CN110560120A - Preparation method of porous carbon nitride material, porous carbon nitride material and application thereof - Google Patents
Preparation method of porous carbon nitride material, porous carbon nitride material and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 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 abstract description 21
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000001782 photodegradation Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 239000008247 solid mixture Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- -1 small-molecule nitrogen-containing compound Chemical class 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 abstract description 3
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- 238000005303 weighing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
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- 239000003054 catalyst Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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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
-
- 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention relates to a preparation method of a porous carbon nitride material, the porous carbon nitride material and application thereof. The method comprises the steps of taking cyanuric acid and a small-molecule nitrogen-containing compound as raw materials, firstly weighing metered cyanuric acid and the small-molecule nitrogen-containing compound, grinding and mixing uniformly, putting the mixture into a crucible with a cover, putting the crucible into a muffle furnace for roasting, heating the muffle furnace to 540-560 ℃ at the speed of 3-10 ℃/min, preserving heat for 3-5 h, and naturally cooling to obtain the porous carbon nitride material; the mass ratio of the cyanuric acid to the small-molecule nitrogen-containing compound is 1: (1-6). The method can simplify the preparation process, reduce the production cost and the pollution to the environment, and improve the product yield; the prepared porous carbon nitride material has large comparative area, can effectively catalyze and photodegrade rhodamine B, has high catalytic activity and good repeatability, and has potential utilization value in the aspect of sewage treatment.
Description
Technical Field
the invention belongs to the technical field of preparation and application of materials, and particularly relates to a preparation method of a porous carbon nitride material, the porous carbon nitride material and application of the porous carbon nitride material.
Background
The carbon nitride is a novel photocatalytic material and has the advantages of high stability, low price, environmental protection and the like. The band gap width of the carbon nitride is about 2.7eV, the carbon nitride can absorb more visible light and has stronger oxidation-reduction capability, so the carbon nitride has wide application prospects in the aspects of photocatalytic degradation of organic pollutants, photocatalytic decomposition of water for hydrogen production, photocatalytic reduction of carbon dioxide and the like. The carbon nitride is prepared by thermal polymerization of melamine or dicyandiamide generally, but the carbon nitride prepared by the method has small specific surface area and lower activity. The carbon nitride prepared by thermal polymerization of urea or thiourea has a large specific surface area, but the yield of the product is about 5% and the yield of the carbon nitride is very low. Therefore, how to efficiently prepare carbon nitride with large specific surface area has been the focus of research.
The preparation of porous carbon nitride by a template method is a common method. The patent with publication number CN108654672A discloses a preparation method and application of a formic acid hydrogen production catalyst, which uses mesoporous silicon as a hard template, carbon tetrachloride as a carbon source and ethylenediamine as a nitrogen source to synthesize mesoporous carbon nitride, and then uses hydrofluoric acid to etch and remove the template, and uses strong corrosive hydrofluoric acid in the preparation process, which is not beneficial to environmental protection. Wang and Wang, etc. adopt a block copolymer and a nonionic surfactant as a soft template to prepare the nano-porous carbon nitride (WangY, Wang X, Antoniettim, Zhang Y. ChemSusChem,2010,3(4): 435-439), but the soft template has higher price and is not beneficial to large-scale production. The patent with publication number CN107758635A discloses a controlled synthesis method of graphene-like carbon nitride ultrathin nanosheets, which is to obtain carbon nitride nanosheets by taking melamine, cyanuric acid and dicyandiamide as raw materials and boric acid or boron oxide as a form control agent through hydrothermal and microwave radiation. The patent with publication number CN105664835A discloses a method for batch preparation of porous carbon nitride material assisted by organic carboxylic acid, which uses melamine as raw material, and organic carboxylic acid such as acetic acid, oxalic acid, benzoic acid or salicylic acid as auxiliary raw material, and adopts a hydrothermal-calcination two-step method to obtain porous carbon nitride material. However, the organic acid or the inorganic acid is only used as a pore-forming agent, which causes a certain waste, not only pollutes the environment, but also increases the production cost. Therefore, the development of a method for efficiently preparing carbon nitride, which has low cost, environmental friendliness and simple process, is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of a porous carbon nitride material, the porous carbon nitride material and application thereof, wherein the method can simplify the preparation process, reduce the production cost and the pollution to the environment and improve the product yield; the prepared porous carbon nitride material has large comparative area and can effectively catalyze photodegradation of rhodamine B.
