CN110339853B - C3N5Material, preparation method and application thereof - Google Patents
C3N5Material, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 88
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 25
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 claims abstract description 16
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011812 mixed powder Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 23
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 230000005284 excitation Effects 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
Abstract
The invention relates to C3N5A material preparation method and application thereof, belonging to the technical field of photocatalysis. The technical problem to be solved by the invention is to provide C3N5A method of preparing a material, the method comprising the steps of: a. reacting 3-amino-1, 2, 4-triazole withUniformly mixing the hexa-nitrogen heterocycles in a weight ratio of 1: 0.8-1.2 to obtain uniformly mixed powder, wherein the hexa-nitrogen heterocycles are at least one of cyanuric acid and barbituric acid; b. heating the uniformly mixed powder to 480-520 ℃, preserving heat for 2.5-3.5 h, cooling, taking out, washing and drying to obtain C3N5A material. In the invention, preparation C3N5When the material is prepared, the 3-amino-1, 2, 4-triazole and the specific hexa-nitrogen heterocycle are mixed as raw materials, the preparation method is simple, and the C obtained by the method3N5The material has good photocatalytic activity and can be widely used as a photocatalyst.
Description
Technical Field
The invention relates to C3N5A material, a preparation method and application thereof, belonging to the technical field of photocatalysis.
Background
The photocatalysis technology is a technology for catalytic reaction under light irradiation by using a photocatalyst, and is a green technology with important application prospect in the fields of energy and environment. The photocatalyst is a key of a photocatalytic technology and is a general name of chemical substances capable of playing a catalytic role under the excitation of photons, and the semiconductor photocatalyst can be excited to generate electrons and holes under the irradiation of light and generate an oxidation-reduction reaction on the surface of a semiconductor, so that the decomposition of water or the decomposition of organic pollutants is realized, and the utilization and the conversion of light energy are realized.
As a novel semiconductor material, C3N5The unique composition and structure and the characteristics of visible light catalytic activity become the hot points of research. Compared with the prior C which is more researched3N4Comparison of materials, C3N5Has higher diffusion limit current density and lower overpotential, so that the photocatalysis performance is better. At present, the method，C3N5There are some reports on the preparation method of (A), but there are few reports on the specific structure of the (A), and C prepared by different methods3N5The photocatalytic activity of the materials is not the same, which may be due to differences in the structure of the materials caused by different methods.
C3N5Can be prepared by self-assembly of 5-amino-1H-tetrazole (5-ATTZ), such as: in Young Kim et al, In the literature "ordered mesoporous C with triazole and triazine skeleton3N5And Graphene complexes thereof (Dr. in Young Kim, Sungho Kim, Dr. Xiaooyan Jin, Dr. Selvarajan Premkumar, Dr. Goutam Chandra, Dr. Nam-Suk Lee, Prof. Gurudas P.Man, Prof. Seong-Ju Hwang, Prof. Siva Umapathiy, Prof. Ajayan Vinu. Ordered Mesoporous C3N5with a Combined Triazone and Graphene hybrid for the Oxygen Reduction Reaction (ORR) [ J. in Young Kim, Sungho Kim, Dr. Xiiaoyan Ji, and J. Selvaraya-Ju H.Wang, and J. Sylva Chan Reaction (ORR) [ J. conjugated Triazole and Graphene hybrid for the Oxygen Reduction Reaction (ORR) ]].Angewandte Chemie,2018,130(52).)
C3N5Can also be prepared by using 3-amino-1, 2, 4-triazole as a raw material, for example, in patent CN109562940A, 3-amino-1, 2, 4-triazole is used as a raw material to prepare C3N5A material. The photocatalytic performance of the material prepared by the method needs to be further improved.
