CN114082433A - Oxygen-doped carbon nitride catalyst and preparation method and application thereof - Google Patents
Oxygen-doped carbon nitride catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000029087 digestion Effects 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
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- 238000005406 washing Methods 0.000 claims abstract description 7
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- 230000008569 process Effects 0.000 claims description 9
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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Images
Classifications
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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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses an oxygen-doped carbon nitride catalyst, a preparation method thereof and application thereof in photocatalytic ammonia production. The preparation method comprises the following steps: (1) roasting melamine to obtain g-C3N4And is marked as BCN; (2) carrying out secondary calcination on BCN to obtain g-C with high specific surface area3N4Denoted as HCN; (3) reacting HCN with H2O2And uniformly mixing the solution, placing the solution in a microwave digestion instrument for constant-temperature digestion, and washing and drying the solid to obtain the oxygen-doped carbon nitride catalyst. The invention increases the g-C by a simple secondary calcination method3N4The specific surface area of the catalyst is combined with a microwave hydrothermal method to dope oxygen atoms into g-C3N4Structure g-C3N4The ammonia production performance of the photocatalyst is greatly improved to reach 3.98 mmol.g‑1·h‑1Is unmodified g-C3N46.22 times of the catalyst.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to an oxygen-doped carbon nitride catalyst and a preparation method and application thereof.
Background
Ammonia gas is an important substance for preparing nitrogen fertilizer and other chemical raw materials, and the traditional haber-bosch method for preparing ammonia at high temperature and high pressure has high energy consumption and high CO content2The discharge amount is contrary to the concept of energy saving and carbon reduction. The nitrogen fertilizer synthesized by the traditional method has low utilization rate, and can cause agricultural non-point source pollution after being applied, thereby causing a large amount of ammonia emission. Ammonia is an important precursor of PM2.5 and other atmospheric pollutants, and the control of the emission amount of the ammonia has great significance for improving the air quality. The patent proposes that an ammonia-producing photocatalyst can be combined with an alcohol sacrificial agent and the like to form an in-situ leaf surface ammonia supply system, so that the slow release effect is realized, and the agricultural non-point source ammonia emission is obviously reduced.
Based on the above, the development of high-efficiency, low-toxicity and environment-friendly ammonia-producing photocatalyst becomes the focus of research on an in-situ leaf surface ammonia supply system.
The total reaction formula of the photocatalytic ammonia production is
The process can be divided into the following steps:
(1) under the excitation of illumination, the catalyst generates a photo-generated electron-hole pair, wherein electrons migrate to a conduction band position, holes are left in a valence band, and the electrons and the holes are separated;
(2) the photo-generated electrons and holes are transferred to the surface of the catalyst, and the recombination of partial photo-generated carriers is also carried out in the process;
(3) electrons successfully transferred to the surface will reduce nitrogen adsorbed on the catalyst surface to produce ammonia, while holes oxidize water or hole traps at the surface to produce oxygen or other intermediates.
Among the numerous photocatalytic materials, g-C3N4The preparation method is simple, the forbidden band width is about 2.7eV, the light absorption edge is about 460nm, the visible light can be absorbed and utilized, and the product has good chemical and thermal stability, is safe and nontoxic, and is used for in-situ ammonia productionHigh-quality alternative of photocatalyst.
But g-C3N4The solar energy-saving solar cell also has the defects of limited utilization of sunlight, small specific surface area, easy recombination of electron-hole pairs and the like.
Doping of non-metallic elements to promote g-C3N4One of the effective ways of photocatalytic performance of catalysts.
Patent specification CN 106694021 a discloses an oxygen-doped graphite phase carbon nitride catalyst. The preparation method comprises the following steps: calcining melamine at 500-600 ℃ for 2-4 h, cooling to obtain light yellow powdery g-C3N4, and grinding; providing a first solution comprising g-C mixed uniformly3N4Powder and H2O2Ultrasonically stirring the first solution to obtain a reactant to be reacted; carrying out hydro-thermal synthesis reaction on the reactant to be reacted to obtain a mixture; cooling the mixture and removing H2O2And drying and grinding the residual graphite phase carbon nitride catalyst to obtain the oxygen-doped graphite phase carbon nitride catalyst.