In order to achieve the aim, the preparation method of the porous carbon nitride material comprises the following steps:
Grinding the metered cyanuric acid and the small molecular nitrogen-containing compound in a mortar, transferring the obtained solid mixture into a crucible with a cover, placing the crucible in a muffle furnace for roasting, heating the muffle furnace to 540-560 ℃ at the speed of 3-10 ℃/min, preserving the temperature for 3-5 h, and naturally cooling to obtain the porous carbon nitride material; the mass ratio of the cyanuric acid to the small molecular nitrogen-containing compound is 1: (1-6).
preferably, the small molecular nitrogen-containing compound is one or more of urea, thiourea, dicyandiamide and cyanamide;
Preferably, the mass ratio between the cyanuric acid and the small molecule nitrogen-containing compound is 1: 3.
preferably, the temperature of the muffle furnace is increased to 550 ℃ at the speed of 6 ℃/min, and the temperature is kept for 4 h.
A porous carbon nitride material is prepared by the preparation method.
The porous carbon nitride material prepared by the preparation method is applied to catalytic photodegradation of rhodamine B.
The invention takes cheap cyanuric acid and small molecular nitrogen-containing compounds as raw materials, and adopts a one-step thermal polymerization method to prepare the porous carbon nitride. By changing the types and the adding amount of the small molecular nitrogen-containing compounds, a plurality of porous carbon nitride materials with different morphological structures and specific surface areas are prepared. In the preparation process, the alkaline small molecule nitrogen-containing compound and cyanuric acid are subjected to acid-base neutralization reaction to generate cyanurate, the cyanurate is further dehydrated and deaminated along with the temperature rise to form a multi-membered ring, and small molecules such as water, ammonia and the like escape in a gas form to play a pore-forming role, so that the porous carbon nitride material is formed finally.
Compared with the prior art, the method takes low-cost and nontoxic small-molecule nitrogen-containing compounds such as cyanuric acid, urea and the like as raw materials to prepare the porous carbon nitride, so that the production cost can be obviously reduced; the porous carbon nitride is directly obtained after calcination, no post-treatment is needed, the reaction is completed in one step, the production process is simplified, and the pollution to the environment is reduced; in addition, the yield of the porous carbon nitride material prepared by the method is up to 45%, and the product yield is improved. The method is carried out under normal pressure, does not need to use complex equipment, and is easy for industrial production. The porous carbon nitride material prepared by the preparation method has large specific surface area, has higher catalytic activity and better repeatability when being used as a catalyst for photodegradation of rhodamine B, and has potential utilization value in the aspect of sewage treatment.
Drawings
FIG. 1 is an X-ray diffraction pattern of a porous carbon nitride material prepared in accordance with example one of the present invention;
FIG. 2 is an infrared spectrum of a porous carbon nitride material prepared according to the first embodiment of the present invention;
FIG. 3 is an isothermal adsorption-desorption curve of the porous carbon nitride material prepared in the first embodiment of the present invention;
FIG. 4 is a TEM image of the porous carbon nitride material prepared in the first example of the present invention;
FIG. 5 is an activity diagram of the porous carbon nitride material prepared in the first embodiment of the invention catalyzing photodegradation of rhodamine B solution;
FIG. 6 is a repeated diagram of the porous carbon nitride material prepared in the first embodiment of the invention catalyzing photodegradation of rhodamine B solution.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
example one
Cyanuric acid and urea are mixed according to a mass ratio of 1: 3, grinding and uniformly mixing in a mortar, transferring the obtained solid mixture into a crucible with a cover, placing the crucible into a muffle furnace for roasting, raising the temperature of the muffle furnace to 550 ℃ at the speed of 6 ℃/min, preserving the temperature for 4h, naturally cooling to obtain the porous carbon nitride material, and obtaining the yield of the porous carbon nitride by calculation, wherein the yield of the porous carbon nitride is 41%.
The prepared material is characterized by an X-ray diffractometer, an infrared spectrometer, a physical adsorption instrument, a transmission electron microscope and the like. The X-ray diffraction pattern, the infrared spectrogram, the isothermal adsorption-desorption curve and the transmission electron microscope image of the material prepared by the steps are respectively shown in figure 1, figure 2, figure 3 and figure 4.
