CN108479836B - Graphite-phase carbon nitride-based photocatalyst and preparation method thereof - Google Patents
Graphite-phase carbon nitride-based photocatalyst and preparation method 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 73
- 239000011941 photocatalyst Substances 0.000 title abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 47
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011229 interlayer Substances 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 229910052573 porcelain Inorganic materials 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 13
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000012300 argon atmosphere Substances 0.000 abstract description 5
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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Abstract
A graphite phase carbon nitride catalyst is a catalyst in which titanium dioxide nanorods are distributed on the surface and the edge of a carbon nitride nanosheet or are inserted into the interlayer of the nanosheet, and/or tungsten disulfide is distributed on the surface of the titanium nitride nanosheet, and the catalyst comprises the following chemical components in percentage by mass: 0-1 part of tungsten disulfide, 0-7 parts of titanium dioxide and the balance of graphite-phase carbon nitride; the preparation method of the catalyst is mainly that a mixture of 0-5mg of tungsten disulfide, 0-35mg of titanium dioxide and 500mg of carbon nitride as the balance is poured into a beaker, 3mL of absolute alcohol is added into each 50mg of the mixture according to the proportion of adding 3mL of absolute alcohol, the mixture is subjected to ultrasonic treatment for 2h and then stirred for 12h, and then dried for 24h at 80 ℃; and then preserving the heat for 2 hours at 250 ℃ in the argon atmosphere to prepare the graphite-phase carbon nitride photocatalyst. The method is simple, and the prepared catalyst has high photocatalytic activity, good photocatalytic stability, stable physical properties, no toxicity and no harm, and is beneficial to industrial large-scale production and practical application.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a photocatalyst and a preparation method thereof.
Background
At present, the demand of human society for fossil energy is increasing day by day, and a large amount of pollutants such as waste gas, waste water, waste residue and the like are discharged to the environment while the fossil energy is used, so that serious energy crisis and ecological environment problems are caused. The increasing energy crisis and environmental problems have attracted global attention, and the search for appropriate solutions has become a research focus and focus of researchers. The photocatalysis technology takes semiconductor materials as media, converts endless solar energy into clean chemical energy for human use, or generates high-activity groups to degrade organic pollutants, thereby solving the environmental problem. Therefore, the photocatalysis technology has bright application prospect in the field of solving energy crisis and environmental problems. The graphite phase carbon nitride is a two-dimensional layered semiconductor material without metal elements, has the advantages of easily obtained raw materials, simple preparation method, stable physical properties, no toxicity, no harm, good photocatalytic activity and the like, and is a widely researched material in the photocatalytic technology. However, the defects of large forbidden band width, low visible light response capability, high photocarrier recombination speed and the like of the graphite-phase carbon nitride seriously restrict the improvement of the catalytic performance of the carbon nitride and limit the industrialized large-scale production and practical use of the carbon nitride.
Disclosure of Invention
The invention aims to provide a graphite-phase carbon nitride-based photocatalyst with high photocatalytic activity and high photocatalytic stability and a preparation method thereof. The invention mainly adopts an immersion method to mix carbon nitride, tungsten disulfide or titanium dioxide to prepare the graphite phase carbon nitride material.
The graphite-phase carbon nitride-based photocatalyst comprises the following chemical components in percentage by mass (wt%): 0-1 percent of tungsten disulfide, 0-7 percent of titanium dioxide and the balance of graphite phase carbon nitride. The material morphology is that titanium dioxide nano-rods are distributed on the surface and the edge of the carbon nitride nano-sheet or are inserted between nano-sheet layers and/or tungsten disulfide is distributed on the surface of the carbon nitride nano-sheet.
The preparation method of the graphite-phase carbon nitride-based photocatalyst comprises the following steps:
(1) putting raw material urea into an alumina porcelain square boat, then placing the porcelain square boat into a muffle furnace for heat treatment, wherein the temperature rise procedure is as follows: raising the temperature from room temperature to 500 ℃ at a heating rate of 10 ℃ per minute, preserving the temperature for 2 hours, and then cooling along with the furnace to synthesize the carbon nitride.
