CN115007182B - Preparation method of potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst - Google Patents
Preparation method of potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 50
- RQPCXPDUSNVHSU-UHFFFAOYSA-N [O].[K] Chemical compound [O].[K] RQPCXPDUSNVHSU-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 21
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- 239000001103 potassium chloride Substances 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 238000001035 drying Methods 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 17
- 239000010439 graphite Substances 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 7
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- 239000002131 composite material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SMQPUZSGLWKXAW-UHFFFAOYSA-N [K].OC=O Chemical compound [K].OC=O SMQPUZSGLWKXAW-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000012986 modification Methods 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a preparation method of a potassium-oxygen co-doped graphite phase carbon nitride photocatalyst, which comprises the following steps: (1) Respectively dissolving melamine and cyanuric acid to obtain a solution A, B, mixing the solution A, B to obtain white precipitate which is supermolecule powder, and mixing the supermolecule powder with potassium chloride powder to obtain a mixed powder A; (2) Placing the mixed powder A into a container A, placing the container A into a container B, adding a wave-absorbing medium into the container B, and carrying out microwave heating to obtain a potassium-doped graphite-phase carbon nitride material; (3) Mixing the potassium-doped graphite-phase carbon nitride material with oxalic acid to obtain mixed powder B, and then carrying out microwave heating according to the method of the step (2) to obtain the composite powder. The secondary microwave method greatly improves the specific surface area of the material, avoids the adverse effect of the doping of potassium chloride on the specific surface area of the carbon nitride, and remarkably improves the photocatalytic activity; short synthesis period, easy operation and can be used for producing hydrogen peroxide by photocatalysis.
Description
Technical Field
The invention relates to a preparation method of a photocatalytic material, in particular to a preparation method of potassium-oxygen co-doped graphite phase carbon nitride.
Background
Hydrogen peroxide, which is a high-efficiency oxidant, has the advantages of high active oxygen content (47.1 wt%) and no pollution (by-products are only water and oxygen), and is widely applied to various fields of pulp and papermaking, organic synthesis, wastewater treatment, metallurgical industry and the like. The traditional method for producing hydrogen peroxide is anthraquinone oxidation, which is dominant in industrial synthesis of hydrogen peroxide, and hydrogen peroxide produced by the process accounts for more than 95% of the total yield. However, this approach has a number of disadvantages: for example, multi-step hydrogenation and oxidation reactions result in higher energy consumption and in addition, large amounts of pollutants such as waste liquid, waste gas, solid waste and the like are produced. Therefore, the research on a low-energy-consumption pollution-free hydrogen peroxide preparation method is needed to reduce the environmental pollution in industrial production and realize economic sustainable development.
The technology for producing hydrogen peroxide by photocatalysis can convert two raw materials of oxygen and water into hydrogen peroxide by utilizing light energy in sunlight at room temperature, and has the characteristics of no pollution and zero carbon emission. Of various photocatalysts capable of producing hydrogen peroxide by photocatalysis, graphite-phase carbon nitride (g-C 3 N 4 ) As a conjugated polymer semiconductor, there is growing interest in having the advantages of good chemical stability, proper band gap, and no metal component. However, g-C is limited by defects in its own structure (only visible light with a wavelength less than 450nm and low conductivity and charge separation efficiency) 3 N 4 The catalyst is applied to the photocatalytic hydrogen peroxide production.
Numerous strategies including elemental doping regulate g-C 3 N 4 The energy band structure, the charge separation capability and the surface morphology of the catalyst can improve the activity of producing hydrogen peroxide by photocatalysis, and particularly potassium doping is considered to be an ideal modification strategy. However, most of the elements are doped with g-C 3 N 4 The preparation of the catalyst often needs high-temperature calcination for several hours, and the preparation methods are complicated and have high energy consumption. In addition, the molten salt method commonly adopted for potassium doping can promote carbon nitride crystallization, reduce the specific surface area of the material and have certain limitations.
Disclosure of Invention
The invention aims to: the invention aims to provide a simple, rapid and low-energy-consumption preparation method of a potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst.
