CN115463682B - Preparation and application of S-shaped crystallized carbon nitride homojunction photocatalytic material - Google Patents
Preparation and application of S-shaped crystallized carbon nitride homojunction photocatalytic material Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 32
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 28
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 claims abstract description 25
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001103 potassium chloride Substances 0.000 claims abstract description 12
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 230000005684 electric field Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 29
- 239000000047 product Substances 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000004306 triazinyl group Chemical group 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007540 photo-reduction reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carbon nitrides Chemical class 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000002737 fuel gas Substances 0.000 description 1
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- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction 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
Classifications
-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention belongs to the field of preparation of semiconductor photocatalytic materials, and particularly relates to preparation of an S-shaped crystallized carbon nitride homojunction photocatalytic material and photocatalytic CO 2 And (5) reducing application. The invention prepares the S-shaped crystallized carbon nitride homojunction photocatalytic material by taking melamine, lithium chloride and potassium chloride as raw materials and combining asynchronous crystallization and electrostatic self-assembly strategies, and explores the application of the material in photocatalysis of CO 2 Application in the field of reduction. The composite material has a 1D/2D face-to-face contact structure and comprises two crystal phases of triazine and heptazine, and the proportion of the two crystal phases can be accurately regulated and controlled. An interfacial electric field exists between the interfaces of the triazine/heptazine two crystal phases, so that photo-generated electrons are promoted to transfer according to an S type. The S-shaped homojunction can be proved by various characterizations, and is not affected by the proportion of two crystalline phases. In the application of photocatalytic carbon dioxide reduction, under the irradiation of visible light, the CO generation rate is as high as 19.38 mu mol g ‑1 h ‑1 And has 81.8. Mu. Mol g ‑1 h ‑1 Electron consumption rate of (a).
Description
Technical Field
The invention belongs to the field of preparation of semiconductor photocatalytic materials, and particularly relates to preparation of an S-shaped crystallized carbon nitride homojunction photocatalytic material and photocatalytic CO 2 And (5) reducing application.
Technical Field
Photocatalytic reduction of carbon dioxide to produce fuel gas such as methane is one of the effective measures for achieving energy conversion. However, smooth progress of the photocatalytic reaction is premised on efficient carrier capture. When the photoexcited semiconductor generates electron-hole pairs, the electrons and the holes are very easy to be combined due to the attraction of coulomb force, so that the electron-hole pairs are annihilated, the problem that the existing single-component semiconductor photocatalyst is easy to combine by photon-generated carriers is generally solved, and the catalytic efficiency is not high. In view of this, the regulation of the spatiotemporal separation of carriers in a semiconductor photocatalyst is critical to enhance the catalytic performance of the photocatalyst.
The composite semiconductor photocatalyst system has an interface electric field, and can provide additional driving force to counteract the restriction of coulomb force on the photogenerated charge carrier, so as to effectively solve the problem that the charge carrier is easy to compound. Generally, compound semiconductor photocatalytic systems are classified into type ii and type S mainly according to charge transfer modes, and are widely used for the regulation of charge transfer kinetics. More advanced than type ii electron transfer, S-type (direct Z-type) electron transfer retains a higher redox capacity in the two-component semiconductor and enables a long-lasting and effective separation of photogenerated charge carriers by interfacial electric field forces, which has been further developed in recent years. To date, designing and manipulating electrons to follow S-type transfer constitutes an attractive method of charge separation.
The crystallized carbon nitride homojunction is a semiconductor catalyst with great potential due to fewer crystal defects, good lattice matching and charge separation efficiency. Since the traditional synthesis method involves simultaneous crystallization of two crystal phases of triazine and heptazine, the obtained product often exists in the form of intramolecular homojunctions, and the synthesized crystallized carbon nitride homojunctions are all of type II according to the report in the literature. So far, the construction of triazine/heptazinyl crystallized carbon nitride S-shaped homojunction photocatalytic materials has not been reported in the literature. The preparation of S-type crystallized carbon nitride homojunctions/heterojunctions has been reported in the literature, but the homojunctions/heterojunctions formed are formed in the same crystal phase (heptazinyl) 1,2 There is no similarity to the present invention.
Disclosure of Invention
The invention prepares the triazine/heptazinyl crystallized carbon nitride S-shaped homojunction photocatalytic material by taking melamine, lithium chloride and potassium chloride as raw materials and combining asynchronous crystallization and electrostatic self-assembly strategies, and explores the photocatalytic material in photocatalysis of CO 2 Application in the field of reduction. The composite material has a 1D/2D face-to-face contact structure and comprises two crystal phases of triazine and heptazine, and the proportion of the two crystal phases can be accurately regulated and controlled. An interfacial electric field exists between the interfaces of the triazine/heptazine two crystal phases, so that photo-generated electrons are promoted to transfer according to an S type. The S-shaped homojunction can be proved by various characterizations, and is not affected by the proportion of two crystalline phases. In the second photo-catalytic stageIn the application of carbon oxide reduction, under the irradiation of visible light, the CO generation rate is as high as 19.38 mu mol g -1 h -1 And has an electron consumption rate of 81.8.
