CN115463682A - Preparation and application of S-type crystallized carbon nitride homojunction photocatalytic material - Google Patents
Preparation and application of S-type 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 41
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 claims abstract description 37
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 33
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 28
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001103 potassium chloride Substances 0.000 claims abstract description 14
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 14
- 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
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
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- 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
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carbon nitrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 125000004306 triazinyl group Chemical group 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
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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-type crystallized carbon nitride homojunction photocatalytic material and photocatalytic CO 2 And (4) reduction application. The S-type crystallized carbon nitride homojunction photocatalytic material is prepared by taking melamine, lithium chloride and potassium chloride as raw materials and combining asynchronous crystallization and electrostatic self-assembly strategies, and the application of the S-type crystallized carbon nitride homojunction photocatalytic material in photocatalysis of CO is explored 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 interface electric field exists between the interfaces of the triazine/heptazine two crystal phases, and the photoproduction electrons are promoted to be transferred according to an S shape. The S-type homojunction can be proved by various characterizations, and the S-type homojunction is not influenced by the proportion of two crystal phases. In the application of photocatalytic carbon dioxide reduction, the CO generation rate is as high as 19.38 mu mol g under the irradiation of visible light ‑1 h ‑1 And has 81.8. Mu. Mol g ‑1 h ‑1 The rate of electron consumption.
Description
Technical Field
The invention belongs to the field of preparation of semiconductor photocatalytic materials, and particularly relates to S-type crystallized carbon nitridePreparation of homojunction photocatalytic material and photocatalytic CO 2 And (4) reduction application.
Technical Field
Photocatalytic reduction of carbon dioxide to produce fuel gas such as methane is one of the effective measures for energy conversion. However, the smooth progress of the photocatalytic reaction is premised on efficient carrier capture. When the light-excited semiconductor generates electron hole pairs, electrons and holes are easy to recombine due to the attraction of coulomb force, so that annihilation is caused, the problem that photo-generated carriers are easy to recombine commonly exists in the existing single-component semiconductor photocatalyst, and the catalytic efficiency is not high. In view of this, regulation of the space-time separation of carriers in semiconductor photocatalysts is crucial to enhancing the catalytic performance of photocatalysts.
The composite semiconductor photocatalyst system has an interface electric field and can provide additional driving force to counteract the constraint of coulomb force on photo-generated charge carriers, thereby effectively solving the problem that the charge carriers are easy to compound. In general, composite semiconductor photocatalytic systems are largely classified into type ii and S according to charge transfer modes, and are widely used for the regulation of charge transfer kinetics. The method is more advanced than the II type electron transfer, the S type (direct Z type) electron transfer reserves higher oxidation reduction capability in a bi-component semiconductor, and can durably and effectively separate photo-generated charge carriers through interfacial electric field force, and further development is achieved in recent years. To date, designing and manipulating electrons to follow an S-type transfer constitutes an attractive method of charge separation.
Crystallized carbon nitride homojunctions are a potentially huge semiconductor catalyst due to fewer crystal defects, good lattice matching, and charge separation efficiency. Because the traditional synthesis method involves the 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 type II according to the reports of the literature. So far, no literature reports exist for constructing triazine/heptazine based crystallized carbon nitride S-type homojunction photocatalytic materials. The preparation of S-type crystallized carbon nitride homojunction/heterojunction is reported in the literature, but the homojunction/heterojunction is formed by forming at the same crystal phase (heptazine phase) 1,2 There is no similarity to the present invention.
Disclosure of Invention
The S-type homojunction photocatalytic material of triazine/heptazine-based crystallized carbon nitride is prepared by taking melamine, lithium chloride and potassium chloride as raw materials and combining asynchronous crystallization and electrostatic self-assembly strategies, and the application of the S-type homojunction photocatalytic material in photocatalysis of CO is explored 2 Application in the field of reduction. The composite material has a 1D/2D face-to-face contact structure and comprises triazine and heptazine crystal phases, 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, and the photoproduced electrons are promoted to be transferred according to an S shape. The S-type homojunction can be proved by various characterizations, and the S-type homojunction is not influenced by the proportion of two crystal phases. In the application of photocatalytic carbon dioxide reduction, the CO generation rate is as high as 19.38 mu mol g under the irradiation of visible light -1 h -1 And has an electron consumption rate of 81.8.