The Zhang YOUYU of the university of Hunan province researches on the preparation of C by using 3-amino-1, 2, 4-triazole as a raw material with the aid of NaOH3N5Materials, g-C was found to increase with NaOH concentration3N5The N vacancy is gradually increased, and excellent photocatalysis and photoelectrochemical properties are shown. (see in detail the literature "porous graphitic carbon nitrides with controlled nitrogen vacancies: ideal catalysts for enhancing the visible light degradation of contaminants", Haiyan Wang, Mingxia Li, Huan Li, Qiujun Lu, Youyu Zhang, shouzhu Yao. porous graphic carbon nitride with controllable nitride nanoparticles of pollutant visible light right [ J.].Materials& design,2018.) in addition, they also studied the preparation of C from 3-amino-1, 2, 4-triazole as the starting material with the aid of KBr3N5Materials, discovery and direct preparation of the resulting materialsIn contrast, C obtained with the aid of KBr3N5The material also exhibits significantly superior photocatalytic properties. (see the literature, salt-oriented Synthesis of mesoporous rods g-C3N5: as good photocatalysts for degrading organic pollutants, Wang, Haiyan, Li, Mingxia, Lu, Qiujun, et al.A. mesoporousrod-like g-C3N5synthesized by salt-regulated catalyst as a peroxiphoresis for degradation of organic polutant [ J].ACS SustainableChemistry&Engineering.)
Disclosure of Invention
The first technical problem solved by the invention is to provide a C3N5Compared with the existing method, the material prepared by the method has better photocatalytic performance.
Invention C3N5The preparation method of the material comprises the following steps:
a. mixing materials: uniformly mixing 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle according to the weight ratio of 1: 0.8-1.2 to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
b. and (3) calcining: heating the uniformly mixed powder, preserving heat for 2.5-3.5 h at 480-520 ℃, cooling, taking out, washing and drying to obtain C3N5A material.
Preferably, the specific operation of the step a is as follows: adding 3-amino-1, 2, 4-triazole and hexa-nitrogen heterocycle into absolute ethyl alcohol, stirring for 1-3 h, then carrying out ultrasonic treatment for 0.5-1.5 h, and drying at 60-80 ℃ to obtain uniformly mixed powder. More preferably for 2h, followed by sonication for 1h and drying at 70 ℃.
Preferably, in step a, the six-membered nitrogen heterocycle is cyanuric acid. More preferably, 3-amino-1, 2, 4-triazole and cyanuric acid are mixed in a weight ratio of 1: 1.
In another preferred mode, in the step a, the six-membered nitrogen heterocycle is cyanuric acid and barbituric acid. More preferably, the weight ratio of 3-amino-1, 2, 4-triazole to cyanuric acid to barbituric acid is 1:1: 0.1.
Preferably, in the step b, the heating rate is 3-8 ℃/min, and the preferred heating rate is 5 ℃/min.
Preferably, step a is followed by step c, wherein step c is as follows: adding the uniformly mixed powder into the aid solution, uniformly stirring, drying, and performing step b on the dried powder; the auxiliary agent is sodium hydroxide or potassium bromide.
Preferably, the concentration of the assistant solution is 0.05-0.15 g/mL, and more preferably, the concentration of the assistant solution is 0.1 g/mL.
Preferably, the weight ratio of the auxiliary agent to the 3-amino-1, 2, 4-triazole is 1: 10-20, and more preferably, the weight ratio of the auxiliary agent to the 3-amino-1, 2, 4-triazole is 1: 15.
The second technical problem solved by the invention is to provide a C3N5A material.
Invention C3N5The material is prepared by the method. As can be seen from the diffuse reflection of ultraviolet and fluorescence emission spectra, the material is similar to C prepared by the prior method3N5Compared with the material, the material has better photocatalytic activity.
The invention also provides the compound C3N5Use of the material in a photocatalyst.
C of the invention3N5The material has good photocatalytic activity and can be used in a photocatalyst. Invention C3N5The material can be used as a photocatalyst alone or in combination with other photocatalysts.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, preparation C3N5When the material is prepared, the 3-amino-1, 2, 4-triazole and the specific hexa-nitrogen heterocycle are mixed as raw materials, the preparation method is simple, and the C obtained by the method3N5The material has good photocatalytic activity and can be widely used as a photocatalyst.