The invention aims to provide a preparation method of an S-shaped crystallized carbon nitride homojunction photocatalytic material and photocatalytic CO 2 The reduction is applied, and the proportion of the triazine and the heptazine crystalline phases can be accurately regulated and controlled. The technical scheme is as follows:
(1) Melamine, lithium chloride and potassium chloride in a certain proportion are uniformly ground, and calcined in a nitrogen atmosphere, and the calcined massive solid is washed by boiling water, filtered and dried. Synthesizing single triazine crystallized carbon nitride;
(2) Calcining a certain amount of melamine to form bulk carbon nitride, uniformly grinding the obtained bulk carbon nitride and a certain proportion of lithium chloride, calcining the obtained bulk carbon nitride under the nitrogen atmosphere, washing the calcined bulk solid with boiling water, filtering and drying. Synthesizing separate heptazine crystallized carbon nitride;
(3) Treating the heptazine crystallized carbon nitride obtained in the step (2) by dilute hydrochloric acid, dispersing the heptazine crystallized carbon nitride treated by the hydrochloric acid in 200mL of deionized water, and forming the triazine crystallized carbon nitride homogeneous-phase photocatalytic carbon dioxide reduction material of the triazine/heptazine crystallized carbon nitride by electrostatic self-assembly with the triazine crystallized carbon nitride obtained in the step (1) with negative charges on the surface. And separating, washing and drying the solid sample to obtain a final product.
In the step (1), the preparation method of the triazine/heptazinyl crystallized carbon nitride S-shaped homojunction photocatalytic material is characterized by comprising the following steps of: in the step (1), the mass ratio of the melamine to the lithium chloride to the potassium chloride is 1:4.5:5.5, the calcination temperature is 400-600 ℃, and the calcination time is 0-24 hours. The boiling water temperature for washing is 60-100deg.C, and the washing time is 0-24 hr.
In the step (2), the mass ratio of the bulk phase carbon nitride to the lithium chloride to the potassium chloride is 1:4.5:5.5, the calcination temperature is 400-600 ℃, and the calcination time is 0-24 hours. The boiling water temperature for washing is 60-100deg.C, and the washing time is 0-24 hr.
In the step (3), the concentration of the dilute hydrochloric acid is 0.5mol/L, and the treatment time of the dilute hydrochloric acid is 0-24 hours.
The invention has the beneficial effects that:
(1) The S-shaped crystallized carbon nitride homojunction photocatalytic material prepared by the invention has a 1D/2D face-to-face contact structure and has two crystal phases of triazine and heptazine, and the proportion of the two crystal phases can be accurately regulated and controlled. An interface electric field exists between the interfaces of the triazine/heptazine two crystal phases, so that photogenerated electrons are promoted to be transferred according to an S shape, and the separation of photogenerated carriers is greatly promoted. The invention provides a synthesis strategy of an S-shaped crystallized carbon nitride homogeneous-phase photocatalytic material with controllable crystal phase proportion.
(2) The S-shaped crystallized carbon nitride homojunction photocatalytic material prepared by the invention has excellent photocatalytic carbon dioxide reduction efficiency and potential application prospect in the field of photocatalytic carbon dioxide reduction.
(3) The S-shaped crystallized carbon nitride homojunction photocatalytic material prepared by the invention has potential application prospect in a light-emitting device.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample of example 1 (triazine/heptazinyl crystallized carbon nitride S-type homojunction), comparative example 1 (triazine-based crystallized carbon nitride) and comparative example 2 (heptazinyl crystallized carbon nitride) according to the present invention.
FIGS. 2a, b, c are Transmission Electron Microscope (TEM) photographs of a sample of comparative example 1, comparative example 2, example 1 according to the present invention. d, e is the high resolution transmission electron microscope pictures of comparative example 1 and comparative example 2.
FIGS. 3a, b and c are the X-ray valence band spectrum, visible light diffuse reflection pattern and ultraviolet electron energy spectrum of the samples of comparative example 1, comparative example 2 and example 1, respectively, according to the present invention. d is a schematic representation of the band positions of the triazine phase and the heptazine phase in example 1.
FIG. 4a, b shows the surface potential distribution at the interface of the triazine phase and the heptazine phase in example 1 in the dark state; c, d surface potential distribution at the interface of triazine phase and heptazine phase in example 1 under light conditions.
