CN111792629A - Method for preparing red crystallized carbon nitride, red crystallized carbon nitride and application - Google Patents
Method for preparing red crystallized carbon nitride, red crystallized carbon nitride and application Download PDFInfo
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- CN111792629A CN111792629A CN202010694315.6A CN202010694315A CN111792629A CN 111792629 A CN111792629 A CN 111792629A CN 202010694315 A CN202010694315 A CN 202010694315A CN 111792629 A CN111792629 A CN 111792629A
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 91
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
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- 230000009467 reduction Effects 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
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- 150000003841 chloride salts Chemical class 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
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- 239000001103 potassium chloride Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 5
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 5
- 229960001553 phloroglucinol Drugs 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 239000004065 semiconductor Substances 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
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- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/39—Photocatalytic properties
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- C01B3/042—Decomposition of water
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- C01B2203/02—Processes for making hydrogen or synthesis gas
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Abstract
The invention provides a method for preparing red crystallized carbon nitride, the red crystallized carbon nitride and application, the method comprises the following steps: the carbon nitride precursor is subjected to thermal polymerization reaction in the presence of a chloride template and copolymer molecules to prepare red crystallized carbon nitride. The invention solves the problems of low light absorption utilization efficiency and poor crystallinity of the carbon nitride photocatalyst. The prepared red crystallized carbon nitride has the advantages of high crystallinity, wide spectral response and the like, can utilize sunlight to the maximum extent, and is expected to be applied to reactions such as large-scale photocatalytic water splitting hydrogen production, carbon dioxide reduction, nitrogen fixation, organic synthesis and the like.
Description
Technical Field
The invention relates to the field of preparation of photocatalytic materials, in particular to a method for preparing red crystallized carbon nitride, the red crystallized carbon nitride and application.
Background
Polymer semiconductor Carbon Nitride (CN) has attracted much attention due to its advantages such as unique semiconductor band structure, excellent chemical stability, and no metal component. As with most conjugated polymer photocatalysts, the semiconducting properties of CN stem from a large pi-conjugated system, which depends largely on its degree of polymerization and crystallinity. CN is generally obtained by thermal polymerization from a nitrogen-containing precursor which is inexpensive and readily available. However, due to the limited mobility of the reaction intermediates, the conventional CN thermal polymerization process always faces the problem of incomplete polymerization, resulting in its amorphous structure. In the amorphous structure, adjacent one-dimensional polymer heptazine ring chains are connected through hydrogen bonds to form a two-dimensional arrangement (see fig. 1), and the transfer of photogenerated carriers on a polymer plane is seriously hindered. In addition, due to the characteristic of high exciton recombination energy of the polymer, the photogenerated electron-hole recombination is serious and the quantum efficiency is low. More importantly, the specific energy band structure determines the sunlight energy of which the sunlight utilization range is only 460nm and less than 10%, and the large-scale popularization and application in the energy photocatalysis field are severely restricted. As shown in fig. 2, it is estimated that the conversion efficiency of solar energy to hydrogen energy is at least 10% and has industrial application value. To achieve a solar-hydrogen conversion efficiency of 10%, the light absorption range of the semiconductor material is 520nm or more and the apparent quantum efficiency is 100%. Unfortunately, the common yellowish CN is not likely to meet this requirement, and to date there are no materials that can meet the minimum requirements for solar-hydrogen conversion efficiency.
Accordingly, the prior art remains to be improved and developed.
Disclosure of Invention
In view of the defects of crystallinity and light absorption of carbon nitride, the invention aims to provide a method for preparing carbon nitride with wide spectral response and high crystallinity, and aims to solve the problems of low light absorption utilization efficiency and poor crystallinity of the existing common light yellow carbon nitride photocatalyst.
The technical scheme of the invention is as follows:
a method for preparing red crystallized carbon nitride, comprising the steps of: the carbon nitride precursor is subjected to thermal polymerization reaction in the presence of a chloride template and copolymer molecules to prepare red crystallized carbon nitride.
Optionally, the mass ratio of the carbon nitride precursor to the chloride salt template to the copolymer molecule is 10:1: 0.1-10: 10: 5.
Optionally, the temperature of the thermal polymerization reaction is between 400 and 650 ℃.
