatalyst by utilizing p/n junction principle Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 74
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 34
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 17
- -1 halogen ammonium salt Chemical class 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
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- 239000007769 metal material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 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
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of nano energy materials, and particularly relates to a method for preparing a novel carbon-nitrogen nonmetal photocatalyst by utilizing a p/n junction principle. The invention comprises the following steps: (1) heating an amine raw material and a solvent to obtain a first product; (2) heating and heating the first product under the protection of inert gas to obtain a p-type CN photocatalyst; (3) mixing an amine raw material with halogen ammonium salt and a solvent, and heating to obtain a second product; (4) heating and heating the second product in an inert gas protective atmosphere to obtain an n-type CN photocatalyst; (5) and grinding and mixing the p-type CN photocatalyst, placing the mixture into a porcelain boat, placing the porcelain boat into a tube furnace, and heating and quenching the porcelain boat under the protection of inert gas to obtain the photocatalyst. The invention utilizes the p/n junction principle to prepare the novel carbon-nitrogen non-metal photocatalyst, has the characteristics of environment-friendly raw materials, no toxicity to the environment, low required conditions and high yield, and does not need expensive instruments and equipment.
Description
Technical Field
The invention belongs to the technical field of preparation of nano energy materials, and particularly relates to a method for preparing a novel carbon-nitrogen nonmetal photocatalyst by utilizing a p/n junction principle.
Background
Two-dimensional (2D) graphene-based carbon-nitrogen photocatalysts (g to CxNy) have recently received extensive research attention due to their good visible light responsiveness, and have advantages of large specific surface area, no toxicity, low price, and the like. However, in the non-metal and fully hydrolyzed fields, the effect of the CN photocatalyst has hardly any major breakthrough in the past decades.
The present inventors searched a large number of patent documents and journal documents before studying the present invention. The search results indicated that all CN photocatalysts were n-type structures due to their different carbon to nitrogen ratios (d.j.martin, k.qiu, s.a.shevlin, a.d.handoko, x.chen, z.guoandj.tang, angelw.chem.int.ed.2014, 53,9240; b) x.h.li, j.s.zhang, x.f.chen, a.fischer, a.thomas, m.antonetti, and x.c.wang, chem.mater.2011,23,4344; c) liu, t.wang, h.b.zhang, x.g.meng, d.hao, k.chang, p.li, t.kakoandj.h.ye, angelw.chem.int.ed.2015, 54,13561.).
In general, most researchers use p-type metal-based materials and n-type CN to compound and obtain photocatalysts, and this idea comes from the pn junction principle of silicon-based solar cells. This structure can greatly improve the efficiency of the photocatalyst. For example, ZnO/g to C3N4Composite materials with pure g-C3N4In contrast, the photocatalyst has good photocatalytic activity (j.x.sun, y.p.yuan, l.g.qiu, x.jiang, a.j.xie, y.h.shen, j.f.zhu, dalton trans.2012,41,6756). However, the above-mentioned composite photocatalysts are not nonmetal photocatalysts, and many metal-based materials are expensive and toxic.
Therefore, aiming at the defects, a p-type nonmetal CN photocatalyst needs to be designed and then compounded with a common n-type nonmetal CN photocatalyst, so that a novel nonmetal p-CN/n-CN photocatalyst structure with a pn junction is invented.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a novel carbon-nitrogen nonmetal photocatalyst by utilizing a p/n junction principle, which has no toxicity to the environment, low required conditions, high yield and no need of expensive instruments and equipment;
the method for preparing the novel carbon-nitrogen non-metal photocatalyst by utilizing the p/n junction principle solves the technical problems by the following technical scheme:
a method for preparing a novel carbon-nitrogen nonmetal photocatalyst by utilizing a p/n junction principle comprises the following steps:
(1) putting an amine raw material and a solvent into a container, and heating to obtain a first product;
(2) placing the first product in a porcelain boat and then in a tube furnace, heating the porcelain boat under the protection of inert gas to obtain a p-type CN photocatalyst;
(3) putting the amine raw material mixed with halogen ammonium salt and a solvent into a container, and heating to obtain a second product;
(4) placing the second product in a porcelain boat and then in a tube furnace, and heating the porcelain boat under the protection of inert gas to obtain an n-type CN photocatalyst;
(5) and grinding and mixing the p-type CN photocatalyst, placing the mixture into a porcelain boat, placing the porcelain boat into a tube furnace, protecting the atmosphere by inert gas, heating and quenching to obtain the non-metal p-CN/n-CN photocatalyst with the pn junction.
