CN113244943A - Composite graphite phase carbon nitride material and preparation method and application thereof - Google Patents
Composite graphite phase carbon nitride material and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000010439 graphite Substances 0.000 title claims abstract description 75
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 64
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 63
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
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- 239000004202 carbamide Substances 0.000 claims description 19
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 5
- 238000012719 thermal polymerization Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- -1 carbon nitrides Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method 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
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B15/027—Preparation from water
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the technical field of nano material preparation, and particularly relates to a composite graphite phase carbon nitride material as well as a preparation method and application thereof. K, P, O and S are doped into the graphite-phase carbon nitride structure by utilizing a thermal polymerization method, and the doping of the elements not only reduces the band gap width of the graphite-phase carbon nitride, but also effectively increases the utilization rate of visible light and accelerates the transmission rate of photon-generated carriers. The visible light catalyst with higher catalytic activity is screened out, and H is promoted2O2Efficient generation of (1).
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a composite graphite phase carbon nitride material as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Hydrogen peroxide is a strong oxidant commonly used in the industry, and has been widely used in organic synthesis, environmental remediation, disinfection, liquid propellants, and the like because the reaction product only generates water and oxygen. Currently, H is commercially produced2O2The anthraquinone process can cause a large amount of energy consumption in the production process and generate pollutants to cause environmental pollution. Therefore, an inexpensive production H was developed2O2The green process of (2) is in great demand.
Graphite phase carbon nitride (g-C)3N4) Is a non-metallic inorganic semiconductor that is of great interest because of its high energy structure suitable for water decomposition, Oxygen Reduction Reaction (ORR) and organic contaminant degradation. Although the photocatalyst has been used for producing H2O2However, the rapid recombination of photo-generated electron-hole pairs in graphite-phase carbon nitride results in a lower H2O2The yield limits the practical application of the graphite phase carbon nitride, and the quantum efficiency and the photocatalytic performance of the graphite phase carbon nitride must be further improved.
Some prior art techniques dope graphite phase carbon nitride materials with elements to raise H2O2Production efficiency, but the inventor researches and discovers that the elements catalyze the preparation of H by the graphite phase carbon nitride material2O2Has limited effect on improving and catalytically produces H with prolonged catalytic time2O2The effect of (A) is reduced to some extent, H2O2The rate of yield increase decreases.
Disclosure of Invention
In order to further improve the catalytic production of H by the graphite phase carbon nitride material2O2The invention provides a composite graphite phase carbon nitride material and a preparation method and application thereof, wherein K, P, O and S are doped into a graphite phase carbon nitride structure by utilizing a thermal polymerization method, and the doping of elements not onlyThe band gap width of graphite-phase carbon nitride is reduced, the utilization rate of visible light is effectively increased, and the transmission rate of photon-generated carriers is accelerated. The visible light catalyst with higher catalytic activity is screened out, and H is promoted2O2Efficient generation of (1).
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, there is provided a composite graphite phase carbon nitride material loaded with K, P, O, S elements.
In a second aspect of the present invention, a method for preparing a composite graphite-phase carbon nitride material is provided, which comprises mixing a potassium source, a phosphorus source, a sulfur source and urea, and sintering.
In a third aspect of the invention, a composite graphite phase carbon nitride material is provided for synthesizing H2O2The use of (1).
In a fourth aspect of the invention, there is provided a method of producing H2O2A synthesis catalyst comprising the composite graphite phase carbon nitride material of claim 1.
One or more embodiments of the present invention have the following advantageous effects:
1) by doping K, P, O and S into the graphite-phase carbon nitride structure, the doping of K, P, O, S element not only reduces the band gap width of the graphite-phase carbon nitride, but also effectively increases the utilization rate of visible light and accelerates the transmission rate of photon-generated carriers. The visible light catalyst with higher catalytic activity is screened out, and H is promoted2O2Efficient generation of (1).