Optionally, the time of the thermal polymerization reaction is between 3 and 12 hours.
Optionally, the carbon nitride precursor is urea, cyanamide, dicyandiamide, thiourea or melamine.
Optionally, the chloride salt template is one or more of potassium chloride, sodium chloride, and lithium chloride.
Optionally, the co-molecule is oxalic acid, malonic acid, acetic acid, phloroglucinol, or barbituric acid.
The red crystallized carbon nitride is prepared by the method.
The invention relates to application of red crystallized carbon nitride as a photocatalyst.
The invention relates to application of red crystallized carbon nitride as a photocatalyst in photocatalytic water splitting hydrogen production, carbon dioxide reduction, nitrogen fixation and organic synthesis.
Has the advantages that: the invention utilizes the thermal polymerization reaction of the carbon nitride precursor under the condition of the existence of a chloride template and copolymer molecules, thereby preparing the red crystallized carbon nitride with wide spectral response and high crystallinity. The invention takes the carbon nitride with wide spectral response and high crystallinity as the photocatalyst, can utilize sunlight to the maximum extent, obtains high activity of generating hydrogen by photocatalytic decomposition, and realizes the effective utilization and capture of the sunlight.
Drawings
FIG. 1 is a molecular structure diagram of an amorphous carbon nitride polymer.
Fig. 2 is a graph showing a relationship between solar energy-hydrogen energy conversion efficiency, apparent quantum efficiency, and absorption wavelength.
FIG. 3 is a solid UV diffuse reflectance spectrum of oxygen-doped red crystallized carbon nitride synthesized in an embodiment of the present invention.
In fig. 4, a, b and c are transmission electron microscopy, high resolution and selected area electron diffraction patterns of the oxygen-doped red crystallized carbon nitride synthesized in the embodiment of the present invention, respectively.
FIG. 5 is a graph of the performance of photolysis of water to produce hydrogen for oxygen-doped red crystallized carbon nitride of greater than 500nm synthesized in the embodiments of the present invention.
Detailed Description
The invention provides a method for preparing red crystallized carbon nitride, red crystallized carbon nitride and application. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The existing common light yellow carbon nitride photocatalyst has low light absorption and utilization efficiency and poor crystallinity, and cannot meet the minimum requirement on solar energy-hydrogen conversion efficiency.
Based on the above, the inventor researches and discovers that the absorption range of red crystallized carbon nitride which has wide spectral response and is controllably prepared is expanded from 460nm to 700nm, and the solar energy which can be utilized is increased from 10% to 45%. On the other hand, molten salt is used as a solvent and a template, so that the polymerization process is remarkably accelerated, the polymerization degree and crystallinity of carbon nitride are improved, defects, disordered structures and the recombination center of a photon-generated carrier are reduced, and the apparent quantum efficiency of photocatalytic hydrogen production is improved. When the photoresponse range of the red crystallized carbon nitride is more than 700nm and the quantum efficiency reaches 40 percent, the minimum requirement of solar energy-hydrogen conversion efficiency can be met, thereby realizing the industrial application value.
Specifically, an embodiment of the present invention provides a method for preparing red crystallized carbon nitride, including the steps of: the carbon nitride precursor is subjected to thermal polymerization reaction in the presence of a chloride template and copolymer molecules to prepare red crystallized carbon nitride.
According to the embodiment of the invention, the red crystallized carbon nitride with wide spectral response and high crystallinity is prepared by performing thermal polymerization reaction on the carbon nitride precursor in the presence of a chloride template and copolymer molecules. On one hand, oxygen elements, benzene rings and pyrimidine rings are introduced into a carbon nitride skeleton for doping, the chemical composition and partial molecular structure of the carbon nitride skeleton are adjusted on the molecular level, a series of polymer photocatalysts with a continuously adjustable pi conjugated system are prepared, the absorption range of the polymer photocatalysts is expanded from 460nm to 700nm, and the solar energy capable of being utilized is increased from 10% to 45%. On the other hand, molten salt is used as a solvent and a template, so that the thermal polymerization process is remarkably accelerated, the polymerization degree and crystallinity of carbon nitride are improved, defects, disordered structures and the recombination center of a photon-generated carrier are reduced, and the apparent quantum efficiency of photocatalytic hydrogen production is improved. According to the embodiment of the invention, the wide spectral response and the high-crystallinity carbon nitride are used as the photocatalyst, so that sunlight can be utilized to the maximum extent, high activity of hydrogen generated by photocatalytic decomposition of water is obtained, and effective utilization and capture of the sunlight are realized.