The technical scheme is as follows: the preparation method of the potassium-oxygen co-doped graphite phase carbon nitride photocatalyst comprises the following steps:
(1) Respectively dissolving melamine and cyanuric acid to obtain a solution A, B, mixing the solution A, B to obtain a white precipitate, and washing and drying to obtain melamine-cyanuric acid supermolecule powder; mixing the supermolecule powder with potassium chloride powder to obtain mixed powder A;
(2) Placing the mixed powder A into a container A, placing the container A into a container B, adding a wave-absorbing medium into the container B, and carrying out microwave heating on the container B to obtain a potassium-doped graphite-phase carbon nitride material;
(3) Mixing the potassium-doped graphite-phase carbon nitride material with oxalic acid to obtain mixed powder B, and then carrying out microwave heating according to the method of the step (2) to obtain the potassium-oxygen co-doped graphite-phase carbon nitride material.
Wherein in the step (1), the mole ratio of melamine to cyanuric acid is 1:1 to 1:3.
wherein in the step (1), the mass ratio of potassium chloride in the mixed powder A is 25-75%.
Wherein the microwave heating power in the step (2) and the step (3) is 500-1200W.
Wherein the microwave time in the step (2) and the step (3) is 3-20 min.
Wherein, in the mixed powder B in the step (3), the oxalic acid accounts for 10 to 40 percent by mass.
In the step (2), the wave-absorbing medium is at least one of graphite powder, graphene, carbon fiber, activated carbon, ferric oxide or copper oxide.
The invention also provides application of the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst prepared by the preparation method of the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst in photocatalytic hydrogen peroxide production.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable effects: (1) The preparation method is simple in preparation process, the product can be synthesized by microwave heating for only two times of minutes, accurate regulation and control are easy, raw materials are simple and easy to obtain, the energy consumption in the preparation process is low, and the operation condition is relatively simple. (2) According to the secondary microwave method, the gas atmosphere formed by oxalic acid heating decomposition is utilized to promote the decomposition and recombination of the carbon nitride structure, the specific surface area of the material is obviously improved, the adverse effect of potassium chloride doping on the specific surface area of the carbon nitride is avoided, and meanwhile, the doping of oxygen elements is realized. (3) According to the invention, the potassium element and the oxygen element are co-doped into the graphite phase carbon nitride, so that the absorption rate of the material to visible light is improved, the recombination of photo-generated electrons and holes is inhibited, the activity of producing hydrogen peroxide by photocatalysis is improved, and the photocatalytic capability of the Yu Shanyuan element doped graphite phase carbon nitride is remarkably improved.
Drawings
FIG. 1 is a schematic diagram of the preparation flow of the potassium-oxygen co-doped graphite phase carbon nitride of example 1;
FIG. 2 is an XRD pattern of the product of example 1, comparative example 1;
FIG. 3 is a UV-vis DRS spectra of the products of example 1, comparative example 1 and comparative example 2;
FIG. 4 is an XPS spectrum of the potassium oxygen co-doped graphite phase carbon nitride of example 1;
FIG. 5 is a graph showing the performance of the products of example 1 and comparative examples 1-3 in producing hydrogen peroxide by photocatalysis.
Detailed Description
The present invention is described in further detail below.
Example 1
As shown in FIG. 1, the invention provides a preparation method of a potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst, which comprises the following steps:
(1) Preparation of a supramolecular precursor: 1g of melamine and 1.02g of cyanuric acid are respectively dissolved in 200mL and 100mL of dimethyl sulfoxide solution to obtain solution A and solution B, and the solution A and the solution B are mixed and sufficiently stirred for 10 minutes to obtain white precipitate. And washing the white precipitate with ethanol for three times, drying at 60 ℃ for 10 hours to obtain a white massive solid, and fully grinding the solid to obtain white powder, namely the melamine-cyanuric acid supermolecule precursor.
(2) First microwave heating: 1g of the supramolecular precursor is taken, uniformly mixed with 0.5g of potassium chloride powder and ground to obtain mixed powder. Transferring the obtained mixed powder into a small crucible, covering a small crucible cover, putting the small crucible cover into the large crucible, adding graphite powder into the large crucible until the small crucible is completely covered, and covering the large crucible cover for later use; the prepared large crucible is placed in a microwave oven, the cover of the microwave oven is closed, the power of the microwave oven is adjusted to 800W, and the crucible is heated in air for 5 minutes. And after the reaction is finished, taking out the product in the small crucible, fully grinding and washing to obtain the potassium doped graphite phase carbon nitride material.