2) The research of the invention discovers that the traditional visible-light-driven photocatalyst is used for producing H under catalysis2O2In the case of the catalyst, the catalytic effect is lowered with the increase in the catalyst use time. The method is beneficial to improving the catalytic production of H by the composite graphite phase carbon nitride material through the interaction of K, P, O, S elements2O2Stability in time.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a scanning electron microscope image of graphite-phase carbon nitride prepared in Experimental example 1 of the present invention;
FIG. 2 shows the K, P, O, S-modified graphite-phase carbonitride (K, P, O, S-g-C) prepared in Experimental example 23N4) Scanning an electron microscope picture;
FIG. 3 is a graph showing graphite-phase carbon nitrides (g-C) prepared in the experimental examples of the present invention and in comparative examples 1 to 43N4) And the proportions of K, P, O-graphite phase carbon nitride (K, P, O-g-C)3N4) And K, P, O, S-graphite phase carbon nitride (K, P, O, S-g-C)3N4) An XRD pattern of (a);
FIG. 4 is a graph showing graphite-phase carbon nitrides (g-C) prepared in the experimental examples of the present invention and in comparative examples 1 to 43N4) And the proportions of K, P, O-graphite phase carbon nitride (K, P, O-g-C)3N4) And K, P, O, S-graphite phase carbon nitride (K, P, O, S-g-C)3N4) H of (A) to (B)2O2A photosynthesizing curve;
FIG. 5 shows graphite-phase carbon nitrides (g-C) prepared in the experimental examples of the present invention and comparative examples 3, 5 and 73N4) K, P, O-graphite phase carbon nitride (K, P, O-g-C)3N4) Single element doped graphite phase carbon nitride and K, P, O, S-graphite phase carbon nitride (K, P, O, S-g-C)3N4) H of (A) to (B)2O2And (4) synthesizing a curve.
Detailed Description
The invention will be further illustrated with reference to the following 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 experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to further improve the catalytic production of H by the graphite phase carbon nitride material2O2The invention provides a composite graphite phase carbon nitride material and a preparation method and application thereof, wherein K, P, O and S are doped into a graphite phase carbon nitride structure by utilizing a thermal polymerization method, and the doping of elements not only reduces the band gap width of the graphite phase carbon nitride, but also effectively increases the utilization rate of visible light and accelerates the transmission rate of photon-generated carriers. The visible light catalyst with higher catalytic activity is screened out, and H is promoted2O2Efficient generation of (1).
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, there is provided a composite graphite phase carbon nitride material loaded with K, P, O, S elements.
Although the prior art discloses doping of K or P elements into graphite phase carbon nitride materials for improving the catalytic production of H from graphite phase carbon nitride materials2O2The inventor researches and discovers that the catalyst has the defects of poor catalytic effect and insufficient stability, so that the S element is introduced into the invention to be cooperated with K, P, O to promote the composite graphite phase carbon nitride material to catalytically produce H2O2Efficiency and stability of the process. The deep analysis principle shows that the doping of the K, P, O, S element not only reduces the band gap width of graphite phase carbon nitride, but also effectively increases the utilization rate of visible light and accelerates the transmission rate of photon-generated carriers. The visible light catalyst with higher catalytic activity is screened out, and H is promoted2O2Efficient generation of (1).
In a second aspect of the present invention, a method for preparing a composite graphite-phase carbon nitride material is provided, which comprises mixing a potassium source, a phosphorus source, a sulfur source and urea, and sintering.
Source of raw material affecting element loadingThe uniformity and the interaction among elements are proved by experiments, when the potassium source is selected from dipotassium hydrogen phosphate, the phosphorus source is selected from dipotassium hydrogen phosphate, and the sulfur source is selected from thiourea, the prepared composite graphite phase carbon nitride material catalyzes and produces H2O2The efficiency of (2) is higher.
Further research shows that K and P have better synergistic effect when the potassium source and the phosphorus source are selected from substances containing potassium and phosphorus at the same time, and dipotassium hydrogen phosphate is preferred, and the catalytic performance of the composite graphite phase carbon nitride material prepared by using the dipotassium hydrogen phosphate is better than that of the composite graphite phase carbon nitride material prepared by using different K sources and P sources.