The invention aims to provide a preparation method of an S-type crystallized carbon nitride homojunction photocatalytic material and photocatalytic CO 2 Reduction application, and the proportion of the two crystal phases of triazine and heptazine can be accurately regulated and controlled. The following technical scheme is adopted:
(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, and drying. Synthesizing single triazine crystallized carbon nitride;
(2) Calcining a certain amount of melamine to form bulk-phase carbon nitride, uniformly grinding the obtained bulk-phase carbon nitride, a certain proportion of lithium chloride and potassium chloride, calcining in a nitrogen atmosphere, washing the calcined blocky 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) with dilute hydrochloric acid, dispersing the heptazine crystallized carbon nitride after hydrochloric acid treatment in 200mL of ionized water, and performing electrostatic self-assembly on the heptazine crystallized carbon nitride and the triazine crystallized carbon nitride with the negatively charged surface obtained in the step (1) to form the triazine/heptazine crystallized carbon nitride homogeneous junction photocatalytic carbon dioxide reduction material. And (4) separating, washing and drying the solid sample to obtain a final product.
In the step (1), the preparation method of the triazine/heptazine based crystallized carbon nitride S-type homojunction photocatalytic material is characterized by comprising the following steps: in the step (1), the mass ratio of melamine to lithium chloride to potassium chloride is 1:4.5:5.5, the calcining temperature is 400-600 ℃, and the calcining time is 0-24 hours. The temperature of boiling water for washing is 60-100 ℃, and the washing time is 0-24 hours.
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 calcining temperature is 400-600 ℃, and the calcining time is 0-24 hours. The temperature of boiling water for washing is 60-100 ℃, and the washing time is 0-24 hours.
In the step (3), the concentration of the dilute hydrochloric acid is 0.5mol/L, and the time duration of the dilute hydrochloric acid treatment is 0-24 hours.
The invention has the beneficial effects that:
(1) The S-type 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 the transfer of photogenerated electrons is promoted 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 homojunction 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 has potential application prospects 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 luminescent devices.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of samples of example 1 (triazine/heptazine based crystalline carbon nitride S type homojunction) of the present invention, comparative example 1 (triazine based crystalline carbon nitride), and comparative example 2 (heptazine based crystalline carbon nitride).
FIGS. 2a, b and c are Transmission Electron Microscope (TEM) photographs of comparative examples 1, 2 and 1 according to the present invention. d, e are high resolution transmission electron microscopy pictures of comparative example 1 and comparative example 2.
FIGS. 3a, b, c are X-ray valence band spectra, visible light diffuse reflectance spectra, ultraviolet photoelectron spectra of the samples of comparative example 1, comparative example 2, and example 1 of the present invention, respectively. d is a schematic illustration of the band positions of the triazine phase and the heptazine phase in example 1.
Figure 4a, b surface potential distribution at the interface of the triazine and heptazine phases in example 1 under dark state conditions; c, d surface potential distribution at the interface of the triazine phase and the heptazine phase in example 1 under light conditions.
5a, b are graphs of the performance of the samples of comparative example 1, comparative example 2, and example 1 in photo-reduction of carbon dioxide to carbon monoxide and methane, respectively. c is a graph of electron consumption rates for the samples of comparative example 1, comparative example 2, and example 1.
The specific implementation mode is as follows:
embodiments of the present invention will be described in detail below with reference to the drawings, but the scope of the present invention is not limited to these embodiments.
Example 1:
(1) 600mg of melamine was 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. And washing the obtained product with boiling water, centrifuging, and drying in a 60-degree oven for 12 hours to obtain the triazine-based crystallized carbon nitride.
