CN115007182A - 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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- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
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- 238000000227 grinding Methods 0.000 description 6
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
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- 238000002441 X-ray diffraction Methods 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
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- 229910052740 iodine Inorganic materials 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
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- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 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
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- Chemical Kinetics & Catalysis (AREA)
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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 a white precipitate which is supramolecular powder, and mixing the supramolecular powder with potassium chloride powder to obtain mixed powder A; (2) putting the mixed powder A into a container A, putting 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) and (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 in the step (2) to obtain the potassium-doped graphite-phase carbon nitride material. 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 carbon nitride, and obviously improves the photocatalytic activity; short synthesis period and 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
The hydrogen peroxide as an efficient oxidant has the advantages of high active oxygen content (47.1 wt%), no pollution (byproducts are only water and oxygen), and the like, and is widely applied to the fields of paper making, organic synthesis, wastewater treatment, metallurgical industry and the like. The traditional method for producing hydrogen peroxide is anthraquinone oxidation, which is dominant in the industrial synthesis of hydrogen peroxide, and the 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, the multi-step hydrogenation and oxidation reactions result in high energy consumption, and in addition, a large amount of pollutants such as waste liquid, waste gas, solid waste and the like are generated. Therefore, a low-energy-consumption pollution-free hydrogen peroxide preparation method needs to be researched to reduce 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. Among various photocatalysts capable of producing hydrogen peroxide by photocatalysis, graphite phase carbon nitride (g-C) 3 N 4 ) As a conjugated polymer semiconductor, there has been an increasing interest in its advantages of good chemical stability, appropriate band gap, and no metal component. However, g-C is limited by its structural defects (visible light only at wavelengths less than 450nm and low conductivity and charge separation efficiency) 3 N 4 The application of the compound as a catalyst in the aspect of photocatalytic hydrogen peroxide production.
Numerous strategies including element doping to modulate g-C 3 N 4 The energy band structure, the charge separation capability and the surface appearance of the material can be improvedPhotocatalytic hydrogen peroxide generation activity, 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 (A) usually requires high-temperature calcination for several hours, and the preparation methods are complicated and have high energy consumption. In addition, a molten salt method commonly adopted by potassium doping can promote carbon nitride crystallization, reduce the specific surface area of the material and have certain limitations.
Disclosure of Invention
The purpose of the invention is as follows: 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; then mixing the supermolecule powder and potassium chloride powder to obtain mixed powder A;
(2) putting the mixed powder A into a container A, putting 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) and (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 in the step (2) to obtain the potassium-oxygen co-doped graphite-phase carbon nitride material.
Wherein in the step (1), the mol ratio of melamine to cyanuric acid is 1: 1-1: 3.
wherein in the step (1), the potassium chloride accounts for 25-75% of the mixed powder A by mass.
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), oxalic acid accounts for 10-40% by mass.
In the step (2), the wave-absorbing medium is at least one of graphite powder, graphene, carbon fiber, activated carbon, iron 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.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) the preparation method has the advantages of simple preparation process, capability of synthesizing the product by microwave heating for only two times of minutes, easiness in precise regulation and control, simplicity and easiness in obtaining of raw materials, low energy consumption in the preparation process and relative simplicity in operation conditions. (2) According to the secondary microwave method, the gas atmosphere formed by oxalic acid heating decomposition is utilized, the decomposition and recombination of the carbon nitride structure are promoted, 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 the doping of oxygen is realized. (3) According to the invention, the potassium element and the oxygen element are codoped into the graphite-phase carbon nitride, so that the absorptivity of the material to visible light is improved, the recombination of photo-generated electrons and holes is inhibited, the activity of hydrogen peroxide generated by photocatalysis is improved, and the photocatalysis capability is obviously higher than that of single element doped graphite-phase carbon nitride.
Drawings
Fig. 1 is a schematic view of a process for preparing potassium-oxygen co-doped graphite-phase carbon nitride in example 1;
FIG. 2 is an SEM image of the product of example 1, comparative example 1;
FIG. 3 is an XRD pattern of the product of example 1, comparative example 1;
FIG. 4 is a graph of the pore structure distribution of the products of example 1, comparative example 1;
FIG. 5 is a UV-vis DRS spectrum of the products of example 1, comparative example 1 and comparative example 2;
FIG. 6 is an XPS spectrum of potassium oxygen co-doped graphite phase carbon nitride of example 1;
FIG. 7 is a graph of the photocatalytic hydrogen peroxide generation performance of the products of example 1 and comparative examples 1-3.
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 supramolecular precursors: dissolving 1g of melamine and 1.02g of cyanuric acid in 200mL and 100mL of dimethyl sulfoxide solution respectively to obtain a solution A and a solution B, mixing the solution A and the solution B, and fully stirring for 10 minutes to obtain a white precipitate. Washing the white precipitate with ethanol for three times, drying at 60 ℃ for 10 hours to obtain a white blocky solid, and fully grinding the solid to obtain white powder, namely the melamine-cyanuric acid supramolecular precursor.
(2) First microwave heating: taking 1g of the supermolecule precursor, uniformly mixing with 0.5g of potassium chloride powder, and grinding to obtain mixed powder. Taking a 50mL large crucible and a 20mL small crucible, transferring the obtained mixed powder into the small crucible, covering a cover of the small crucible, putting the small crucible into the large crucible, adding graphite powder into the large crucible until the small crucible is completely covered, and covering the cover of the large crucible 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 the 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) second microwave heating: 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 mark is K/O-CN.
Example 2
On the basis of example 1, the difference from example 1 is:
(1) preparation of supramolecular precursors: 5g of melamine and 15.30g of cyanuric acid were dissolved in 400mL and 400mL of dimethyl sulfoxide solution, respectively, to obtain solution A and solution B.