The loading capacity of elements in the composite graphite phase carbon nitride material is determined by the raw material proportion, and when the mass ratio of dipotassium hydrogen phosphate, the sulfur source and the urea is as follows: 0.02-2.28:9-14:9-14, the molar ratio of K, P, O and S elements is 0.02-2: 0.01-1: 15-28: 11-18, under the condition of the element proportion, the four elements can obviously promote the composite graphite phase carbon nitride material to catalytically produce H2O2The efficiency of (c).
The inventor finds that when the mass ratio of the dipotassium hydrogen phosphate to the sulfur source to the urea is as follows: when the ratio of H to H is 0.68:11.42:11.42, the composite graphite phase carbon nitride material still has high catalytic performance after being used for 180min in catalysis, and H2O2The yield still increased. While the traditional catalyst has the problem of catalytic stop after being used for 180min, H2O2The yield is not increased any more.
Experiments also find that when the mass ratio of the sulfur source to the urea is 1:1, the prepared composite graphite phase carbon nitride material is used for catalyzing 160-180min to produce H2O2Still have a high level of efficiency.
In the preparation process, the sintering temperature and time influence the morphology and element distribution of the composite graphite phase carbon nitride material, when the sintering temperature is 500-600 ℃, and the sintering temperature is kept for 2-5h, the graphite phase carbon nitride has a complete lamellar structure, which is beneficial to the uniform distribution of K, P, O and S elements.
The temperature rise rate in the sintering process affects the uniformity of elements, is too fast, elements are not distributed in the graphite phase carbon nitride lamellar structure in time, and is too slow, so that the generation of the graphite phase carbon nitride lamellar structure is not facilitated, and therefore, in one or more embodiments of the invention, the temperature rise rate in the sintering process is 5-10 ℃/min.
In one or more embodiments of the invention, the temperature rise rate is 5 ℃/min, the temperature rises to 550 ℃, and the composite graphite phase carbon nitride material prepared has good catalytic stability when the temperature is maintained for 3 hours.
In a third aspect of the invention, a composite graphite phase carbon nitride material is provided for synthesizing H2O2The use of (1).
Preferably, H is synthesized under visible light2O2The use of (1).
In a fourth aspect of the invention, there is provided a method of producing H2O2A synthesis catalyst comprising the composite graphite phase carbon nitride material of claim 1.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
In the following method of the invention, the equipment and reagents used are as follows:
TABLE 1 Instrument set
TABLE 2 major reagents
Experimental example 1 graphite phase carbon nitride powder (g-C)3N4) Preparation of
50g of urea was weighed into a porcelain crucible with a lid, placed in a forced air drying oven until the urea was completely dried, and then transferred to a muffle furnace. Raising the temperature to 550 ℃ at the temperature rise rate of 5 ℃/min, and keeping the temperature for 3 hours to finally obtain the faint yellow graphite phase carbon nitride powder.
Experiment ofExample 2K, P, O, S-graphite phase carbon nitride (K, P, O, S-g-C)3N4) Preparation of the powder
0.68g of dipotassium hydrogen phosphate, 11.42g of thiourea and 11.42g of urea are weighed respectively, uniformly mixed, ground, placed into a porcelain crucible with a cover and transferred into a muffle furnace. Raising the temperature to 550 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3h to finally prepare the graphite-phase carbon nitride powder modified by K, P, O and S with the mass ratio of 5% (the molar ratio of K: P: O: S is 0.7:0.3:20:15), namely the sum of the mass of the elements of K, P, O and S-graphite-phase carbon nitride, K, P, O and S is 5% of that of the composite catalyst.
Comparative example 1
22.84mg of dipotassium hydrogenphosphate and 22.84g of urea were weighed, mixed, ground, placed in a porcelain crucible with a lid, and transferred to a muffle furnace. Heating to 550 ℃ at a heating rate of 5 ℃/min, and keeping for 3 hours to obtain the K, P, O modified graphite phase carbon nitride (K, P, O-g-C) with the mass ratio of 0.1 percent3N4) The sum of the mass of the powder, K, P and O elements is 0.1 percent of the composite catalyst.