Preferably, the method comprises:
(1) placing an amine raw material and a solvent in a container, and heating for 6-24 hours at 100-180 ℃ to obtain a first product; the weight volume ratio of the amine raw material to the solvent is (1-10) g: (15-25) ml;
(2) placing the first product obtained in the step (1) in a porcelain boat, then putting the porcelain boat into a tube furnace, heating the porcelain boat to 500-650 ℃ at a heating rate of 1-6 ℃/min under the protection of inert gas, and heating the porcelain boat for 1-4 hours to obtain a p-type CN photocatalyst;
(3) putting the amine raw material mixed with halogen ammonium salt and a solvent into a container, and heating for 1-6 h at 100-180 ℃ to obtain a second product;
the weight volume ratio of the amine raw material to the solvent is as follows: (1-10) g: (15-25) ml;
(1) in the step (3), the solvent is at least one of deionized water or an organic solvent;
(4) placing the second product in a porcelain boat and then in a tube furnace, heating to 500-650 ℃ at a heating rate of 1-6 ℃/min under the protection of inert gas, and heating for 1-4 h to obtain an n-type CN photocatalyst;
(5) grinding and mixing the p-type CN photocatalyst obtained in the step (2) and the n-type CN photocatalyst obtained in the step (4) according to the mass ratio of 1:1, placing the mixture into a porcelain boat, placing the porcelain boat into a tubular furnace, raising the temperature to 500-650 ℃ at the temperature rise rate of 1-6 ℃/min under the protection of inert gas, and quenching for 0.5-1 h to obtain the non-metal p-CN/n-CN photocatalyst with the pn junction.
(1) And (3) the amine raw material is at least one of melamine, urea and polyethylene diamine.
(1) And (3), the solvent is at least one of deionized water, ethanol and tetrahydrofuran.
(3) In the method, the halogen ammonium salt is at least one of ammonium fluoride, ammonium chloride and ammonium iodide as a solvent.
The inert gas is at least one of argon and nitrogen.
The product is added into a photocatalytic performance tester to test the photocatalytic performance, and the performance is as follows: the yield of hydrogen production is 17028.82 mu molh-1g-1The total water splitting result was achieved without adding any sacrificial agent and noble metal in the water, and the average hydrogen production and average oxygen production were 270.9. mu. molh, respectively-1g-1And 115.21. mu. molh-1g-1。
Compared with the prior proposal mentioned in the background technology, the experimental result in the invention shows that the nonmetal p-CN/n-CN photocatalyst of the novel nonmetal pn junction provided by the invention has good photocatalysis effect, and the novel nonmetal p-CN/n-CN photocatalyst has good photocatalysis effectThe yield of hydrogen production is 17028.82 mu molh-1g-1The catalytic performance of the photocatalyst is much better than that of other pure CN photocatalysts under the same experimental conditions. More importantly, the results of full water splitting were achieved without adding any sacrificial agent and noble metal to the water, with an average hydrogen production and an average oxygen production of 270.9. mu. molh, respectively-1g-1And 115.21. mu. molh-1g-1. Therefore, the novel CN photocatalyst with the p-n structure has wide application prospect.
The method has the advantages that the novel carbon-nitrogen nonmetal photocatalyst is prepared by utilizing the p/n junction principle, the equipment is simple, the raw materials are environment-friendly, the method has the characteristics of no toxicity to the environment, low required conditions and high yield, and expensive equipment is not needed.
Drawings
FIG. 1 is a scanning electron micrograph of a two-dimensional carbon nitrogen photocatalytic material prepared by the invention. Wherein a is a p-type semiconductor photocatalyst, b is an n-type, c is a p-n junction heterostructure CN photocatalyst, and d is a common carbon nitrogen photocatalyst;
FIG. 2 shows the photocatalytic performance of the two-dimensional carbon nitrogen photocatalytic material prepared by the present invention in water. Wherein a is the comparison of hydrogen production amount of CN photocatalysts with different structures, b is the comparison of hydrogen production efficiency of CN photocatalysts with different structures, c is the yield of hydrogen and oxygen prepared by hydrolyzing water by a p-n junction heterostructure CN photocatalyst under a 300w xenon lamp, and d is the efficiency of preparing hydrogen and oxygen by hydrolyzing water by a p-n junction heterostructure CN photocatalyst;
FIG. 3 is a diagram of the mechanism of hydrogen and oxygen generation for a p-n junction heterostructure CN photocatalyst prepared in accordance with the present invention;
FIG. 4 is a flow diagram of a process for preparing the catalyst of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments so that those skilled in the art may better understand the invention, but the invention is not limited thereto.