Drawings
FIG. 1 shows C prepared in examples 1 to 4 of the present invention and comparative examples 1 to 23N5XRD pattern of (a).
FIG. 2 shows examples 1 to 4 of the present invention and comparative examples 1 to E2 preparation of C3N5Ultraviolet diffuse reflectance spectrum.
FIG. 3 shows C prepared in examples 1 to 4 of the present invention and comparative examples 1 to 23N5Fluorescence emission pattern under 366nm excitation.
Detailed Description
Invention C3N5The preparation method of the material comprises the following steps:
a. mixing materials: uniformly mixing 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle according to the weight ratio of 1: 0.8-1.2 to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
b. and (3) calcining: heating the uniformly mixed powder to 480-520 ℃, preserving heat for 2.5-3.5 h, cooling, taking out, washing and drying to obtain C3N5A material.
The step a is mainly used for uniformly mixing the raw materials according to the proportion, and preferably, the specific operation of the step a is as follows: adding 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle into absolute ethyl alcohol, stirring for 1-3 h, then carrying out ultrasonic treatment for 0.5-1.5 h, and drying at 60-80 ℃ to obtain uniformly mixed powder; preferably stirred for 2h, then sonicated for 1h and dried at 70 ℃.
In one embodiment, in step a, the six-membered nitrogen heterocycle is cyanuric acid. Preferably, the 3-amino-1, 2, 4-triazole and cyanuric acid are mixed uniformly in a weight ratio of 1: 1.
As another embodiment, in step a, the six-membered azacyclic ring is cyanuric acid and barbituric acid. Research shows that C is obtained after 3-amino-1, 2, 4-triazole, cyanuric acid and barbituric acid are added3N5The photocatalytic activity of the material is better than that of the material prepared by only adding 3-amino-1, 2, 4-triazole and cyanuric acid, namely adding barbituric acid, and the photocatalytic performance of the synthesized material is improved. Preferably, the weight ratio of 3-amino-1, 2, 4-triazole to cyanuric acid to barbituric acid is 1:1: 0.1.
b step is calcining to obtain C3N5And (5) material processing. The calcination of the step can be carried out in the air without protective gas, the operation is simple, and no special requirement is made on calcination equipmentFor example, the uniformly mixed powder may be directly put into a muffle furnace to be heated and calcined.
Preferably, in the step b, the heating rate is 3-8 ℃/min, and the preferred heating rate is 5 ℃/min.
Preferably, step a is followed by step c, wherein step c is as follows: adding the uniformly mixed powder into the aid solution, uniformly stirring, drying, and performing step b on the dried powder; the auxiliary agent is sodium hydroxide or potassium bromide. After addition of auxiliaries, C is obtained3N5The performance of the material is better.
Preferably, the concentration of the assistant solution is 0.05-0.15 g/mL, and more preferably, the concentration of the assistant solution is 0.1 g/mL.
Preferably, the weight ratio of the auxiliary agent to the 3-amino-1, 2, 4-triazole is 1: 10-20, and more preferably, the weight ratio of the auxiliary agent to the 3-amino-1, 2, 4-triazole is 1: 15.
Invention C3N5The material is prepared by the method. As can be seen from the diffuse reflection of ultraviolet and fluorescence emission spectra, the material is similar to C prepared by the prior method3N5Compared with the material, the material has better photocatalytic activity.
The invention also provides the compound C3N5Use of the material in a photocatalyst.
C of the invention3N5The material has good photocatalytic activity and can be used in a photocatalyst. Invention C3N5The material can be used as a photocatalyst alone or in combination with other photocatalysts.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
5g of 3-amino-1, 2, 4-triazole and 5g of cyanuric acid are each weighed out into a beaker and 100mL of absolute ethanol are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. Drying the suspension in an oven at 70 deg.C to obtain powder, and mixing the powder with the suspensionThe mixture is put into a 50mL crucible with a cover, moved to a muffle furnace, heated to 500 ℃ at a heating rate of 5 ℃/min and then kept for 3 h. After cooling, the sample was filled into a beaker and 100mL of distilled water was added, and then placed in an ultrasonic machine for ultrasonic dispersion for 3 hours, followed by centrifugation and drying of the sample to obtain C3N5The material, 3-C-1. The XRD spectrum of the material is shown in figure 1, the ultraviolet diffuse reflection spectrum is shown in figure 2, and the fluorescence emission spectrum under 366nm excitation is shown in figure 3.
