CN111672528A - Modified carbon nitride photocatalyst and preparation method and application thereof - Google Patents
Modified carbon nitride photocatalyst and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 30
- 150000002367 halogens Chemical class 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
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- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 6
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- 238000010438 heat treatment Methods 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 10
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 9
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
The invention discloses a modified carbon nitride photocatalyst, which takes graphite-phase carbon nitride as a main body and is doped with sulfur and halogen elements, wherein the mass fraction of the halogen elements is 0.1-40%; the catalyst is formed by mixing and calcining a sulfur-containing compound and a halogen-containing compound, and can be applied to photocatalytic degradation of organic pollutants in water. The preparation method of the modified carbon nitride is simple and easy to implement, has small danger, has no specific requirement on gas atmosphere, enhances the separation capability of photoproduction holes and electrons of the graphite-phase carbon nitride by introducing sulfur and halogen impurities, and can reduce the forbidden bandwidth; meanwhile, the introduced halogen influences the electronic potential of a valence band, so that the photocatalytic performance of the material is improved; the obtained modified carbon nitride has good stability and can be used as a catalyst to greatly improve the degradation capability of organic pollutants in water under visible light, so that the modified carbon nitride can be widely applied to treatment of printing and dyeing wastewater and chemical wastewater.
Description
Technical Field
The invention belongs to the field of material preparation and photocatalysis, and particularly relates to a catalytic material taking carbon nitride as a main body and application thereof in photocatalytic degradation of pollutants.
Background
With the increasing pollution in recent years, the environmental protection problem is more and more emphasized by people. Among them, photocatalytic oxidation technology is more and more favored because of its green and high-efficiency characteristics. With the development of photocatalytic materials, graphite-phase carbon nitride has received attention as a new photocatalyst. This material has the following advantages: (1) the band gap is 2.7eV, so that certain visible light response is realized; (2) the catalyst has high chemical stability and thermal stability, so the catalyst has good catalytic stability; (3) due to its non-metallic construction, it is relatively inexpensive and readily available. But at the same time, the graphite-phase carbon nitride also has the problem to be solved in the application process of photocatalysis (1) because of the forbidden bandwidth of 2.7eV, the utilization rate of visible light is extremely low, and only a small amount of visible light can excite the separation of photo-generated electrons and holes; (2) meanwhile, the photo-generated holes and electrons are easy to recombine, and the conduction efficiency of photo-generated carriers is low. In view of the above application defects, studies on modification based on carbon nitride have attracted attention of scholars, including doping modification, construction of composite heterojunction semiconductors, and the like, but the commonly reported modification methods are complicated in preparation process and high in synthesis cost, so that development of a cheap and easily available high-efficiency carbon nitride catalytic material is urgently needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified carbon nitride photocatalyst with higher electron and hole separation capability.
The technical scheme provided by the invention is to provide a modified carbon nitride photocatalyst, which takes graphite-phase carbon nitride as a main body and is doped with sulfur and halogen elements, wherein the mass fraction of the halogen elements is 0.1-40%.
Preferably, the halogen element is chlorine element.
The invention further provides a preparation method of the modified carbon nitride, which comprises the following steps:
s1, mixing and grinding a sulfur-containing compound and a halogen-containing compound;
s2, transferring the mixture obtained in the step S1 into a closed crucible, and heating and calcining.
Wherein the mass ratio of the sulfur-containing compound to the halogen-containing compound in step S1 is 1: 0.01-0.4; preferably, the sulfur-containing compound is thiourea and the halogen-containing compound is ammonium chloride.
In the step S2, the heating and calcining process is to heat up to 450-650 ℃ at a heating rate of 2-10 ℃/min and calcine for 2-4 h.
The invention also aims to provide the application of the modified carbon nitride in photocatalytic degradation of organic pollutants in water, wherein the organic pollutants comprise rhodamine B, 4-nitrophenol and the like.