(2) Certain amount of melamine is heated to 500 ℃ in air at the speed of 12 degrees per minute, and the melamine is calcined for 4 hours at constant temperature to obtain the bulk phase carbon nitride. 600mg of bulk-phase carbon nitride was uniformly ground with 3.3g of KCl and 2.7g of LiCl in a crucible. Then the uniformly ground mixture is heated to 550 ℃ in a muffle furnace at the heating rate of 5 ℃/min and calcined for 4 hours in the nitrogen atmosphere. The obtained product is washed by boiling water, centrifuged and dried in an oven at 60 ℃ for 12 hours, and the obtained product is heptazine-based crystallized carbon nitride.
(3) 450mg of heptazinyl crystalline carbon nitride is dispersed in 200mL of dilute hydrochloric acid (0.5 mol/L) solution for ultrasonic dispersion for 1h, then stirred for 4 h, filtered, washed and dried, and the collected product is the heptazinyl crystalline carbon nitride after acid treatment.
(4) 120mg of acid-treated heptazinyl crystalline carbon nitride was dispersed in 100mL of water, and then 30mg of triazinyl crystalline carbon nitride was added, and ultrasonic dispersion was carried out for 30 minutes, followed by stirring for 4 hours. And (3) carrying out suction filtration, washing and drying on the product of the mixed system to obtain the triazine/heptazine based crystallized carbon nitride S-type homojunction photocatalytic material.
Comparative example 1:
600mg of melamine was ground with 3.3g of KCl and 2.7g of LiCl in a crucible. Then, the uniformly ground mixture is heated to 550 ℃ in a muffle furnace at a heating rate of 5 ℃/min n, and is calcined for 4 hours in a nitrogen atmosphere. Washing the obtained product with boiling water, centrifuging, and drying in an oven at 60 ℃ for 12 hours to obtain the triazine-based crystallized carbon nitride.
Comparative example 2:
heating a certain amount of melamine to 500 ℃ in the air at the speed of 12 ℃/min per minute, and calcining at constant temperature for 4 hours to obtain the bulk-phase carbon nitride. 600mg of bulk-phase carbon nitride was uniformly ground with 3.3g of KCl and 2.7g of LiCl in a crucible. Then the uniformly ground mixture is heated to 550 ℃ in a muffle furnace at the heating rate of 5 ℃/min and calcined for 4 hours in the nitrogen atmosphere. The obtained product is washed by boiling water, centrifuged and dried in an oven at 60 ℃ for 12 hours to obtain the heptazine-based crystallized carbon nitride.
Photocatalytic reduction of CO was carried out on the materials obtained in the above example 1, comparative examples 1 to 2 2 The activity test comprises the following specific steps:
(1) Placing 30mg sample in a crucible cover, adding 3ml ethanol, and ultrasonically dispersing for 5min;
(2) Drying the sample subjected to ultrasonic dispersion to form a film, and then dropwise adding 0.5mL of deionized water;
(3) Checking the airtightness of the reaction, evacuating the reactor and then 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 photocatalytic online analysis system (Perfect Light laboratory 6A); starting a 300W xenon lamp to start photocatalytic reduction of CO 2 And (4) performing a reduction experiment. Detection of CO by gas chromatography 2 The product of photoreduction.
FIG. 1 is an XRD pattern of samples of example 1, comparative example 1 and comparative example 2, and it can be seen that XRD diffraction peaks of triazine/heptazine based S-type crystalline carbon nitride homojunction photocatalytic materials comprise two crystal phases of triazine and heptazine, which proves that triazine/heptazine based crystalline carbon nitride homojunctions are successfully prepared.
FIGS. 2a, b and c are TEM photographs of samples of comparative example 1, comparative example 2 and example 1, and it can be clearly seen that comparative example 1 and comparative example 2 respectively present morphologies of nanotubes and nanosheets, and example 1 presents a morphology in which nanotubes and nanosheets are grown alternately. d, e are high resolution transmission electron microscopy pictures of comparative example 1 and comparative example 2. The clear lattice fringes and exact interplanar spacing reveal the successful preparation of triazine-based and heptazine-based crystalline carbon nitrides.
