CN111841597A - Composite photocatalytic material of cobalt-loaded nitrogen-doped graphene oxide/mesoporous thin-layer carbon nitride and preparation method thereof - Google Patents
Composite photocatalytic material of cobalt-loaded nitrogen-doped graphene oxide/mesoporous thin-layer carbon nitride and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 30
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 20
- 239000010941 cobalt Substances 0.000 title claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 239000001257 hydrogen Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000707 layer-by-layer assembly Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 42
- 239000010410 layer Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a composite photocatalytic material of cobalt-loaded aza-oxidized graphene/mesoporous thin-layer carbon nitride and a preparation method thereof, wherein the preparation method comprises the following steps: (1) and uniformly mixing cobalt chloride and the graphene oxide solution, and freeze-drying. (2) And calcining the aza in a tube furnace under the conditions of argon and ammonia gas. (3) And (3) carrying out electrostatic self-assembly on the cobalt-loaded aza-graphene oxide and the mesoporous thin-layer carbon nitride, and carrying out annealing treatment to obtain the cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride composite photocatalytic material. The preparation method can be applied to various metal materials, is simple and convenient, and the obtained cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride photocatalytic material can effectively improve the electron transmission efficiency of the surface interface and is beneficial to improving the performance of photocatalytic decomposition of water to produce hydrogen.
Description
Technical Field
The research field of the invention focuses on energy catalysis and material preparation, and particularly relates to a cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride composite photocatalytic material and a preparation method thereof, and hydrogen is produced by decomposing water through energy photocatalysis.
Background
Energy and environment are important issues in this century, and concern the sustainable development of mankind. The hydrogen is used as secondary energy, and has considerable combustion performance and green and clean combustion products, so that the hydrogen has great application prospect. Therefore, many researchers strive to develop hydrogen in the fields of fuel cells, electrocatalysis and photocatalysis.
The photocatalytic hydrogen production decomposition technology refers to that electrons absorb energy and are excited to jump to a conduction band and holes are left in a valence band under the irradiation of visible light by a semiconductor catalyst, so that the separation of electron-hole pairs is promoted, and the electrons and water undergo an oxidation-reduction reaction on the surface of a semiconductor material to finally produce hydrogen.
However, the hydrogen production performance of the traditional semiconductor catalyst in water is not ideal, so that a promoter is introduced to help electrons of the excited transition to be better transmitted to the surface of the semiconductor catalyst to participate in the reaction. Platinum (Pt), the best performing promoter at present, has been reported in a number of studies on platinum as a promoter. The orange osmanthus, etc. adopts titanium dioxide (TiO)2) Study of Pt/TiO as support2The active site for photolyzing water to produce hydrogen is provided in TiO 2Platinum oxide of the surface. Al-Thabaiti et Al use self-assembly method to grow platinum particles in situ on TiO2In the wall of the nano tube, Pt/TiO is further improved2The photocatalytic water decomposition hydrogen production performance of the system. Xuqujen et al used cadmium sulfide (CdS) as a carrier to regulate the morphology of platinum nanoparticles and study the influence of the cadmium sulfide (CdS) on the performance of photolyzed water. Irvine et al used non-goldBelongs to graphite phase carbon nitride as a carrier, and researches on reduction of Pt/g-C of platinum nanoparticles under different environments3N4The influence of the photolysis on the hydrogen production performance.
In fact, the key influence of platinum as a promoter on the hydrogen production activity of the photocatalyst is its size and dispersibility. When individual platinum nanoparticles are dispersed on a carrier, agglomeration often occurs easily, and the platinum is reduced in size, increased in specific surface area and sharply increased in surface free energy, so that the agglomeration phenomenon is more serious and even leads to catalyst deactivation. Spherical, two-dimensional, thin layers are often used, and the mesopores are used as carriers, rather than semiconductor materials with large surface areas, to promote better dispersion of platinum nanoparticles. In addition, the carrier may be subjected to a surface modification treatment so that the platinum nanoparticles can be uniformly dispersed on the carrier. Polyvinylpyrrolidone (PVP) is a common surfactant and stabilizer, the size and dispersity of platinum nanoparticles can be well controlled, but the limitation is that PVP is difficult to remove in subsequent treatment, so that the later synthesis or performance characterization is affected.