The invention has the advantages and beneficial effects that:
1, the separation capability of photoproduction holes and electrons of graphite-phase carbon nitride is enhanced by introducing sulfur and halogen impurities, and the forbidden bandwidth can be reduced; meanwhile, the introduced halogen influences the electronic potential of a valence band, so that the photocatalytic performance of the material is improved;
2, the method successfully carries out doping modification on graphite-like phase carbon nitride by adopting a sulfur-halogen co-doping technology which is simple and easy to implement and low in raw material, and prepares and synthesizes the carbon nitride catalytic material with high visible light catalytic activity efficiency; the preparation method is simple and easy to implement, has small danger, has no specific requirements on gas atmosphere, and the obtained material has good photocatalytic effect, so the method is a synthesis method with application prospect;
3 under visible light, the degradation capability of the modified carbon nitride as a catalyst on organic pollutants in water, such as rhodamine B and 4-nitrophenol, is greatly improved, so that the modified carbon nitride can be widely applied to printing and dyeing wastewater and chemical wastewater treatment.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of undoped modified carbon nitride (labeled as carbon nitride in the figure) and modified carbon nitride (labeled as sulfur-halogen co-doped carbon nitride in the figure) prepared in example 1.
Fig. 2 is a graph of the uv-vis diffuse reflectance spectra of undoped modified carbon nitride (labeled as carbon nitride in the figure) and modified carbon nitride (labeled as sulfur-halogen co-doped carbon nitride in the figure) obtained in example 1.
FIG. 3 is a graph of time-degradation of undoped modified carbon nitride (labeled as carbon nitride in the figure) and modified carbon nitride (labeled as sulfur-halogen co-doped carbon nitride in the figure) prepared in example 1 for rhodamine B in water.
Figure 4 is a graph of the time-degradation of undoped modified carbon nitride (labeled carbon nitride in the figure) and the modified carbon nitride prepared in example 1 (labeled sulfur-halogen co-doped carbon nitride in the figure) for 4-nitrophenol in water.
FIG. 5 is a graph of the cyclic degradation of undoped modified carbon nitride (labeled as carbon nitride in the figure) and modified carbon nitride (labeled as sulfur-halogen co-doped carbon nitride in the figure) prepared in example 1 for rhodamine B in water.
FIG. 6 is a graph of the cyclic degradation of undoped modified carbon nitride (labeled carbon nitride in the figure) with the modified carbon nitride prepared in example 1 (labeled sulfur-halogen co-doped carbon nitride in the figure) versus 4-nitrophenol in water.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
Step 1: respectively weighing 10g of thiourea and 0.1g of ammonium chloride, adding the two substances into a mortar, and grinding;
step 2: adding the ground mixed powder into a corundum crucible, covering the corundum crucible with a cover, and performing primary sealing treatment; heating to 550 ℃ in a muffle furnace at the heating rate of 2 ℃/min, preserving the heat at 550 ℃ for 2 hours, and cooling to room temperature to obtain the sample.
Example 2
Step 1: respectively weighing 10g of thiourea and 0.4g of ammonium chloride, adding the two substances into a mortar, and grinding;
step 2: adding the ground mixed powder into a corundum crucible, covering the corundum crucible with a cover, and performing primary sealing treatment; heating to 450 ℃ in a muffle furnace at the heating rate of 4 ℃/min, preserving the heat for 4 hours at 550 ℃, and cooling to room temperature to obtain the sample.
Example 3
Step 1: respectively weighing 10g of thiourea and 1g of ammonium chloride, adding the two substances into a mortar, and grinding;
step 2: adding the ground mixed powder into a corundum crucible, covering the corundum crucible with a cover, and performing primary sealing treatment; heating to 500 ℃ in a muffle furnace at the heating rate of 7 ℃/min, preserving the heat for 3 hours at 550 ℃, and cooling to room temperature to obtain the sample.