FIGS. 3a, b, c are X-ray valence band spectra, visible light diffuse reflectance spectra, ultraviolet photoelectron spectra of the samples of comparative example 1, comparative example 2, and example 1 of the present invention, respectively. According to the results, the corresponding band structures of the triazine phase and the heptazine phase in example 1 are shown in fig. d, and due to the difference of work functions, a built-in electric field exists between the two crystal phases in example 1.
Fig. 4 clearly shows that electrons are transferred from the triazine phase to the heptazine phase by comparing the change in the surface potential distribution at the interface of the triazine phase and the heptazine phase in example 1 under light and dark conditions, thus demonstrating that the triazine/heptazine based crystalline carbon nitride homojunction is an S-type homojunction.
FIGS. 5a and b are graphs of the performance of the photo-reduction of carbon dioxide to carbon monoxide and methane for the samples of comparative example 1, comparative example 2, and example 1, respectively. It can be seen from the figure that the examples exhibit a significantly enhanced photocatalytic activity thanks to the efficient separation of the photogenerated carriers by transfer of the S-type electrons, with CO and CH 4 The yield of the product respectively reaches 19.38 and 5.29 mu mol g -1 h -1 . c is a graph of the electron consumption rate of the samples of comparative example 1, comparative example 2 and example 1, and since the electron transfer of the S-type inhibits the carrier recombination, the electron consumption rate of example 1 is the highest and the surface reaction rate is faster.
Reference to the literature
1.Y.Ma,F.Liu,Y.Liu,X.Lan,Y.Zhu,J.Shi,W.Jiang,G.Wang and S.H.Park,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 (5)
1. Homojunction photocatalytic CO 2 A reducing material, characterized by: the homojunction consists of triazine and heptazine crystallized carbon nitride, the crystal phase proportion is adjustable, the electron transfer type is S type, and the structure is 1D/2D.
2. The method for preparing the S-shaped crystallized carbon nitride homojunction photocatalytic material as claimed in claim 1, wherein: the 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, and drying. Synthesizing single triazine crystallized carbon nitride;
(2) Calcining a certain amount of melamine to form bulk-phase carbon nitride, uniformly grinding the obtained bulk-phase carbon nitride with a certain proportion of lithium chloride and potassium chloride, calcining in a nitrogen atmosphere, washing the calcined massive solid with boiling water, filtering, and drying. Synthesizing single heptazine crystallized carbon nitride;
(3) Treating the heptazine crystallized carbon nitride obtained in the step (2) with dilute hydrochloric acid, dispersing the heptazine crystallized carbon nitride after hydrochloric acid treatment in 200mL of ionized water, and forming the S-shaped crystallized carbon nitride homojunction photocatalytic carbon dioxide reduction material with the triazine crystallized carbon nitride obtained in the step (1) with negative surface through electrostatic self-assembly. And (4) separating, washing and drying the solid sample to obtain a final product.
3. The method for preparing S-type crystallized carbon nitride homojunction photocatalytic material according to claim 2, wherein: in the step (1), the mass ratio of melamine to lithium chloride to potassium chloride is 1:4.5:5.5, the calcining temperature is 400-600 ℃, and the calcining time is 0-24 hours. The temperature of boiling water for washing is 60-100 ℃, and the washing time is 0-24 hours.
4. The method for preparing S-type crystallized carbon nitride homojunction photocatalytic material according to claim 2, 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, the calcining temperature is 400-600 ℃, and the calcining time is 0-24 hours. The temperature of boiling water for washing is 60-100 ℃, and the washing time is 0-24 hours.
5. The method for preparing S-type crystallized carbon nitride homojunction photocatalytic material according to claim 2, wherein: in the step (3), the concentration of the dilute hydrochloric acid is 0.5mol/L, and the time duration of the dilute hydrochloric acid treatment is 0-24 hours.
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| CN115084315A (en) * | 2022-06-14 | 2022-09-20 | 哈尔滨工业大学 | Preparation method of homojunction ultraviolet photoelectric detector based on zinc oxide quantum dots |
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