Therefore, the research on a simple method capable of uniformly dispersing the platinum with the ultra-small size in the pore channel structure of the mesoporous semiconductor material at the present stage has important significance in the field of photocatalytic decomposition of hydrogen production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride composite photocatalytic material with ultra-small platinum loaded in a mesoporous material pore channel structure. The preparation method is simple and effective, and the photocatalyst loaded with platinum prepared by selecting the mesoporous material with large specific surface area as the carrier has excellent performance of photocatalytic water decomposition to produce hydrogen.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride composite photocatalytic material comprises the following steps:
(1) weighing melamine, putting the melamine into a ceramic crucible provided with a nickel screen, putting the ceramic crucible into a muffle furnace for calcining at 550 ℃, pouring the product into hydrochloric acid aqueous solution to remove residual metallic nickel, and drying to obtain mesoporous thin-layer carbon nitride;
(2) weighing graphene oxide, putting the graphene oxide into a beaker, adding ultrapure water, carrying out ultrasonic treatment until the graphene oxide is completely dispersed, and adding CoCl 2Aqueous solution, sonication, followed by freeze drying;
(3) placing the sample subjected to freeze drying into a tubular furnace, and calcining at high temperature in the atmosphere of argon and ammonia gas to obtain cobalt-loaded aza-oxidized graphene;
(4) weighing cobalt-loaded aza-graphene oxide, adding absolute ethyl alcohol, ultrasonically dispersing uniformly, weighing mesoporous thin-layer carbon nitride, adding the mesoporous thin-layer carbon nitride, ultrasonically stirring continuously, centrifuging, and vacuum drying at 60 ℃;
(5) and grinding the dried sample into powder, transferring the powder into a ceramic ark, and annealing under the argon condition to finally obtain the cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride composite photocatalytic material.
Preferably, in the above-mentioned production method: the concentration of the hydrochloric acid used in the step (1) is 6M.
Preferably, in the above-mentioned production method: CoCl in step (2)2The concentration of the aqueous solution was 3 mg/mL.
Preferably, in the above-mentioned production method: in the step (3), the calcining temperature of the tubular furnace is 750 ℃, the heating rate is 15 ℃/min, and the mixing volume ratio of argon and ammonia gas is 3: 1.
Preferably, in the above-mentioned production method: the annealing temperature of the tubular furnace in the step (5) is 300 ℃, and the heating rate is 5 ℃/min.
Preferably, in the above-mentioned production method: the weight ratio of the melamine to the graphene oxide to the mesoporous thin-layer carbon nitride is 25-35:0.8-1.2: 1-3.
The cobalt monoatomic group is anchored on the aza-graphene and is compounded with the mesoporous thin-layer carbon nitride through electrostatic self-assembly, so that the surface interface electron transmission efficiency is improved, and the aim of improving the performance of photocatalytic decomposition of water hydrogen is fulfilled. The preparation method can be applied to various metal materials, is simple and convenient, and the obtained cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride photocatalytic material can effectively improve the electron transmission efficiency of the surface interface and is beneficial to improving the performance of photocatalytic decomposition of water to produce hydrogen.
Drawings
Fig. 1 is an SEM image of a cobalt-supported aza-graphene oxide/mesoporous thin-layer carbon nitride photocatalytic material prepared in example 1 of the present invention;
fig. 2 is a hydrogen production activity diagram of the cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride photocatalytic material prepared in example 1 of the present invention.
Detailed description of the invention
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
Weighing 100 mg of mesoporous TiO2Adding 37mL of deionized water to disperse the solution, adding 13 mL of chloroplatinic acid solution (1 mg/mL), carrying out ultrasonic treatment for 30 min, placing the filter membrane at the filter opening of the sand core funnel, opening a vacuum pump, and pouring the mixed solution into the sand core funnel at a constant speed. After draining, the filtrate was recovered and poured into the funnel again, and this was repeated 10 times. Adding a small amount of deionized water to clean chloroplatinic acid on the surface layer, after suction filtration is finished, putting the filtered product into a vacuum drying oven to dry for 7-8 h at 60 ℃. Drying, slightly grinding, dispersing the solid powder in 10 mL of deionized water, adding 10 mL of sodium borohydride solution, stirring for 3h for reduction, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 7-8 h to obtain Pt/TiO 2. (Pt/TiO obtained in this example)2Has good photocatalytic hydrogen production performance, and the size of the Pt nano-particles is 4-7 nm. But TiO 22Has a forbidden band width of 3.2 eV, which is more easily excited by light than carbon nitride (-2.7 eV) of the non-metallic phase.