The patent specification with the publication number CN 107649168A discloses O-g-C with controllable oxygen doping amount3N4The preparation method comprises the following steps: 1) roasting melamine at 550 ℃ for 4 hours, grinding and sieving to obtain g-C3N4(ii) a 2) Taking g-C3N4Adding H2O2Magnetically stirring, washing with deionized water to neutrality, drying, and sieving to obtain product H2O2-g-C3N4(ii) a 3) The obtained H2O2-g-C3N4Calcining at 500 deg.C for 2 hr to obtain O-g-C product3N4。
Disclosure of Invention
The present invention addresses the restriction g-C3N4The factor of improving the efficiency of the photocatalyst is researched for nonmetal modification, and the preparation method of the oxygen-doped carbon nitride catalyst is provided, wherein the g-C is increased by a simple secondary calcination method3N4Specific surface area of catalyst and doping of oxygen atoms into g-C by microwave hydrothermal method3N4The structure improves the sunlight utilization rate. On the basis of constructing a high-efficiency photocatalyst, glycerin integrating the functions of moisture retention and hole trapping is combined to develop and construct a novel in-situ leaf surface ammonia supply system.
Oxygen-doped carbon nitride (g-C)3N4) Catalyst (noted as O-g-C)3N4) The preparation method comprises the following steps:
(1) roasting melamine to obtain g-C3N4And is marked as BCN;
(2) carrying out secondary calcination on BCN to obtain g-C with high specific surface area3N4Denoted as HCN;
(3) reacting HCN with H2O2And uniformly mixing the solution, placing the solution in a microwave digestion instrument for constant-temperature digestion, and washing and drying the solid to obtain the oxygen-doped carbon nitride catalyst.
Oxygen-doped g-C of the invention3N4The preparation method of the catalyst utilizes a secondary calcination method to prepare g-C with high specific surface area3N4After the matrix is prepared, the catalyst is further subjected to oxygen doping modification by adopting a rapid microwave hydrothermal method, and the preparation method has the advantages of simplicity, convenience and low cost and is easy for large-scale production.
In a preferred example, in the preparation method of the oxygen-doped carbon nitride catalyst, in the step (1), the temperature rise rate in the roasting process is 1-10 ℃/min, the roasting temperature is 500-550 ℃, and the roasting time is 30-210 min.
In a preferred embodiment, in the preparation method of the oxygen-doped carbon nitride catalyst, in the step (2), O is generated during the calcination process2And N2The volume ratio is 0.25-4: 1.
In a preferred example, in the preparation method of the oxygen-doped carbon nitride catalyst, in the step (2), the temperature rise rate in the calcination process is 2-10 ℃/min, the calcination temperature is 450-550 ℃, and the calcination time is 30-210 min.
In a preferred embodiment, in the preparation method of the oxygen-doped carbon nitride catalyst, in the step (3), H is2O2H in solution2O2The mass concentration of (A) is 5-30%.
In a preferable example, in the preparation method of the oxygen-doped carbon nitride catalyst, in the step (3), the temperature rise rate in the digestion process is 20-50 ℃/min, the digestion temperature is 120-200 ℃, and the time is 30-90 min.
The invention also provides the oxygen-doped carbon nitride catalyst prepared by the preparation method.
The invention also provides application of the oxygen-doped carbon nitride catalyst in photocatalytic ammonia production.
The oxygen-doped carbon nitride catalyst is used for catalytically reducing N in an alcohol solution under simulated sunlight2The use of (1).
The oxygen-doped carbon nitride catalyst can be compounded with alcohol sacrificial agents and the like, is sprayed on the surfaces of crop leaves and is used as a green leaf fertilizer, and ammonia is generated in situ for crops to utilize.
Compared with the prior art, the invention has the main advantages that:
1. the invention prepares g-C with high specific surface area by a secondary calcination method3N4Matrix (HCN) overcoming g-C obtained by direct calcination of melamine3N4The (BCN) has the defects of small specific surface area, simple preparation process and high yield.
2. According to the invention, the rapid microwave hydrothermal method is adopted to further carry out O doping modification on HCN, so that the composition of photon-generated carriers can be inhibited, the adsorption and activation process of nitrogen molecules can be promoted, and the photocatalytic performance of the catalyst can be further improved. The method has the advantages of uniform heating, low energy consumption, and capability of improving the production efficiency, and the prepared catalyst is relatively stable. Experiments prove that the photocatalyst prepared by the invention has extremely high photocatalytic ammonia production activity, and is not calcined or doped with g-C3N46.22 times of.