Comparative example 2
228.44mg of dipotassium hydrogen phosphate and 22.84g of urea were weighed, mixed, ground, placed in a porcelain crucible with a lid, and transferred to a muffle furnace. Heating to 550 ℃ at the heating rate of 5 ℃/min, and keeping for 3 hours to prepare the K, P, O modified graphite phase carbon nitride (K, P, O-g-C) with the mass ratio of 1 percent3N4) The sum of the mass of the powder, K, P and O elements is 1 percent of the composite catalyst.
Comparative example 3
1.14g of dipotassium hydrogenphosphate and 22.84g of urea were weighed, mixed, ground, placed in a porcelain crucible with a lid, and transferred into a muffle furnace. Heating to 550 ℃ at the heating rate of 5 ℃/min, and keeping for 3 hours to prepare the K, P, O modified graphite phase carbon nitride (K, P, O-g-C) with the mass ratio of 5 percent3N4) The sum of the mass of the powder, K, P and O elements is 5 percent of the composite catalyst.
Comparative example 4
2.28g of dipotassium hydrogenphosphate and 22.84g of urea are weighed, mixed, ground and processedPut into a porcelain crucible with a cover and transferred into a muffle furnace. Heating to 550 ℃ at the heating rate of 5 ℃/min, and keeping for 3 hours to obtain the K, P, O modified graphite phase carbon nitride (K, P, O-g-C) with the mass ratio of 10 percent3N4) The sum of the mass of the powder, K, P and O elements is 10 percent of the composite catalyst.
Comparative example 5
11.42g of thiourea and 11.42g of urea were weighed, mixed uniformly, ground, placed in a porcelain crucible with a lid, and transferred into a muffle furnace. Heating to 550 deg.C at a rate of 5 deg.C/min, and maintaining for 3 hr to obtain S-modified graphite phase carbon nitride powder, i.e. S-graphite phase carbon nitride (S-g-C)3N4)。
Comparative example 6
12g of urea and 0.4g of KNO are weighed3Dissolved in 60mL of deionized water, stirred and water bath dried at 70 ℃. The mixture was ground, placed in a porcelain crucible with a lid, and transferred to a muffle furnace. Raising the temperature to 550 ℃ at the temperature rising rate of 5 ℃/min and keeping the temperature for 3 hours. Subsequently, the product was pulverized and calcined at 350 ℃ for 3 hours in the atmosphere at a heating rate of 10 ℃ to finally obtain K-modified graphite phase carbon nitride powder, i.e., K-graphite phase carbon nitride (K-g-C)3N4)。
Comparative example 7
10g of urea, 0.2g of diammonium hydrogen phosphate and 50mL of deionized water are weighed, uniformly mixed and transferred to a crucible, dried at 65 ℃ for 12 hours, ground, placed in a ceramic crucible with a cover and transferred to a muffle furnace. Heating to 500 deg.C at a rate of 5 deg.C/min, and maintaining for 3 hr to obtain P-modified graphite phase carbon nitride powder, i.e. P-graphite phase carbon nitride (P-g-C)3N4)。
H2O2Catalytic experiment
In 135mL of deionized water and 15mL of an isopropyl alcohol mixed solvent (isopropyl alcohol volume fraction: 10 vol%), dilute hydrochloric acid was slowly added dropwise to a pH of 3.0 to 4.0, followed by addition of 0.15g of the photocatalyst prepared in the above examples and comparative examples, and high purity oxygen was introduced for 30min to bring the solution to an oxygen saturation state, and the solution was irradiated with 300W (λ >420nm) of xenon lamp for 150 min. After the reaction solution was extracted, the reaction solution was placed in a colorimetric tube containing a mixed solution of 8mL of 1M KI and 0.2mL of 0.01M ammonium molybdate, and the absorbance value of the reaction solution at a wavelength of 352nm was measured by an ultraviolet-visible spectrophotometer.