Example 2 (in addition to example 1, the kind of mesoporous material was changed)
Weighing 100 mg of mesoporous graphite phase carbon nitride (mpg-C)3N4) Adding 41mL of deionized water to disperse the solution, adding 9 mL of chloroplatinic acid solution (1 mg/mL), carrying out ultrasonic treatment for 20 min, placing the filter membrane at the filter opening of the sand core funnel, opening a vacuum pump, and pouring the mixed solution into the sand core funnel at a constant speed. After draining, the filtrate was recovered and poured into the funnel again, and this was repeated 10 times. Adding a small amount of deionized water to clean chloroplatinic acid on the surface layer, after suction filtration is finished, putting the filtered product into a vacuum drying oven to dry for 7-8 h at 60 ℃. Drying, slightly grinding, dispersing the solid powder in 10 mL of deionized water, adding 10 mL of sodium borohydride solution, stirring for 3 h for reduction, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 7-8 h to obtain Pt/mpg-C3N4. (Pt/mpg-C obtained in this example) 3N4Easier to be excited by light than example 1, and the Pt nanoparticles size was 3-5 nm).
Example 3 (varying the concentration of chloroplatinic acid solution based on example 2)
Weighing 100 mg of mpg-C3N4Adding 37 mL of deionized water to disperse the solution, adding 13 mL of chloroplatinic acid solution (0.2 mg/mL), carrying out ultrasonic treatment for 20 min, placing the filter membrane at the filter opening of the sand core funnel, opening a vacuum pump, and pouring the mixed solution into the sand core funnel at a constant speed. After draining, the filtrate was recovered and poured into the funnel again, and this was repeated 10 times. Adding a small amount of deionized water to clean chloroplatinic acid on the surface layer, after suction filtration is finished, putting the filtered product into a vacuum drying oven to dry for 7-8 h at 60 ℃. After drying, slightly grinding, dispersing the solid powder in 10 mL of deionized water, adding 5 mL of sodium borohydride solution, stirring for 3h for reduction, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 7-8 h to obtain Pt/mpg-C3N4. (the Pt nanoparticles obtained in this example were 1-3nm in size, and the Pt size was further reduced compared to example 2. in addition, for an equivalent mpg-C3N4And a chloroplatinic acid solution, and found that Pt/mpg-C obtained by the present invention was used 3N4The photocatalytic hydrogen production activity of (a) is higher than that of a sample obtained by photoreduction).
Claims (7)
1. A preparation method of a cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride composite photocatalytic material is characterized by comprising the following steps of: the method comprises the following steps:
(1) weighing melamine, putting the melamine into a ceramic crucible provided with a nickel screen, putting the ceramic crucible into a muffle furnace for calcining at 550 ℃, pouring the product into hydrochloric acid aqueous solution to remove residual metallic nickel, and drying to obtain mesoporous thin-layer carbon nitride;
(2) weighing graphene oxide, putting the graphene oxide into a beaker, adding ultrapure water, carrying out ultrasonic treatment until the graphene oxide is completely dispersed, and adding CoCl2Aqueous solution, sonication, followed by freeze drying;
(3) placing the sample subjected to freeze drying into a tubular furnace, and calcining at high temperature in the atmosphere of argon and ammonia gas to obtain cobalt-loaded aza-oxidized graphene;
(4) weighing cobalt-loaded aza-graphene oxide, adding absolute ethyl alcohol, ultrasonically dispersing uniformly, weighing mesoporous thin-layer carbon nitride, adding the mesoporous thin-layer carbon nitride, ultrasonically stirring continuously, centrifuging, and vacuum drying at 60 ℃;
(5) and grinding the dried sample into powder, transferring the powder into a ceramic ark, and annealing under the argon condition to finally obtain the cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride composite photocatalytic material.
2. The method of claim 1, wherein: the concentration of the hydrochloric acid used in the step (1) is 6M.
3. The method of claim 1, wherein: CoCl in step (2)2The concentration of the aqueous solution was 3 mg/mL.
4. The method of claim 1, wherein: in the step (3), the calcining temperature of the tubular furnace is 750 ℃, the heating rate is 15 ℃/min, and the mixing volume ratio of argon and ammonia gas is 3: 1.
5. The method of claim 1, wherein: the annealing temperature of the tubular furnace in the step (5) is 300 ℃, and the heating rate is 5 ℃/min.
6. The method of claim 1, wherein: the weight ratio of the melamine to the graphene oxide to the mesoporous thin-layer carbon nitride is 25-35:0.8-1.2: 1-3.
7. A composite photocatalytic material of cobalt-loaded aza-graphene oxide/mesoporous thin-layer carbon nitride, which is characterized by being prepared by the method of any one of claims 1 to 6.
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