FIGS. 5a, b are graphs of the performance of a sample of comparative example 1, comparative example 2, example 1 in photo-reduction of carbon dioxide to carbon monoxide and methane, respectively. c is a graph of the electron consumption rate of the sample of comparative example 1, comparative example 2, example 1.
The specific embodiment is as follows:
embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to these embodiments.
Example 1:
(1) 600mg of melamine are ground with 3.3g of KCl and 2.7g of LiCl in a crucible. The uniformly ground mixture was then heated to 550 ℃ in a muffle furnace at a heating rate of 5 ℃/min and calcined in a nitrogen atmosphere for 4 hours. The obtained product is washed with boiling water, centrifuged and dried in an oven at 60 ℃ for 12 hours, and the obtained product is triazinyl crystallized carbon nitride.
(2) An amount of melamine was heated in air at a rate of 12 degrees per minute to 500 degrees celsius and calcined at constant temperature for 4 hours to obtain bulk carbon nitride. 600mg of bulk carbon nitride was taken and uniformly ground in a crucible with 3.3g KCl and 2.7g LiCl. The uniformly ground mixture was then heated to 550 ℃ in a muffle furnace at a heating rate of 5 ℃/min and calcined in a nitrogen atmosphere for 4 hours. The obtained product is washed by boiling water, centrifuged and dried in an oven at 60 ℃ for 12 hours, and the obtained product is heptazinyl crystallized carbon nitride.
(3) 450mg of heptazinyl crystallized carbon nitride is taken to be dispersed in 200mL of dilute hydrochloric acid (0.5 mol/L) solution for 1 hour, then stirred for 4 hours, filtered, washed and dried, and the collected product is the heptazinyl crystallized carbon nitride after acid treatment.
(4) 120mg of acid-treated heptazinyl crystalline carbon nitride was dispersed in 100mL of water, then 30mg of triazinyl crystalline carbon nitride was added, and the dispersion was carried out by ultrasonic dispersion for 30 minutes, followed by stirring for 4 hours. And filtering, washing and drying the mixed system product to obtain the product which is the triazine/heptazinyl crystallized carbon nitride S-shaped homojunction photocatalytic material.
Comparative example 1:
600mg of melamine are ground with 3.3g of KCl and 2.7g of LiCl in a crucible. The uniformly ground mixture was then heated to 550 ℃ in a muffle furnace at a heating rate of 5 ℃/min n and calcined in a nitrogen atmosphere for 4 hours. The obtained product is washed with boiling water, centrifuged and dried in an oven at 60 ℃ for 12 hours, and the obtained product is triazinyl crystallized carbon nitride.
Comparative example 2:
a certain amount of melamine is heated to 500 ℃ in air at a speed of 12 ℃/min per minute, and the melamine is calcined at constant temperature for 4 hours, so as to obtain bulk carbon nitride. 600mg of bulk carbon nitride was taken and uniformly ground in a crucible with 3.3g KCl and 2.7g LiCl. The uniformly ground mixture was then heated to 550 ℃ in a muffle furnace at a heating rate of 5 ℃/min and calcined in a nitrogen atmosphere for 4 hours. The obtained product is washed by boiling water, centrifuged and dried in an oven at 60 ℃ for 12 hours, and the obtained product is heptazinyl crystallized carbon nitride.
The materials obtained in comparative examples 1 to 2 were subjected to photocatalytic reduction of CO in example 1 2 The activity test comprises the following specific steps:
(1) Placing 30mg of sample in a crucible cover, adding 3ml of ethanol, and performing ultrasonic dispersion for 5min;
(2) Drying the ultrasonically dispersed sample to form a film, and then dropwise adding 0.5mL of deionized water;
(3) Checking the air tightness of the reaction, vacuumizing the reactor, and introducing CO 2 And the system pressure is kept to be about 70-80 Kpa; starting a water circulation device to ensure that the temperature of the reactor is maintained at room temperature; setting the reaction duration and period of a photocatalysis online analysis system (Perfect Light Labsolar A); starting the 300W xenon lamp to start the photocatalytic reduction of CO 2 And (5) reduction experiment. Detection of CO by gas chromatography 2 A product of the photo-reduction.
The XRD patterns of the samples of example 1, comparative example 1 and comparative example 2 of FIG. 1 can show that the XRD diffraction peaks of the triazine/heptazinyl S-type crystallized carbon nitride homojunction photocatalytic material comprise two crystal phases of triazine and heptazine, and prove that the triazine/heptazinyl crystallized carbon nitride homojunction is successfully prepared.