Example 1
The method for preparing the novel carbon-nitrogen nonmetal photocatalyst by utilizing the p/n junction principle comprises the following steps of:
(1) weighing 5g of melamine material and 15ml of deionized water, putting the melamine material and the 15ml of deionized water into a container, and heating the mixture at 180 ℃ for 24 hours to obtain a first product;
(2) putting the first product into a porcelain boat, then putting the porcelain boat into a tubular furnace, heating the porcelain boat to 550 ℃ at the heating rate of 3 ℃/min under the protection of argon gas, and heating the porcelain boat for 1h to obtain a p-type CN photocatalyst;
(3) putting 1g of melamine mixed ammonium fluoride and 15ml of deionized water into a container, and heating for 1h at 100 ℃ to obtain a second product;
(4) putting the second product into a porcelain boat and then into a tube furnace, heating to 500 ℃ at the heating rate of 1 ℃/min under the protection of argon gas, and preserving heat for 1h to obtain an n-type CN photocatalyst;
(5) grinding and mixing the p-type CN photocatalyst and the n-type CN photocatalyst according to the mass ratio of 1:1, putting the mixture into a porcelain boat, putting the porcelain boat into a tubular furnace, heating to 5000 ℃ at the heating rate of 1 ℃/min under the protection of argon gas, and quenching for 0.5h to obtain the nonmetal p-CN/n-CN photocatalyst with the pn junction;
(6) and adding the product into a photocatalytic performance tester to test the photocatalytic performance.
Scanning electron microscope photographs of the prepared carbon-nitrogen photocatalytic materials with different structures, photocatalytic performance in water and catalytic water splitting mechanism are respectively shown in figure 1, figure 2 and figure 3;
example 2
The present embodiment is different from embodiment 1 in that: the procedure of example 1 was repeated except that urea was added as an amine-based raw material in steps (1) and (3).
Example 3
The present embodiment is different from embodiment 1 in that: the amount of melamine material added in steps (1) and (3) was 8 kg.
Example 4
The present embodiment is different from embodiment 1 in that: and (3) changing the solvent of the deionized water added in the step (1) into tetrahydrofuran.
Example 5
This example differs from examples 1-4 in that: the volume of deionized water added in steps (1) and (3) was 22 ml.
Example 6
The present embodiment is different from embodiment 1 in that: the heating temperature in steps (1) and (3) was 140 ℃.
Example 7
The present embodiment is different from embodiment 1 in that: the heating time in the step (1) is 20 h.
Example 8
The present embodiment is different from embodiment 1 in that: the heating time in the step (3) is 2 h.
Example 9
The present embodiment is different from embodiment 1 in that: the protective gas in steps (2), (4) and (5) is nitrogen.
Example 10
The present embodiment is different from embodiment 1 in that: the temperature rise rate in steps (2), (4) and (5) was 4 ℃/min.
Example 11
The present embodiment is different from embodiment 1 in that: the temperature is raised to a temperature of about 600 ℃ in steps (2), (4) and (5).
Example 12
The present embodiment is different from embodiment 1 in that: the heat preservation time in the step (4) is 3 hours.
Example 13
The present embodiment is different from embodiment 1 in that: the heat preservation time in the step (5) is 0.8 h.
Example 14
Testing hydrogen production and oxygen production of water photolysis by the carbon-nitrogen nonmetal photocatalyst in the embodiment 1-13 through gas chromatography; the specific method comprises the following steps:
50mg of the prepared non-metal photocatalyst is put into a photocatalytic hydrogen production instrument, a 300w xenon lamp is used as simulated sunlight, and the hydrogen production and oxygen production by water photolysis are tested through gas chromatography. Experimental results show that the novel nonmetal p-CN/n-CN photocatalyst of nonmetal pn junction has good photocatalytic effect, and the hydrogen production yield is 17028.82 mu molh-1g-1Ratio of the same experiment conditionsCatalytic performance of other pure CN photocatalyst 441.2 mu molh-1g-1Much better. More importantly, the results of full water splitting were achieved without adding any sacrificial agent and noble metal to the water, with an average hydrogen production and an average oxygen production of 270.9. mu. molh, respectively-1g-1And 115.21. mu. molh-1g-1. Therefore, the novel CN photocatalyst with the p-n structure has wide application prospect.