As can be seen from fig. 1, the XRD curves of the samples prepared in this example have two distinct diffraction peaks at 13.2o and 27.3o, which are characteristic peaks of carbon nitride material and correspond to (100) and (002) crystal planes of carbon nitride, respectively, indicating that the prepared samples are porous carbon nitride material.
As can be seen from FIG. 2, the sample prepared in this example was 1236cm-1、1329cm-1、1405cm-1、1467cm-1And 1569cm-1The peak is the stretching vibration peak of C-N bond, 1691cm-1Is C ═ N bond stretching vibration peak, 807cm-1Is the stretching vibration peak of the triazine ring, 3170cm-1Stretching vibration peaks of O-H and N-H for absorbing water molecules are positioned; the material contains triazine ring and amino, and the prepared sample is further shown to be a porous carbon nitride material.
From FIG. 3, it can be calculatedThe BET specific surface area of the sample prepared in this example was 34.1m2/g。
As can be seen from fig. 4, the sample prepared in this example has more pores, indicating that the material is a porous material.
a porous carbon nitride material is prepared by the preparation method.
In order to test the photocatalytic performance of the porous carbon nitride material prepared in this example, the porous carbon nitride material prepared in this example was used to catalyze the reaction of photodegradation of rhodamine B, and the photocatalytic activity thereof was tested. The specific test process is as follows:
200mL of 10mg/L rhodamine B solution is measured and put into a beaker, 0.2g of the porous carbon nitride material prepared in the embodiment is added, the beaker is put into a photocatalytic reactor, and the light source is a 500W xenon lamp. Turning on magnetic stirring, carrying out dark reaction for 60min without turning on a lamp, and turning on a xenon lamp to carry out photocatalytic reaction after the dark reaction is finished; from the start of the dark reaction, 5mL of the reaction liquid was extracted every 20min with a syringe equipped with a filter, and the progress of the reaction was monitored by measuring the absorbance at 554nm with an ultraviolet-visible spectrophotometer. After the reaction is finished, centrifugally separating the catalyst, washing the recovered catalyst for 3 times by using deionized water, repeatedly using the catalyst, and testing the repeatability of the material. In addition, a comparative experiment without adding the porous carbon nitride material is carried out, and other processes are the same, so that the carbon nitride prepared by the method has photocatalytic activity.
Fig. 5 is a reaction result diagram of photocatalytic degradation of rhodamine B solution by porous carbon nitride prepared in this example. The upper curve is the reaction result without adding the carbon nitride material, and the lower curve is the reaction result with adding the porous carbon nitride material prepared in this example. As can be seen from FIG. 5, the concentration of rhodamine B in the control group without the carbon nitride material is almost unchanged in the dark reaction stage, the concentration of rhodamine B is slowly reduced under illumination, and the degradation rate is less than 10% at 120min, which indicates that the degradation effect of rhodamine B without the carbon nitride material is not ideal. The carbon nitride prepared in the embodiment is added as a catalyst, the concentration of rhodamine B is obviously reduced at the early stage of dark reaction, which shows that part of rhodamine B is adsorbed by the carbon nitride material, and the concentration change of the solution at the later stage of dark reaction is not large, which shows that adsorption balance is achieved; after the illumination is started, the concentration of rhodamine B is gradually reduced, the rhodamine B is basically and completely degraded within 120min, and the catalytic effect is obvious.
FIG. 6 is a repetitive diagram of the porous carbon nitride material prepared in this example for catalyzing photodegradation of rhodamine B, and it can be seen from FIG. 6 that the activity change is not great for the first 5 times and is significantly reduced for the 6 th time, indicating that the catalytic activity of the material is relatively stable and can be used for multiple times; after the first 5 uses, there was a small decrease in catalytic activity, mainly due to a small loss of the material during the separation.
Example two
Cyanuric acid and cyanamide are mixed according to a mass ratio of 1: and 6, grinding and uniformly mixing the mixture in a mortar, transferring the obtained solid mixture into a crucible with a cover, roasting the crucible in a muffle furnace, raising the temperature of the muffle furnace to 560 ℃ at the speed of 3 ℃/min, preserving the temperature for 3h, naturally cooling to obtain the porous carbon nitride material, and obtaining the porous carbon nitride with the yield of 36 percent by calculation.
a porous carbon nitride material is prepared by the preparation method.