Fig. 2a, b, c are TEM photographs of the samples of comparative example 1, comparative example 2, and it is clear that comparative example 1 and comparative example 2 exhibit morphology of nanotubes and nanoplates, respectively, and that example 1 exhibits morphology of staggered growth of nanotubes and nanoplates. d, e is the high resolution transmission electron microscope pictures of comparative example 1 and comparative example 2. The clear lattice fringes and exact interplanar spacing reveal successful preparation of triazinyl and heptazinyl crystalline carbon nitrides.
FIGS. 3a, b and c are the X-ray valence band spectrum, visible light diffuse reflection pattern and ultraviolet electron energy spectrum of the samples of comparative example 1, comparative example 2 and example 1, respectively, according to the present invention. According to the characterized results, the energy band structures corresponding to the triazine phase and the heptazine phase in the example 1 are shown in a graph d, and due to the difference of work functions, two crystal phases exist in the built-in electric field in the example 1.
Fig. 4 clearly shows that the change in the surface potential distribution at the interface of the triazine phase and the heptazine phase in example 1 is clear by comparing the light irradiation and dark state conditions, and electrons are transferred from the triazine phase to the heptazine phase, thus proving that the triazine/heptazine-based crystallized carbon nitride homojunction is an S-type homojunction.
FIGS. 5a, b are graphs of the performance of a sample of comparative example 1, comparative example 2, example 1 in photo-reduction of carbon dioxide to carbon monoxide and methane, respectively. From the figure it can be seen that the examples show significantly enhanced photocatalytic activity thanks to the efficient separation of the photogenerated carriers by S-type electron transfer, wherein CO and CH 4 Yields of 19.38 and 5.29. Mu. Mol g, respectively -1 h -1 . c is a graph of electron consumption rate of the samples of comparative example 1, comparative example 2 and example 1, and the electron consumption rate of example 1 is highest and the surface reaction rate is faster because the S-type electron transfer inhibits carrier recombination.
Reference to the literature
1.Y.Ma,F.Liu,Y.Liu,X.Lan,Y.Zhu,J.Shi,W.Jiang,G.Wang and S.H.Pa rk,Chemical Engineering Journal,2021,414,128802.
2.S.Tang,S.Yang,Y.Chen,Y.Yang,Z.Li,L.Zi,Y.Liu,Y.Wang,Z.Li,Z.Fu and Y.Li,Carbon,2023,201,815-828.
Claims (4)
1. Homojunction photocatalyst is in photocatalysis CO 2 The application in the reduction is characterized in that: the homojunction photocatalyst consists of triazine crystallized carbon nitride and heptazine crystallized carbon nitride, the crystal phase proportion is adjustable, the electron transfer type is S-shaped, and the structure is 1D/2D; the preparation method of the homojunction photocatalyst comprises the following steps ofThe method comprises the following steps:
(1) Uniformly grinding melamine, lithium chloride and potassium chloride in a certain proportion, calcining in a nitrogen atmosphere, washing the calcined massive solid with boiling water, filtering, drying, and synthesizing single triazine crystallized carbon nitride;
(2) Calcining a certain amount of melamine to form bulk carbon nitride, uniformly grinding the obtained bulk carbon nitride and a certain proportion of lithium chloride, calcining the obtained bulk carbon nitride under the nitrogen atmosphere, washing the calcined bulk solid with boiling water, carrying out suction filtration, and drying to synthesize independent heptazine crystallized carbon nitride;
(3) Treating the heptazine crystallized carbon nitride obtained in the step (2) by dilute hydrochloric acid, dispersing the heptazine crystallized carbon nitride treated by the hydrochloric acid in 200mL of deionized water, forming a triazine crystallized carbon nitride and heptazine crystallized carbon nitride homogeneous photocatalytic carbon dioxide reduction material by electrostatic self-assembly with the triazine crystallized carbon nitride obtained in the step (1) with negative surface charge, separating, washing and drying a solid sample, and obtaining a final product.
2. The use according to claim 1, wherein: in the step (1), the mass ratio of the melamine to the lithium chloride to the potassium chloride is 1:4.5:5.5, the calcination temperature is 400-600 ℃, and the calcination time is 4-24 hours.
3. The use according to claim 1, wherein: in the step (2), the mass ratio of the bulk phase carbon nitride to the lithium chloride to the potassium chloride is 1:4.5:5.5, calcining at 400-600 ℃ for 4-24 hours.
4. The use according to claim 1, wherein: in the step (3), the concentration of the dilute hydrochloric acid is 0.5mol/L, and the treatment time of the dilute hydrochloric acid is 5-24 hours.
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| 石墨相氮化碳的光生电荷迁移调控方法及其光催化降解污染物和产氢性能;曾振兴;中国博士学位论文全文数据库 工程科技Ⅰ辑(第03期);第22页、第24页 * |
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