3. The high-efficiency ammonia-producing photocatalyst can be combined with alcohol sacrificial agents such as ethylene glycol and glycerol to prepare an environment-friendly and harmless in-situ leaf surface ammonia supply system.
Drawings
FIG. 1 shows TEM photographs (a) and HAADF-STEM photographs (b) of the catalyst prepared in example 1 and their element distribution diagrams (c to e);
FIG. 2 is SEM photographs of the catalyst prepared in example 1 before and after microwave hydrothermal treatment, wherein the left image is BCN and the right image is OCN 10;
fig. 3 is an XRD pattern before and after microwave hydrothermal treatment of the catalyst prepared in example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
The preferred embodiment of the present invention provides an oxygen-doped-g-C3N4The preparation method of the catalyst comprises the following steps:
s1, placing a ceramic crucible filled with 5.0g of melamine in a muffle furnace without a cover for calcination. The heating rate of calcination is 2.5 ℃ min-1And keeping the temperature for 120min after the temperature is raised to 520 ℃, and collecting the obtained sample after cooling to obtain the catalyst matrix BCN.
S2, placing the BCN prepared in the step S1 in a muffle furnace, and performing reaction in an atmosphere of O2：N 230%: calcining in 70% (volume ratio) atmosphere at a temperature rise rate of 5 deg.C/min-1Keeping the temperature for 120min after the temperature is raised to 520 ℃ to obtain g-C with high specific surface area3N4Catalyst HCN.
S3, mixing HCN with 30mL H2O2(10 wt%) and then mixed by magnetic stirring in a water bath at a constant temperature of 70 ℃ for 2 hours. Then the mixed solution is transferred into a digestion tank, and the digestion tank is sealed and then placed into a microwave digestion instrument. The program is set to heat to 140 ℃ for 60min, and the heating rate is 55 ℃ min-1. And after natural cooling, carrying out suction filtration and separation on the obtained mixed solution, fully washing solid powder by using deionized water and absolute ethyl alcohol respectively, putting the washed solid powder into an oven at 80 ℃ for drying, and collecting an obtained sample OCN 10.
The product OCN10 obtained in example 1 was examined by Transmission Electron Microscopy (TEM) and the results are shown in FIG. 1 a.
The OCN10 product obtained in example 1 was observed by high-angle annular dark-field image transmission electron microscope (HAADF-STEM) and its element distribution image, and the results are shown in FIGS. 1b to 1 e.
The product OCN10 obtained in Experimental example 1 and the BCN obtained in step S1 were observed by a Scanning Electron Microscope (SEM), and the appearance morphology is shown in FIG. 2.
The product OCN10 obtained in Experimental example 1 and BCN obtained in step S1 were subjected to X-ray diffraction (XRD), and the diffraction patterns thereof are shown in FIG. 3. OCN10 and BCN have two characteristic peaks at diffraction angles 2 theta of 13.1 degrees and 27.5 degrees, which correspond to g-C3N4The (100) and (002) crystal planes of (a). The characteristic peak at 13.1 degrees is weaker and is formed by stacking of planar structures of triazine rings, and the characteristic peak at 27.5 degrees is related to the stacking of conjugated aromatic systems. It can be seen from the figure that after the second calcination and oxygen doping treatment, the crystal structure of OCN10 is the same as that of BCN, indicating that the crystal structure is not significantly changed. Compared with BCN, the diffraction peak intensity of OCN10 is obviously enhanced, which shows that the crystallinity of the crystal is improved after the secondary calcination and the microwave hydrothermal treatment.
The performance of the BCN, HCN and OCN10 in example 1 in photocatalytic nitrogen fixation under simulated sunlight irradiation was tested respectively, and the results are shown in Table 1. As can be seen from the table, the photocatalytic ammonia production rate of the OCN10 catalyst prepared by the invention reaches 3.98mmol g-1·h-1It was 6.22 times as much as BCN and 1.49 times as much as HCN.