Example 4
Step 1: respectively weighing 10g of thiourea and 4g of ammonium chloride, adding the two substances into a mortar, and grinding;
step 2: adding the ground mixed powder into a corundum crucible, covering the corundum crucible with a cover, and performing primary sealing treatment; heating to 650 ℃ at the heating rate of 10 ℃/min in a muffle furnace, preserving the heat for 2 hours at 550 ℃, and cooling to room temperature to obtain the sample. Comparative example
Step 1: 10g of melamine is put into a corundum crucible, and the corundum crucible is covered with a cover to carry out primary sealing treatment;
step 2: heating to 550 ℃ at the heating rate of 2 ℃/min in a muffle furnace, preserving the heat at 550 ℃ for 2 hours, and cooling to room temperature to obtain a sample, namely the graphite-like phase carbon nitride g-C3N4。
And (3) performing characterization and photocatalytic activity evaluation on the prepared sample (taking the sample of example 1 as an example, and the results of the samples of other examples are similar and are not repeated):
1. characterization of modified carbon nitride
Figure 1 is an X-ray diffraction pattern of undoped modified carbon nitride (labeled carbon nitride in the figure) and the modified carbon nitride prepared in example 1 (labeled sulfur-halogen co-doped carbon nitride in the figure). As can be seen from fig. 1, the characteristic peak of the mixed doped sample is similar to that of pure carbon nitride, which proves that the co-doped sample has a structure consistent with that of pure carbon nitride. However, pure carbon nitride has characteristic peaks of 13.0 ° and 27.7 ° in XRD diffraction, and characteristic peaks of co-doping of S and Cl of 12.7 ° and 27.6 °, corresponding to the (100) crystal plane and the (002) crystal plane, respectively. It can be known from the peak position that, compared with pure graphite phase carbon nitride, the co-doping of S, Cl makes the interplanar spacing larger, and the forbidden bandwidth narrower, so that the electron transition energy is reduced, the photo-generated electrons-holes are easier to generate and the stability is better, that is, the catalytic performance of the carbon nitride modified by doping sulfur and halogen is improved.
Fig. 2 is a graph of the uv-vis diffuse reflectance spectra of undoped modified carbon nitride (labeled as carbon nitride in the figure) and modified carbon nitride (labeled as sulfur-halogen co-doped carbon nitride in the figure) obtained in example 1. As can be seen from fig. 2, the change in the micro-crystal structure of the sulfur-halogen modified carbon nitride affects the band gap width and the valence band electron potential, so that electrons are more easily excited by light, and thus the modified carbon nitride has a stronger light absorption property than pure carbon nitride.
2. Photocatalytic degradation of rhodamine B dye in water by sample
0.025g of samples prepared in example 1 and comparative example are weighed respectively, added into 100ml of rhodamine B solution with the concentration of 10mg/L respectively, then a magnetic rotor is added, the solution is placed in a dark room and stirred for 30min to enable the carbon nitride material to reach adsorption balance, the solution is placed under a xenon lamp light source with a filter (lambda is more than or equal to 420nm), degradation of rhodamine B is measured by a blank control, the comparative example and the example 1, and the result is shown in figure 3. From the measurement result, after the visible light is irradiated for 40 minutes, rhodamine in water is basically unchanged under the condition of not adding a catalyst, the degradation rate of the added unmodified carbon nitride group is 24.9%, and after the modified doped carbon nitride of the embodiment 1 is added, the degradation rate of rhodamine B in water reaches 98.2%, and the degradation efficiency is obviously improved.
The degradation stability test is to centrifuge the reaction solution to obtain the previously weighed solid sample of example 1, repeatedly rinse it with deionized water, and centrifuge. Finally, the sample was placed in an oven and dried at 60 ℃ for 8 hours, and as a result, the sample still showed good stability after 5 cycles as shown in fig. 5.
3. Photocatalytic degradation of 4-nitrophenol in water by sample
0.2g of the samples prepared in example 1 and comparative example were weighed, added to 50ml of 5 mg/L4-nitrophenol solution, added to a magnetic rotor, stirred in a dark room for 60min to allow the carbon nitride material to reach adsorption equilibrium, the solution was placed under a xenon lamp light source with a filter (lambda. is not less than 420nm), and the degradation of 4-nitrophenol in the blank control, comparative example and example 1 was measured, with the results shown in FIG. 4. From the measurement results, it can be seen that after 120 minutes of visible light irradiation, 4-nitrophenol in water is not changed basically without adding a catalyst, the degradation rate is 18.7% when unmodified carbon nitride is added, and after the modified doped carbon nitride of example 1 is added, the degradation rate of 4-nitrophenol in water reaches 79.1%, and the degradation efficiency is obviously improved.
The degradation stability test is to centrifuge the reaction solution to obtain the previously weighed solid sample of example 1, repeatedly rinse it with deionized water, and centrifuge. Finally, the sample was placed in an oven and dried at 60 ℃ for 8 hours, and as a result, the sample still showed good stability after 5 cycles as shown in fig. 6.