Example 2
5g of 3-amino-1, 2, 4-triazole, 5g of cyanuric acid and 0.5g of barbituric acid are each weighed out into a beaker and 100mL of absolute ethanol are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. Then putting the suspension into an oven at 70 ℃ for drying to obtain white powder, putting the white powder into a crucible with a cover of 50mL, moving the crucible to a muffle furnace, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 3 h. After cooling, the sample was filled into a beaker and 100mL of distilled water was added, and then placed in an ultrasonic machine for ultrasonic dispersion for 3 hours, followed by centrifugation and drying of the sample to obtain C3N5The material is marked as 3-C-1-2. The XRD spectrum of the material is shown in figure 1, the ultraviolet diffuse reflection spectrum is shown in figure 2, and the fluorescence emission spectrum under 366nm excitation is shown in figure 3.
Example 3
4.5g of 3-amino-1, 2, 4-triazole and 4.5g of cyanuric acid are each weighed out into a beaker and 100mL of absolute ethanol are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. Then putting the suspension into a 70 ℃ oven for drying to obtain powder, adding a KBr solution (adding 3mL of distilled water into 0.3g of KBr), uniformly stirring, then putting into an 80 ℃ oven for drying to obtain a solid, transferring the solid into a 50mL crucible with a cover, transferring into a muffle furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min, and then preserving the heat for 3 h. After cooling, putting the sample into a beaker, adding 100mL of distilled water, then putting the beaker into an ultrasonic machine for ultrasonic dispersion for 3 hours, washing the sample for a plurality of times, centrifuging and drying to obtain C3N5The material, 3-C-K-1. The XRD spectrum of the material is shown in figure 1, the ultraviolet diffuse reflection spectrum is shown in figure 2, and the fluorescence emission spectrum under 366nm excitation is shown in figure 3.
Example 4
4.5g of 3-amino-1, 2, 4-triazole, 4.5g of cyanuric acid and 0.45g of barbituric acid are each weighed out into a beaker and 100mL of absolute ethanol are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. Then putting the suspension into a 70 ℃ oven for drying to obtain powder, adding a KBr solution (adding 3mL of distilled water into 0.3g of KBr), uniformly stirring, then putting into an 80 ℃ oven for drying to obtain a solid, transferring the solid into a 50mL crucible with a cover, transferring into a muffle furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min, and then preserving the heat for 3 h. After cooling, putting the sample into a beaker, adding 100mL of distilled water, then putting the beaker into an ultrasonic machine for ultrasonic dispersion for 3 hours, washing the sample for a plurality of times, centrifuging and drying to obtain C3N5The material is marked as 3-C-K-1-2. The XRD spectrum of the material is shown in figure 1, the ultraviolet diffuse reflection spectrum is shown in figure 2, and the fluorescence emission spectrum under 366nm excitation is shown in figure 3.
Comparative example 1
6g of 3-amino-1, 2, 4-triazole is weighed into a 50mL crucible with a cover, the crucible is moved to a muffle furnace, the temperature is raised to 500 ℃ at the heating rate of 5 ℃/min, and then the temperature is preserved for 3 h. After cooling, the sample was filled into a beaker and 100mL of distilled water was added, and then placed in an ultrasonic machine for ultrasonic dispersion for 3 hours, followed by centrifugation and drying of the sample to obtain C3N5The material, 3-C. The XRD spectrum of the material is shown in figure 1, the ultraviolet diffuse reflection spectrum is shown in figure 2, and the fluorescence emission spectrum under 366nm excitation is shown in figure 3.