TABLE 1
Example 2
The preferred embodiment of the present invention provides an oxygen-doped-g-C3N4The preparation method of the catalyst comprises the following steps:
s1, placing a ceramic crucible filled with 5.0g of melamine in a muffle furnace without a cover for calcination. The heating rate of calcination is 2.5 ℃ min-1And keeping the temperature for 120min after the temperature is raised to 520 ℃, and collecting the obtained sample after cooling to obtain the catalyst matrix BCN.
S2, placing the BCN prepared in the step S1 in a muffle furnace, and performing reaction in an atmosphere of O2：N 220%: calcining in 80% (volume ratio) atmosphere at a temperature rise rate of 6 deg.C/min-1Keeping the temperature for 90min after the temperature is raised to 520 ℃ to obtain g-C with high specific surface area3N4Catalyst HCN.
S3, mixing HCN with 30mL H2O2(20 wt%) and then mixed by magnetic stirring in a water bath at a constant temperature of 70 ℃ for 2 hours. Then the mixed solution is transferred into a digestion tank, and the digestion tank is sealed and then placed into a microwave digestion instrument. The program is set to heat to 140 ℃ for 60min, and the heating rate is 50 ℃ min-1. And after natural cooling, carrying out suction filtration and separation on the obtained mixed solution, fully washing solid powder by using deionized water and absolute ethyl alcohol respectively, putting the washed solid powder into an oven at 80 ℃ for drying, and collecting an obtained sample OCN 20.
Example 3
The preferred embodiment of the present invention provides an oxygen-doped-g-C3N4The preparation method of the catalyst comprises the following steps:
s1, placing a ceramic crucible filled with 5.0g of melamine in a muffle furnace without a cover for calcination. The heating rate of calcination is 2.5 ℃ min-1And keeping the temperature for 120min after the temperature is raised to 520 ℃, and collecting the obtained sample after cooling to obtain the catalyst matrix BCN.
S2, placing the BCN prepared in the step S1 in a muffle furnace, and performing reaction in an atmosphere of O2：N 240%: calcining in 60% (volume ratio) atmosphere at a heating rate of 7 deg.C/min-1Keeping the temperature for 120min after the temperature is raised to 520 ℃ to obtain g-C with high specific surface area3N4Catalyst HCN.
S3, mixing HCN with 30mL H2O2(30 wt.%) and mixing by magnetic stirring in a water bath at 70 deg.C for 2 hr. Then the mixed solution is transferred into a digestion tank, and the digestion tank is sealed and then placed into a microwave digestion instrument. The program is set to heat to 140 ℃ for 60min, and the heating rate is 50 ℃ min-1. After natural cooling, carrying out suction filtration separation on the obtained mixed solution, fully washing solid powder with deionized water and absolute ethyl alcohol respectively, putting the washed solid powder into an oven at 80 ℃ for drying, and collecting the obtained sampleProduct OCN 30.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of an oxygen-doped carbon nitride catalyst is characterized by comprising the following steps:
(1) roasting melamine to obtain g-C3N4And is marked as BCN;
(2) carrying out secondary calcination on BCN to obtain g-C with high specific surface area3N4Denoted as HCN;
(3) reacting HCN with H2O2And uniformly mixing the solution, placing the solution in a microwave digestion instrument for constant-temperature digestion, and washing and drying the solid to obtain the oxygen-doped carbon nitride catalyst.
2. The preparation method according to claim 1, wherein in the step (1), the temperature rise rate in the roasting process is 1-10 ℃/min, the roasting temperature is 500-550 ℃, and the roasting time is 30-210 min.
3. The method according to claim 1, wherein in the step (2), O is generated during calcination2And N2The volume ratio is 0.25-4: 1.
4. The preparation method according to claim 1, wherein in the step (2), the temperature rise rate in the calcination process is 2-10 ℃/min, the calcination temperature is 450-550 ℃, and the calcination time is 30-210 min.
5. The process according to claim 1, wherein in the step (3), H is2O2H in solution2O2The mass concentration of (A) is 5-30%.
6. The preparation method according to claim 1, wherein in the step (3), the temperature rise rate in the digestion process is 20-50 ℃/min, the digestion temperature is 120-200 ℃, and the time is 30-90 min.
7. The oxygen-doped carbon nitride catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the oxygen-doped carbon nitride catalyst according to claim 7 for photocatalytic ammonia production.
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