In one embodiment, the mass ratio of the carbon nitride precursor to the chloride salt template to the co-polymer molecule is between 10:1:0.1 and 10:10: 5. Taking carbon nitride precursor as urea, chloride salt template as potassium chloride and copolymer molecule as oxalic acid as an example, the optimal mass ratio of the photocatalytic hydrogen production activity is 10:10: 1.
In one embodiment, the temperature of the thermal polymerization reaction is between 400 and 650 ℃. Taking carbon nitride precursor as urea, chloride salt template as potassium chloride and copolymer molecule as oxalic acid as an example, the thermal polymerization reaction temperature with optimal photocatalytic hydrogen production activity is 600 ℃.
In one embodiment, the thermal polymerization reaction time is between 3 and 12 hours. Taking carbon nitride precursor as urea, chloride salt template as potassium chloride and copolymer molecule as oxalic acid as an example, the thermal polymerization reaction time with optimal photocatalytic hydrogen production activity is 6 h.
In one embodiment, the carbon nitride precursor is urea, cyanamide, dicyandiamide, thiourea, melamine, or the like, but is not limited thereto.
In one embodiment, the chloride salt template is one or more of potassium chloride, sodium chloride, lithium chloride, and the like, but is not limited thereto.
In the embodiment of the present invention, the copolymer molecule is a small molecule, for example, the copolymer molecule is oxalic acid, malonic acid, acetic acid, phloroglucinol or barbituric acid, but not limited thereto.
The red crystallized carbon nitride is prepared by the method provided by the embodiment of the invention.
The invention discloses application of red crystallized carbon nitride as a photocatalyst.
The red crystallized carbon nitride provided by the embodiment of the invention is applied as a photocatalyst in photocatalytic water splitting hydrogen production, carbon dioxide reduction, nitrogen fixation and organic synthesis.
The red crystallized carbon nitride disclosed by the embodiment of the invention has the advantages of high crystallinity, wide spectral response and the like, can utilize sunlight to the maximum extent, and is expected to be applied to reactions such as large-scale photocatalytic water splitting hydrogen production, carbon dioxide reduction, nitrogen fixation, organic synthesis and the like.
The present invention will be described in detail below with reference to specific examples.
Taking urea as a carbon nitride precursor, potassium chloride as a chloride salt template and oxalic acid or phloroglucinol as a small copolymerization molecule as an example, the red crystallized carbon nitride doped with oxygen and benzene ring can be respectively obtained, and the specific preparation method comprises the following steps:
(1) controllable preparation of oxygen-doped red crystallized carbon nitride
Uniformly mixing 10g of urea, 10g of potassium chloride and 1g of oxalic acid in a 50mL crucible at room temperature, then transferring the mixture into a muffle furnace, preserving the heat at 600 ℃ for 6 hours, naturally cooling the mixture to the room temperature, and carrying out suction filtration and washing on the obtained oxygen-doped red powder for multiple times by using deionized water. Finally, the oxygen-doped red powder obtained after washing was dried in vacuum at 70 ℃ for further use. The characterization of the prepared oxygen-doped red crystallized carbon nitride is shown in figures 3-4. FIG. 3 is a graph showing the UV diffuse reflectance spectra of oxygen-doped red crystallized carbon nitride obtained by adding different amounts of oxalic acid. With the increase of the added amount of oxalic acid, the visible light absorption edge obviously extends from 460nm to 700nm, even in a near infrared region, the visible light absorption edge has certain light absorption, and the color of the product gradually changes from light yellow to orange red, red and dark red. In fig. 4, a, b and c are transmission electron microscope, high resolution and selected area electron diffraction patterns of the oxygen-doped red crystalline carbon nitride, respectively, and thus it can be seen that the carbon nitride maintains very good crystallinity.
(2) Controllable preparation of benzene ring doped red crystallized carbon nitride
By adopting the synthesis conditions similar to those of oxygen-doped red crystallized carbon nitride, when the mass of the copolymerized micromolecule phloroglucinol is 0.1g, the benzene ring-doped red crystallized carbon nitride can be obtained.