Materials, reagents and experimental equipment related to the embodiment of the invention are all commercial products conforming to the field of photocatalytic materials unless otherwise specified.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and these modifications and decorations shall also fall within the protection scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (8)
1. A modified carbon nitride photocatalyst is characterized in that: the graphite-phase carbon nitride is used as a main body and is doped with sulfur and halogen elements, wherein the mass fraction of the halogen elements is 0.1-40%.
2. The modified carbon nitride photocatalyst according to claim 1, wherein the halogen element is chlorine element.
3. The method for preparing a modified carbon nitride photocatalyst according to any one of claims 1 to 2, characterized by comprising the steps of:
s1, mixing and grinding a sulfur-containing compound and a halogen-containing compound;
s2, transferring the mixture obtained in the step S1 into a closed crucible, and heating and calcining.
4. The method for preparing a modified carbon nitride photocatalyst according to claim 3, wherein the mass ratio of the sulfur-containing compound to the halogen-containing compound in step S1 is 1: 0.01-0.4.
5. The method of claim 3, wherein in step S1, the sulfur-containing compound is thiourea, and the halogen-containing compound is ammonium chloride.
6. The preparation method of the modified carbon nitride photocatalyst according to claim 3, wherein the heating and calcining process of step S2 is to heat up to 450-650 ℃ at a heating rate of 2-10 ℃/min for 2-4 h.
7. Use of the modified carbon nitride photocatalyst according to any one of claims 1 to 2 for photocatalytic degradation of organic pollutants in water.
8. The use of the modified carbon nitride photocatalyst as claimed in claim 7, wherein the organic contaminant is one of rhodamine B or 4-nitrophenol.
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| CN112264072A (en) * | 2020-10-27 | 2021-01-26 | 福建农林大学 | Preparation method of modified nano-cellulose thermally-linked and serially-connected carbon nitride photosynthetic hydrogen peroxide |
| CN115814834A (en) * | 2022-11-30 | 2023-03-21 | 江汉大学 | Simple modification method for enhancing performance of graphite carbon nitride material through solvent post-treatment |
| CN116216665A (en) * | 2023-02-01 | 2023-06-06 | 四川农业大学 | Method for degrading trimethoprim by using advanced oxidation technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669760A (en) * | 2016-12-28 | 2017-05-17 | 广州中国科学院沈阳自动化研究所分所 | Sulfur-doped carbon nitride photocatalyst as well as preparation method and application thereof |
| CN107961807A (en) * | 2017-11-24 | 2018-04-27 | 江苏大学 | A kind of preparation method of the pre-assembled azotized carbon nano pipe photochemical catalyst of supermolecule |
| CN108654665A (en) * | 2018-03-30 | 2018-10-16 | 广东工业大学 | A kind of ultra-thin carbon nitride photocatalyst and its preparation method and application |
-
2019
- 2019-04-11 CN CN201910286860.9A patent/CN111672528A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669760A (en) * | 2016-12-28 | 2017-05-17 | 广州中国科学院沈阳自动化研究所分所 | Sulfur-doped carbon nitride photocatalyst as well as preparation method and application thereof |
| CN107961807A (en) * | 2017-11-24 | 2018-04-27 | 江苏大学 | A kind of preparation method of the pre-assembled azotized carbon nano pipe photochemical catalyst of supermolecule |
| CN108654665A (en) * | 2018-03-30 | 2018-10-16 | 广东工业大学 | A kind of ultra-thin carbon nitride photocatalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| BICHENG ZHU等: ""First principle investigation of halogen-doped monolayer g-C3N4 photocatalyst"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264072A (en) * | 2020-10-27 | 2021-01-26 | 福建农林大学 | Preparation method of modified nano-cellulose thermally-linked and serially-connected carbon nitride photosynthetic hydrogen peroxide |
| CN112264072B (en) * | 2020-10-27 | 2022-12-20 | 福建农林大学 | Preparation method of modified nano-cellulose thermally-linked and serially-connected carbon nitride photosynthetic hydrogen peroxide |
| CN115814834A (en) * | 2022-11-30 | 2023-03-21 | 江汉大学 | Simple modification method for enhancing performance of graphite carbon nitride material through solvent post-treatment |
| CN116216665A (en) * | 2023-02-01 | 2023-06-06 | 四川农业大学 | Method for degrading trimethoprim by using advanced oxidation technology |
| CN116216665B (en) * | 2023-02-01 | 2024-02-23 | 四川农业大学 | Method for degrading trimethoprim by using advanced oxidation technology |
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