Comparative example 2
Weighing 4.5g of 3-amino-1, 2, 4-triazole, putting into a beaker, adding a KBr solution (adding 3mL of distilled water into 0.3g of KBr), stirring uniformly, then putting into an oven at 80 ℃ for drying to obtain a solid, transferring the solid into a 50mL crucible with a cover, transferring into a muffle furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min, and then preserving the heat for 3 h. After cooling, putting the sample into a beaker, adding 100mL of distilled water, then putting the beaker into an ultrasonic machine for ultrasonic dispersion for 3 hours, washing the sample for a plurality of times, centrifuging and drying to obtain C3N5The material, 3-C-K. The XRD spectrum of the material is shown in figure 1, the ultraviolet diffuse reflection spectrum is shown in figure 2, and the fluorescence emission spectrum under 366nm excitation is shown in figure 3.
FIG. 1 shows C prepared in examples 1 to 4 of the present invention and comparative examples 1 to 23N5The XRD pattern of (A) is similar to that of C prepared by the prior art method, as can be seen from figure 13N5Compared with the materials (namely comparative examples 1-3), the material prepared by the method has the diffraction peak in XRD test and is compared with C prepared by the existing method3N5The positions of diffraction peaks of the materials are consistent, so that the C is successfully prepared by the invention3N5Materials, and C obtained by the invention3N5The XRD diffraction peak of the material is higher than that of C prepared by the prior method3N5The diffraction peak of the material is wider, which shows that the crystal form is reduced to some extent, the specific surface area is improved to some extent, and the photocatalytic performance is improved.
FIG. 2 shows C prepared in examples 1 to 4 of the present invention and comparative examples 1 to 23N5The ultraviolet diffuse reflection spectrum can be seen from the spectrum, and is similar to C prepared by the prior method3N5Compared with the material, the material prepared by the method has wider absorption spectrum range and is more beneficial to realizing photocatalysis under visible light or sunlight.
FIG. 3 shows C prepared in examples 1 to 4 of the present invention and comparative examples 1 to 23N5Fluorescence emission pattern under 366nm excitation. It is well known to those skilled in the art that when a photocatalyst is excited by light, electrons and holes are generated, wherein a part of the electrons and holes perform redox action, another part of the electrons and holes recombine, and energy is released in the form of light, while in general, when the electrons and holes recombine, fluorescence is emitted, so that the lower the fluorescence emission intensity, the lower the electron-hole recombination rate, and the higher the photocatalytic activity. As can be seen from FIG. 3, C prepared by the method of the present invention3N5The fluorescence emission intensity of the material is lower than that of C prepared by the prior method3N5Materials showing C obtained by the method of the invention3N5The material has high photocatalytic activity. The photocatalytic activity of 3-C-1-2 is better than that of 3-C-1, 3-C-K-1-2, which indicates that the C added with barbituric acid and cyanuric acid is better than that of 3-C-K-1 during the preparation3N5The material has higher photocatalytic activity than that of cyanuric acid only.In addition, the photocatalytic activity of 3-C-K-1 is better than that of 3-C-1, 3-C-K-1-2 is better than that of 3-C-1-2, which shows that the addition of the auxiliary agent potassium bromide is helpful to improve the photocatalytic activity of the material.
Claims (16)
1.C3N5The preparation method of the material is characterized by comprising the following steps:
a. mixing materials: uniformly mixing 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle according to the weight ratio of 1: 0.8-1.2 to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
b. and (3) calcining: heating the uniformly mixed powder, preserving heat for 2.5-3.5 h at 480-520 ℃, cooling, taking out, washing and drying to obtain C3N5A material.
2. C according to claim 13N5The preparation method of the material is characterized by comprising the following steps: the specific operation of the step a is as follows: adding 3-amino-1, 2, 4-triazole and hexa-nitrogen heterocycle into absolute ethyl alcohol, stirring for 1-3 h, then carrying out ultrasonic treatment for 0.5-1.5 h, and drying at 60-80 ℃ to obtain uniformly mixed powder.