(3) Preparation of other red crystallized carbon nitrides
When the carbon nitride precursor is cyanamide, dicyandiamide, thiourea or melamine, the thermal polymerization temperature is 400-650 ℃, and the chloride template is one or more of potassium chloride, sodium chloride, lithium chloride and the like, the corresponding red crystallized carbon nitride can be obtained through similar synthesis steps.
(4) Triethanolamine is used as a cavity sacrificial agent, and hydrogen is generated by photocatalytic decomposition of water as follows:
50mg of prepared red crystallized carbon nitride is taken as a photocatalyst, 50mL of 20 vol% triethanolamine solution is taken as a hole sacrificial agent solution, the solution is transferred into a quartz glass reaction tank, and ultrasonic treatment is carried out for 30 min. Then, a chloroplatinic acid solution is added, and a xenon lamp is used for illuminating and loading 3.0 wt% of Pt nano particles as a cocatalyst. An online hydrogen production system is adopted, and the amount of produced hydrogen is measured by an online gas chromatograph under the irradiation conditions of a 300W xenon lamp and a UVCUT-500nm optical filter, so that the hydrogen production performance of the photocatalyst is represented. FIG. 5 is a graph showing the performance of photolysis of water to produce hydrogen of oxygen-doped red crystallized carbon nitride with a wavelength greater than 500nm, wherein the hydrogen production activity of the carbon nitride is improved by 45 times compared with that of common carbon nitride.
In conclusion, the invention develops a method for preparing red crystallized carbon nitride, which prepares the red crystallized carbon nitride by performing thermal polymerization reaction on a carbon nitride precursor in the presence of a chloride template and a small copolymerized molecule, and solves the problem of low light absorption and utilization efficiency of a carbon nitride photocatalyst. The obtained photocatalyst has the advantages of high crystallinity, wide spectral response and the like, so that sunlight can be utilized to the maximum extent, and high activity of photocatalytic decomposition of water to produce hydrogen is obtained.
It should be understood that the application of the present invention is not limited to the above examples, and can also be applied to reactions such as carbon dioxide reduction, nitrogen fixation, and organic synthesis. Modifications and variations will occur to those skilled in the art in light of the foregoing description, and it is intended to cover all such modifications and variations as fall within the true spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method of preparing red crystalline carbon nitride, comprising the steps of: the carbon nitride precursor is subjected to thermal polymerization reaction in the presence of a chloride template and copolymer molecules to prepare red crystallized carbon nitride.
2. The method for preparing red crystallized carbon nitride according to claim 1, wherein the mass ratio of the carbon nitride precursor, the chloride salt template and the copolymer molecule is 10:1: 0.1-10: 10: 5.
3. The method of claim 1, wherein the thermal polymerization temperature is between 400 ℃ and 650 ℃.
4. The method for preparing red crystallized carbon nitride according to claim 1, wherein the time of the thermal polymerization reaction is between 3 and 12 hours.
5. The method for preparing red crystallized carbon nitride according to claim 1, wherein the carbon nitride precursor is urea, cyanamide, dicyandiamide, thiourea or melamine.
6. The method of claim 1, wherein the chloride salt template is one or more of potassium chloride, sodium chloride, and lithium chloride.
7. The method of claim 1, wherein the co-polymer molecule is oxalic acid, malonic acid, acetic acid, phloroglucinol, or barbituric acid.
8. A red crystalline carbon nitride, characterized in that it is obtained by a process according to any one of claims 1 to 7.
9. Use of the red crystalline carbon nitride of claim 8 as a photocatalyst.
10. The use of the red crystalline carbon nitride of claim 8 as a photocatalyst in photocatalytic water splitting for hydrogen production, carbon dioxide reduction, nitrogen fixation, and organic synthesis.
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| WO2023010175A1 (en) * | 2021-08-04 | 2023-02-09 | The University Of Newcastle | Carbon nitrides with highly crystalline framework and process for producing same |
| CN115155641A (en) * | 2022-07-22 | 2022-10-11 | 东北大学 | Oxygen atom in-situ self-doped high-crystallinity carbon nitride photocatalyst and preparation method thereof |
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