(2) First microwave heating: and 3g of the supermolecule precursor is taken, uniformly mixed with 1g of potassium chloride powder and ground to obtain mixed powder. The microwave oven was set at 1200W and heated in air for 3 minutes.
(3) And (3) second microwave heating: mixing potassium-doped graphite-phase carbon nitride with oxalic acid according to a mass ratio of 9: 1. The heating power and the heating time were changed to 500W for 20 minutes.
Example 3
On the basis of example 1, the difference from example 1 is:
(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 obtain solution A and solution B.
(2) First microwave heating: and (3) taking 1g of the supermolecule precursor, uniformly mixing with 3g of potassium chloride powder, and grinding to obtain mixed powder. The microwave oven was set at 500W and heated in air for 3 minutes.
(3) And (3) second microwave heating: mixing potassium-doped graphite-phase carbon nitride with oxalic acid according to the mass ratio of 3: 2. The heating power and the heating time were changed to 1200W for 20 minutes.
Comparative example 1
On the basis of example 1, the difference from example 1 is: 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: in the step (2), 1g of the supermolecule precursor is taken and mixed with 0.5g of oxalic acid powder uniformly and ground to obtain mixed powder. And 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:
in the step (2): and (3) taking 1g of the supermolecule precursor, uniformly mixing with 0.5g of oxalic acid powder, and grinding to obtain mixed powder. And obtaining the oxygen-doped graphite-phase carbon nitride material.
In the step (3): mixing oxygen-doped graphite-phase carbon nitride and potassium chloride according to the mass ratio of 2: 1. And obtaining the oxygen-potassium co-doped graphite-phase carbon nitride material marked as O/K-CN.
Synthesis of H 2 O 2 Experiment: three 50mL portions of 10% by volume isopropanol solution were prepared and placed in a 100mL beaker. 50mg of the photocatalyst was taken out and added to the above isopropyl alcohol solution. And introducing oxygen into the suspension in a dark place for 20min, and stirring in a dark place for 30min to ensure that the photocatalyst achieves oxygen adsorption-desorption balance. Next, a 300W xenon lamp was used to simulate the solar irradiation of the solution while a constant amount of oxygen was continuously fed. 2mL of the suspension was removed at specified intervals and filtered to give 1mL of supernatant for use.
H in solution 2 O 2 The concentration was measured by iodometric titration: 1mL of unknown concentration H is taken 2 O 2 0.5mL of a mixed solution of 1mol/L KI and 1mol/L potassium hydrogen phthalate, and I in the solution - Ion quilt H 2 O 2 Oxidized to iodonium triion. Iodine three ion has strong absorption peak at 352nm, so that the ultraviolet-visible spectrophotometer can be used for measuring H with known gradient concentration 2 O 2 Absorbance at this point, giving Standard H 2 O 2 Concentration-absorbance working curve. For unknown concentration of H 2 O 2 The solution can be obtained by measuring the absorbance of the solution at 352nm and combining the working curve to obtain H 2 O 2 In the presence of a specific concentration of (c).
As can be seen from FIG. 2, compared with K-CN, the spherical carbon nitride is broken and recombined into a porous hollow cluster structure in the K/O-CN obtained by the secondary microwave heating.
As can be seen from FIG. 3, compared with K-CN, the (002) peak of K/O-CN obtained by secondary microwave heating is obviously reduced, which indicates that the crystallinity of carbon nitride is reduced, the thickness of the nanosheet is reduced, and the specific surface area of the material is increased, which is consistent with the target expected by us.
As can be seen from FIG. 4, the mesopores with the distribution of K/O-CN in the range of 2-10 nm obtained by the secondary microwave heating are greatly increased compared with K-CN. By combining the specific surface areas of K-CN and K/O-CN, the specific surface area of K/O-CN is about 3.5 times of that of K-CN, which shows that the specific surface area of K-CN can be greatly improved by 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 the specific surface area of the photocatalyst with the pore structure for different samples
| Sample (I) | 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. 5, the K/O-CN has an improved absorption capacity for both UV and visible light compared to K-CN and O-CN. The light absorption capacity of the potassium-oxygen co-doping is higher than that of the single element-doped carbon nitride, and the higher light absorption capacity is helpful for improving the photocatalytic performance.
As can be seen from FIG. 6, the XPS spectrum of K/O-CN shows peaks of C-O bond and K2 p, indicating that both the doped double elements are present in the form of chemical bonds in the carbon nitride.
As can be seen from FIG. 7, H is synthesized by photocatalysis of a sample under the irradiation of simulated sunlight of a 300W xenon lamp 2 O 2 Two-element doped K/O-CN can produce 40 after two hours reaction12 μ M H 2 O 2 The performance is obviously higher than that of O-CN and K-CN doped by single element. Meanwhile, the performance of the K/O-CN is better than that of the O/K-CN because the specific surface area of the material can be effectively improved by a secondary microwave method of doping potassium chloride and then doping oxalic acid, and the defects of carbon nitride crystallization and specific surface area reduction caused by potassium chloride molten salt are overcome.
Claims (8)
1. A preparation method of a potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst is characterized by comprising 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 supramolecular powder; then mixing the supermolecule powder and potassium chloride powder to obtain mixed powder A;
(2) putting the mixed powder A into a container A, putting 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) and (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 in 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 preparation method of the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein in the step (1), the potassium chloride in the mixed powder A accounts for 25-75% by mass.
4. The preparation method of the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein the microwave heating power in the steps (2) and (3) is 500-1200W.
5. The preparation method of the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst according to claim 1, wherein the microwave time in the steps (2) and (3) is 3-20 min.
6. The preparation method of 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, iron oxide or copper oxide.
8. The method for preparing the potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst 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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