(3) And (3) carrying out microwave heating for the second time: mixing the potassium-doped graphite phase carbon nitride with oxalic acid according to the mass ratio of 2:1, uniformly grinding to obtain mixed powder, and changing the heating time to 5 minutes by adopting the same method as the first microwave heating. And after the reaction is finished, taking out the product in the small crucible to obtain the potassium-oxygen co-doped graphite phase carbon nitride material, wherein the K/O-CN is marked.
Example 2
On the basis of example 1, the difference from example 1 is that:
(1) Preparation of a supramolecular precursor: 5g of melamine and 15.30g of cyanuric acid were dissolved in 400mL and 400mL of dimethyl sulfoxide solution, respectively, to give solution A and solution B.
(2) First microwave heating: taking 3g of the supermolecule precursor, uniformly mixing with 1g of potassium chloride powder, and grinding to obtain mixed powder. The power of the microwave oven was adjusted to 1200W and heated in air for 3 minutes.
(3) And (3) carrying out microwave heating for the second time: mixing the potassium-doped graphite phase carbon nitride with oxalic acid according to the mass ratio of 9:1. The heating power and heating time were changed to 500W for 20 minutes.
Example 3
On the basis of example 1, the difference from example 1 is that:
(1) Preparation of a supramolecular precursor: 10g of melamine and 15.30g of cyanuric acid were dissolved in 400mL and 400mL of dimethyl sulfoxide solution, respectively, to give solution A and solution B.
(2) First microwave heating: taking 1g of the supermolecule precursor, uniformly mixing with 3g of potassium chloride powder, and grinding to obtain mixed powder. The power of the microwave oven was adjusted to 500W and heated in air for 3 minutes.
(3) And (3) carrying out microwave heating for the second time: mixing the potassium-doped graphite phase carbon nitride with oxalic acid according to the mass ratio of 3:2. The heating power and heating time were changed to 1200W for 20 minutes.
Comparative example 1
On the basis of example 1, the difference from example 1 is that: step (2) is omitted. The obtained potassium-doped graphite phase carbon nitride material is named as K-CN.
Comparative example 2
On the basis of example 1, the difference from example 1 is that: in the step (2), 1g of the supramolecular precursor is taken, uniformly mixed with 0.5g of oxalic acid powder and ground to obtain mixed powder. Obtaining the oxygen doped graphite phase carbon nitride material O-CN. Step (3) is omitted.
Comparative example 3
On the basis of example 1, the difference from example 1 is that:
in the step (2): 1g of the supramolecular precursor is taken, uniformly mixed with 0.5g of oxalic acid powder and ground to obtain mixed powder. Obtaining the oxygen doped graphite phase carbon nitride material.
In the step (3): mixing oxygen-doped graphite phase carbon nitride with potassium chloride according to a mass ratio of 2:1. The oxygen-potassium co-doped graphite phase carbon nitride material is obtained and is marked as O/K-CN.
Synthesis of H 2 O 2 Experiment: three portions of 50mL of 10% volume fraction isopropyl alcohol solution were prepared and placed in a 100mL beaker. 50mg of the photocatalyst was taken and added to the above isopropanol solution. And then introducing oxygen into the suspension for 20min in a dark place, and stirring for 30min in a dark place to ensure that the photocatalyst reaches the balance of oxygen adsorption and desorption. Next, a 300W xenon lamp was used to simulate the sunlight irradiation solution while continuously introducing a certain amount of oxygen. 2mL of the suspension was taken out at specified intervals and filtered to give 1mL of supernatant for use.
H in solution 2 O 2 The concentration was measured by iodine titration: 1mL of unknown concentration H is taken 2 O 2 0.5mL of KI at a concentration of 1mol/L and 0.5mL of phthalic acid at a concentration of 1mol/L were addedIn the mixed solution of potassium hydrogen formate, I in the solution - Ion quilt H 2 O 2 Oxidized into iodic tri-ion. Iodine tri-ion has strong absorption peak at 352nm, so that H with known gradient concentration can be measured by ultraviolet-visible spectrophotometer 2 O 2 Absorbance at this point, standard H was obtained 2 O 2 Concentration-absorbance working curve. For unknown concentrations of H 2 O 2 The solution can be combined with the working curve to obtain H by measuring the absorbance of the solution at 352nm 2 O 2 Specific concentration of (3).