The prepared sample is characterized by an X-ray diffractometer, an infrared spectrometer, a physical adsorption instrument, a transmission electron microscope and the like, and the result shows that the prepared sample is a porous carbon nitride material with the specific surface area of 40.7m2/g。
The porous carbon nitride carbon material prepared by the embodiment is used for catalyzing the reaction of photodegradation of rhodamine B, and test results show that the material has high catalytic activity and good repeatability.
EXAMPLE III
Cyanuric acid and thiourea are mixed according to the mass ratio of 1: and 6, grinding and uniformly mixing the mixture in a mortar, transferring the obtained solid mixture into a crucible with a cover, roasting the crucible in a muffle furnace, raising the temperature of the muffle furnace to 540 ℃ at the speed of 3 ℃/min, preserving the temperature for 5 hours, naturally cooling to obtain the porous carbon nitride material, and obtaining the yield of the porous carbon nitride by calculation, wherein the yield of the porous carbon nitride is 33%.
a porous carbon nitride material is prepared by the preparation method.
the prepared sample is characterized by an X-ray diffractometer, an infrared spectrometer, a physical adsorption instrument, a transmission electron microscope and the like, and the result shows that the prepared sample is a porous carbon nitride material with the specific surface area of 37.2m2/g。
The porous carbon nitride carbon material prepared by the embodiment is used for catalyzing the reaction of photodegradation of rhodamine B, and test results show that the material has high catalytic activity and good repeatability.
Example four
Cyanuric acid and dicyandiamide are mixed according to a mass ratio of 1: 1 grinding and uniformly mixing in a mortar, transferring the obtained solid mixture into a crucible with a cover, placing the crucible into a muffle furnace for roasting, raising the temperature of the muffle furnace to 560 ℃ at the speed of 10 ℃/min, preserving the temperature for 3h, naturally cooling to obtain the porous carbon nitride material, and obtaining the yield of the porous carbon nitride by calculation, wherein the yield of the porous carbon nitride is 45%.
a porous carbon nitride material is prepared by the preparation method.
The prepared sample is characterized by an X-ray diffractometer, an infrared spectrometer, a physical adsorption instrument, a transmission electron microscope and the like, and the result shows that the prepared sample is a porous carbon nitride material with the specific surface area of 28.9m2/g。
The porous carbon nitride carbon material prepared by the embodiment is used for catalyzing the reaction of photodegradation of rhodamine B, and test results show that the material has high catalytic activity and good repeatability.
Claims (6)
1. A preparation method of a porous carbon nitride material is characterized by comprising the following preparation steps: grinding the metered cyanuric acid and the small molecular nitrogen-containing compound in a mortar, transferring the obtained solid mixture into a crucible with a cover, placing the crucible in a muffle furnace for roasting, heating the muffle furnace to 540-560 ℃ at the speed of 3-10 ℃/min, preserving the temperature for 3-5 h, and naturally cooling to obtain the porous carbon nitride material; the mass ratio of the cyanuric acid to the small molecular nitrogen-containing compound is 1: (1-6).
2. The method for preparing the porous carbon nitride material as claimed in claim 1, wherein the small molecular nitrogen-containing compound is one or more of urea, thiourea, dicyandiamide and cyanamide.
3. The method for preparing a porous carbon nitride material according to claim 1 or 2, wherein the mass ratio of the cyanuric acid to the small molecular nitrogen-containing compound is 1: 3.
4. The method for preparing a porous carbon nitride material according to claim 1 or 2, wherein the muffle furnace is heated to 550 ℃ at a rate of 6 ℃/min and is kept for 4 h.
5. A porous carbon nitride material produced by the production method according to any one of claims 1 to 4.
6. The use of the porous carbon nitride material according to claim 5 in catalyzing photodegradation of rhodamine B.
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| CN113044817A (en) * | 2019-12-27 | 2021-06-29 | 香港城市大学深圳研究院 | Colored carbon nitride-based film and preparation method thereof |
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| CN114733505A (en) * | 2022-03-30 | 2022-07-12 | 广东工业大学 | AgI/GO/UCN photocatalyst and preparation method and application thereof |
| CN114671416A (en) * | 2022-04-13 | 2022-06-28 | 北京理工大学 | Method for preparing carbon nitride ultra-rapidly |
| CN114671416B (en) * | 2022-04-13 | 2024-03-15 | 北京理工大学 | Method for preparing carbon nitride in ultra-fast way |
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Application publication date: 20191213 |