3. C according to claim 23N5The preparation method of the material is characterized by comprising the following steps: stirring for 2h, then ultrasonic treating for 1h, and drying at 70 ℃.
4. C according to claim 13N5The preparation method of the material is characterized by comprising the following steps: in the step a, the six-membered nitrogen heterocycle is cyanuric acid.
5. C according to claim 43N5The preparation method of the material is characterized by comprising the following steps: 3-amino-1, 2, 4-triazole and cyanuric acid are uniformly mixed according to the weight ratio of 1: 1.
6. C according to claim 13N5The preparation method of the material is characterized by comprising the following steps: in step a, the six-membered nitrogen heterocycle isCyanuric acid and barbituric acid.
7. C according to claim 63N5The preparation method of the material is characterized by comprising the following steps: according to the weight ratio, 3-amino-1, 2, 4-triazole, cyanuric acid and barbituric acid are 1:1: 0.1.
8. C according to claim 13N5The preparation method of the material is characterized by comprising the following steps: in the step b, the heating rate is 3-8 ℃/min.
9. C according to claim 83N5The preparation method of the material is characterized by comprising the following steps: in the step b, the heating rate is 5 ℃/min.
10. C according to any one of claims 1 to 93N5The preparation method of the material is characterized by comprising the following steps: c, after the step a, performing step c, wherein the step c comprises the following steps: adding the uniformly mixed powder into the aid solution, uniformly stirring, drying, and performing step b on the dried powder; the auxiliary agent is sodium hydroxide or potassium bromide.
11. The C of claim 103N5The preparation method of the material is characterized by comprising the following steps: the concentration of the auxiliary agent solution is 0.05-0.15 g/mL.
12. C according to claim 113N5The preparation method of the material is characterized by comprising the following steps: the concentration of the assistant solution is 0.1 g/mL.
13. The C of claim 103N5The preparation method of the material is characterized by comprising the following steps: the weight ratio of the auxiliary agent to the 3-amino-1, 2, 4-triazole is 1: 10-20.
14. C according to claim 133N5The preparation method of the material is characterized by comprising the following steps: auxiliaries and 3-ammoniaThe weight ratio of the 1,2, 4-triazole group is 1: 15.
15. C according to any one of claims 1 to 143N5Preparation method of material C3N5A material.
16. C of claim 153N5Use of the material in a photocatalyst.
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| CN110560125B (en) * | 2019-09-06 | 2020-10-27 | 北京交通大学 | N-g-C3N4Preparation method and application of visible light catalytic material |
| CN111330620A (en) * | 2020-03-11 | 2020-06-26 | 中国科学技术大学 | Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof |
| CN113075272B (en) * | 2021-04-01 | 2022-07-22 | 西南大学 | Novel photo-induced electrochemical biosensor constructed based on carbon, nitrogen and nitrogen |
| CN113042090B (en) * | 2021-04-01 | 2023-05-19 | 辽宁石油化工大学 | Nonmetallic photocatalyst with charge transfer chain and preparation method and application thereof |
| CN113333012B (en) * | 2021-06-02 | 2022-08-19 | 成都理工大学 | Bi-doped porous carbon nitrogen compound and preparation method thereof |
| CN113210005B (en) * | 2021-06-02 | 2022-07-26 | 成都理工大学 | Cl-doped C 3 N 5 And method for preparing the same |
| CN113893845B (en) * | 2021-11-01 | 2024-03-22 | 塔里木大学 | Yb-doped g-C 3 N 5 Composite photocatalytic material and preparation method and application thereof |
| CN114192179B (en) * | 2021-12-31 | 2024-03-26 | 宁波碧城生态科技有限公司 | Preparation method, product and application of nitrogen-defect carbon nitride composite silver phosphate photocatalyst |
| CN114904547B (en) * | 2022-04-11 | 2024-02-02 | 塔里木大学 | Mixed crystal phase WO 3 @g-C 3 N 5 Preparation method of composite photocatalyst |
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