As shown in fig. 1, the graphite-phase carbon nitride prepared in experimental example 1 exhibited a two-dimensional sheet-like and layered porous structure. The K, P, O, S-graphite phase carbon nitride (figure 2) prepared in the experimental example 2 can observe that the K, P, O, S-graphite phase carbon nitride still presents a stacked layered structure, and is more obvious, and the structure is beneficial to the catalyst to adsorb more reaction substances and improve the reaction activity.
FIG. 3 is XRD patterns of experimental examples and comparative examples 1 to 4. After three elements of K, P and O are doped into the graphite phase carbon nitride framework structure in situ, K is added2HPO4The increase in the content shifts the (002) plane of the graphite phase carbon nitride slightly to a smaller angle because the S atom radius is larger than that of the N atom in the graphite phase carbon nitride after the S is substituted for the N atom, and thus the presence of the S atom can be confirmed.
FIG. 4 shows the synthesis of H under visible light for the experimental example and comparative examples 1 to 42O2And (4) an efficiency map. The production of all catalysts increased with time. The yield of pure graphite phase carbon nitride under the above test conditions was very low, while the yield of hydrogen peroxide after doping with the impurity elements was gradually increased, with the highest yield of K, P, O, S-graphite phase carbon nitride.
FIG. 5 shows the synthesis of H under visible light for experimental examples and comparative examples 3, 5 to 72O2And (4) an efficiency map. The production of all catalysts increased with time. Wherein H of K, P, O, S-graphite phase carbon nitride2O2The yield is the highest and is higher than that of graphite phase carbon nitride doped with single element and pure graphite phase carbon nitride. And over prolonged catalytic time, H of K, P, O, S-graphite phase carbon nitride2O2The yield is still in an increasing trend, which shows that the K, P, O, S-graphite phase carbon nitride catalyst has a continuous catalytic effect, and the single-element graphite phase carbon nitride and simple graphite phase carbon nitride, K, P, O-graphite phase carbon nitride catalyst has a continuous catalytic effect which is not as good as that of the K, P, O, S-graphite phase carbon nitride catalyst.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A composite graphite phase carbon nitride material, wherein the composite graphite phase carbon nitride material carries K, P, O, S elements.
2. The method of producing a composite graphite-phase carbon nitride material according to claim 1, comprising mixing a potassium source, a phosphorus source, a sulfur source, and urea, and sintering.
3. The method of producing the composite graphite phase carbon nitride material according to claim 2, wherein the potassium source is selected from the group consisting of dipotassium hydrogen phosphate, the phosphorus source is selected from the group consisting of dipotassium hydrogen phosphate, and the sulfur source is selected from the group consisting of thiourea;
preferably, the potassium source and the phosphorus source are selected from substances comprising both potassium and phosphorus, preferably dipotassium hydrogen phosphate.
4. The method for preparing a composite graphite-phase carbon nitride material according to claim 3, wherein the mass ratio of the dipotassium hydrogen phosphate, the sulfur source and the urea is as follows: 0.02-2.28:9-14: 9-14;
preferably, the mass ratio of the sulfur source to the urea is 1: 1.
5. The method for preparing a composite graphite-phase carbon nitride material according to claim 3, wherein the mass ratio of the dipotassium hydrogen phosphate, the sulfur source and the urea is as follows: 0.68:11.42:11.42.
6. The method for preparing a composite graphite phase carbon nitride material according to claim 2, wherein the sintering temperature is 500-600 ℃ and is maintained for 2-5 h.
7. The method of preparing a composite graphite phase carbon nitride material according to claim 2, wherein the temperature rise rate during the sintering process is 5 to 10 ℃/min.
8. The method for preparing a composite graphite-phase carbon nitride material according to claim 2, wherein the temperature is raised to 550 ℃ at a rate of 5 ℃/min for 3 hours.
9. Synthesis of H from the composite graphite phase carbon nitride material of claim 12O2The use of (1);
preferably, H is synthesized under visible light2O2The use of (1).
10. H2O2A synthesis catalyst comprising the composite graphite phase carbon nitride material of claim 1.
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