Compared with K-CN, the K/O-CN obtained by the secondary microwave heating is broken, and spherical carbon nitride is recombined into a porous hollowed-out cluster structure.
As can be seen from fig. 2, the (002) peak of K/O-CN obtained by the secondary microwave heating is significantly reduced compared with that of K-CN, which means that the crystallinity of carbon nitride is reduced and the thickness of the nanoplatelets is reduced, which is more beneficial to increase the specific surface area of the material, which is consistent with our intended objective.
Compared with K-CN, the distribution of K/O-CN obtained by secondary microwave heating is greatly increased in the mesopores of 2-10 nm. The specific surface area of the K/O-CN is about 3.5 times of that of the K-CN by combining the specific surface areas of the K-CN and the K/O-CN, so that the specific surface area of the K-CN can be greatly improved by the secondary microwave heating, and the defect of reduced specific surface area caused by the traditional molten salt method is avoided. The specific surface areas and pore volumes of K-CN and K/O-CN are shown in Table 1.
TABLE 1 comparison of specific surface area to pore Structure of the photocatalyst of different samples
| Sample of | Specific surface area (m) 2 g -1 ) | Pore volume (cm) 3 g -1 ) |
| K/O-CN | 65.396 | 0.153 |
| K-CN | 18.753 | 0.2209 |
As can be seen from FIG. 3, the absorption capacity of K/O-CN for both ultraviolet and visible light is improved compared to that of K-CN and O-CN. The potassium-oxygen co-doping has stronger light absorption capacity than carbon nitride doped by single element, and the stronger light absorption capacity is helpful for improving the photocatalysis performance.
As can be seen from FIG. 4, the XPS spectrum of K/O-CN shows peaks of C-O bond and K2 p, indicating that the doped double elements are all present in the form of chemical bonds in carbon nitride.
As can be seen from FIG. 5, the sample was photo-catalytically synthesized to H under simulated solar irradiation from a 300W xenon lamp 2 O 2 After two hours of reaction, the dual element doped K/O-CN is capable of generating 4012. Mu.M H 2 O 2 The performance is significantly higher than Yu Shanyuan plain doped O-CN and K-CN. The performance of K/O-CN is better than that of O/K-CN, because the secondary microwave method of doping potassium chloride and oxalic acid can effectively improve the specific surface area of the material, and overcomes the defects of carbon nitride crystallization and specific surface area reduction caused by potassium chloride molten salt.
Claims (8)
1. The preparation method of the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst is characterized by comprising the following steps of:
(1) Respectively dissolving melamine and cyanuric acid to obtain a solution A, B, mixing the solution A, B to obtain a white precipitate, and washing and drying to obtain melamine-cyanuric acid supermolecule powder; mixing the supermolecule powder with potassium chloride powder to obtain mixed powder A;
(2) Placing the mixed powder A into a container A, placing the container A into a container B, adding a wave-absorbing medium into the container B, and carrying out microwave heating on the container B to obtain a potassium-doped graphite-phase carbon nitride material;
(3) Mixing the potassium-doped graphite-phase carbon nitride material with oxalic acid to obtain mixed powder B, and then carrying out microwave heating according to the method of the step (2) to obtain the potassium-oxygen co-doped graphite-phase carbon nitride material.
2. The method for preparing the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein in the step (1), the molar ratio of melamine to cyanuric acid is 1: 1-1: 3.
3. the method for preparing the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein in the step (1), the mass ratio of potassium chloride in the mixed powder A is 25-75%.
4. The method for preparing the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein the microwave heating power in the step (2) and the step (3) is 500-1200W.
5. The method for preparing the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein the microwave time in the step (2) and the step (3) is 3-20 min.
6. The method for preparing the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein oxalic acid accounts for 10-40% of the mixed powder B in the step (3).
7. The method for preparing a potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein in the step (2), the wave-absorbing medium is at least one of graphite powder, graphene, carbon fiber, activated carbon, ferric oxide or copper oxide.
8. The application of the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst prepared by the method according to claim 1, wherein the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst is applied to photocatalytic hydrogen peroxide production.
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