TABLE 1 Hydrogen and oxygen production by photocatalyst in examples 1 to 13
| Hydrogen production (. mu. molh)-1g-1) | Oxygen production (μmolh)-1g-1) | |
| Example 1 | 271.6 | 115.21 |
| Example 2 | 270.5 | 114.36 |
| Example 3 | 269.9 | 115.54 |
| Example 4 | 271.4 | 114.68 |
| Example 5 | 269.3 | 114.95 |
| Example 6 | 271.5 | 115.62 |
| Example 7 | 271.6 | 114.54 |
| Example 8 | 269.6 | 115.63 |
| Example 9 | 271.8 | 115.47 |
| Example 10 | 271.4 | 115.84 |
| Example 11 | 271.4 | 115.48 |
As can be seen from the data in the above table, in the present invention, the hydrogen production of the catalysts of examples 1 to 13 was 270.9. mu. molh on average-1g-1About 115.21 mu molh of oxygen production-1g-1Left and right; it has good repeatability.
Claims (7)
1. A method for preparing a novel carbon-nitrogen nonmetal photocatalyst by utilizing a p/n junction principle comprises the following steps:
(1) putting an amine raw material and a solvent into a container, and heating to obtain a first product;
(2) placing the first product in a porcelain boat and then in a tube furnace, heating the porcelain boat under the protection of inert gas to obtain a p-type CN photocatalyst;
(3) putting the amine raw material mixed with halogen ammonium salt and a solvent into a container, and heating to obtain a second product;
(4) placing the second product in a porcelain boat and then in a tube furnace, and heating the porcelain boat under the protection of inert gas to obtain an n-type CN photocatalyst;
(5) and grinding and mixing the p-type CN photocatalyst, placing the mixture into a porcelain boat, placing the porcelain boat into a tube furnace, protecting the atmosphere by inert gas, heating and quenching to obtain the non-metal p-CN/n-CN photocatalyst with the pn junction.
2. The method for preparing the novel carbon nitrogen non-metal photocatalyst by using the p/n junction principle as claimed in claim 1, comprising the following steps:
(1) placing an amine raw material and a solvent in a container, and heating for 6-24 hours at 100-180 ℃ to obtain a first product; the weight volume ratio of the amine raw material to the solvent is (1-10) g: (15-25) ml;
(2) placing the first product obtained in the step (1) in a porcelain boat, then putting the porcelain boat into a tube furnace, heating the porcelain boat to 500-650 ℃ at a heating rate of 1-6 ℃/min under the protection of inert gas, and heating the porcelain boat for 1-4 hours to obtain a p-type CN photocatalyst;
(3) putting the amine raw material mixed with halogen ammonium salt and a solvent into a container, and heating for 1-6 h at 100-180 ℃ to obtain a second product;
the weight volume ratio of the amine raw material to the solvent is as follows: (1-10) g: (15-25) ml;
(1) in the step (3), the solvent is at least one of deionized water or an organic solvent;
(4) placing the second product in a porcelain boat and then in a tube furnace, heating to 500-650 ℃ at a heating rate of 1-6 ℃/min under the protection of inert gas, and heating for 1-4 h to obtain an n-type CN photocatalyst;
(5) grinding and mixing the p-type CN photocatalyst obtained in the step (2) and the n-type CN photocatalyst obtained in the step (4) according to the mass ratio of 1:1, placing the mixture into a porcelain boat, placing the porcelain boat into a tubular furnace, raising the temperature to 500-650 ℃ at the temperature rise rate of 1-6 ℃/min under the protection of inert gas, and quenching for 0.5-1 h to obtain the non-metal p-CN/n-CN photocatalyst with the pn junction.
3. The method for preparing a novel carbon-nitrogen non-metal photocatalyst by using the p/n junction principle as claimed in claim 1, wherein (1) and (3) said amine raw material is at least one of melamine, urea and polyethylene diamine.
4. The method for preparing a novel carbon-nitrogen non-metal photocatalyst by using the p/n junction principle as claimed in claim 1, wherein in (1) and (3), the solvent is at least one of deionized water, ethanol and tetrahydrofuran.
5. The method for preparing a novel carbon nitrogen non-metal photocatalyst by using the p/n junction principle as claimed in claim 1, wherein in (3), the halogen ammonium salt is at least one of ammonium fluoride, ammonium chloride and ammonium iodide.
6. The method for preparing the novel carbon nitrogen non-metal photocatalyst by using the p/n junction principle as claimed in claim 1, wherein the inert gas is at least one of argon and nitrogen.
7. The method for preparing a novel carbon-nitrogen non-metal photocatalyst by using the p/n junction principle as claimed in claim 1, wherein the obtained product is added into a photocatalytic performance tester to test the photocatalytic performance, and the performance is as follows: the yield of hydrogen production is 17028.82 mu molh-1g-1The total water splitting result was achieved without adding any sacrificial agent and noble metal in the water, and the average hydrogen production and average oxygen production were 270.9. mu. molh, respectively-1g-1And 115.21. mu. molh-1g-1。
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