(2) According to the mass ratio of the titanium carbide to the urea of 1:100, putting the titanium carbide raw material into another porcelain ark, carrying out heat treatment in a muffle furnace, heating to 350 ℃ from room temperature at the heating rate of 10 ℃/min, and preserving heat for 1h to synthesize titanium dioxide; according to the proportion of adding 60mL of sodium hydroxide into 1g of titanium dioxide, pouring the titanium dioxide and the sodium hydroxide with the concentration of 10mol/L into a polytetrafluoroethylene inner container, and carrying out ultrasonic treatment for 30min to fully disperse the titanium dioxide; then the reaction kettle is placed in an oven at 130 ℃ for heat preservation for 24h, concentrated hydrochloric acid is added into the obtained reaction solution dropwise until the pH value is 3, then deionized water is used for washing for a plurality of times to ensure that the pH value is 7, the obtained precipitate is dried for 24h at 80 ℃, and the obtained dried powder is subjected to heat treatment for 2h in a muffle furnace at 350 ℃.
(3) According to the mass ratio of tungsten chloride to thioacetamide of 1: 1.9, adding tungsten chloride and thioacetamide into a beaker, adding 10mL of deionized water into a mixture of tungsten chloride and thioacetamide per gram, pouring the mixture into deionized water, carrying out ultrasonic treatment for 1h, transferring the solution into a reaction kettle, reacting for 24h at 220 ℃, filtering and washing the obtained precipitate, and drying for 24h at 80 ℃ to obtain the tungsten disulfide.
(4) And (3) pouring the tungsten disulfide in the step (3), the titanium dioxide in the step (2) and the carbon nitride in the step (1) into a container, wherein the total mass of three phases is 500mg, the tungsten disulfide is 0-5mg, the titanium dioxide is 0-35mg, and the balance is the carbon nitride, adding 3mL of anhydrous alcohol into every 50mg of two or three mixtures, carrying out ultrasonic treatment on the mixture for 2 hours, stirring the mixture for 12 hours, and drying the mixture for 24 hours at 80 ℃.
Compared with the prior art, the invention has the following advantages:
1. the preparation method is simple;
2. the prepared graphite-phase carbon nitride-based photocatalyst still retains the advantages of pure tungsten disulfide, titanium dioxide and carbon nitride, such as low preparation cost, easily available raw materials, stable physical and chemical properties, no toxicity, no harm and the like;
3. the prepared graphite-phase carbon nitride-based photocatalyst has higher photocatalytic activity, and is more suitable for industrial large-scale application in the field of photocatalysis compared with pure titanium dioxide and carbon nitride.
Drawings
Fig. 1 is an X-ray powder diffraction pattern (XRD) of the graphite-phase carbon nitride-based photocatalyst prepared in example 1 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the graphite-phase carbon nitride-based photocatalyst prepared in example 1 of the present invention;
fig. 3 is a diagram of hydrogen production by water splitting by graphite-phase carbon nitride-based photocatalyst and pure carbon nitride obtained in examples 1, 3 and 5 of the present invention.
Detailed Description
Example 1
30 g of urea (Tianjin Kaiton chemical reagent Co., Ltd.) was put into an alumina porcelain ark, and then the porcelain ark was put into a muffle furnace to be heat-treated, and the temperature was raised from room temperature to 500 ℃ at a rate of 10 ℃ per minute, and after 2 hours of heat preservation, it was cooled in the furnace to synthesize carbon nitride. Taking 0.3g of titanium carbide (Shanghai field nanometer materials Co., Ltd.) and putting into a porcelain ark, carrying out heat treatment in a muffle furnace, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, and keeping the temperature for 1h to synthesize titanium dioxide; 1g of titanium dioxide and 60mL of sodium hydroxide with the concentration of 10mol/L are weighed and poured into a polytetrafluoroethylene inner container, and ultrasonic treatment is carried out for 30min to fully disperse the titanium dioxide. The reaction vessel was then placed in an oven at 130 ℃ for 24h, concentrated hydrochloric acid was then added dropwise to the resulting reaction solution to a PH of 3, washed several times with deionized water to a PH of 7, the resulting precipitate was dried at 80 ℃ for 24h, and the resulting dried powder was heat treated in a muffle furnace at 350 ℃ for 2 h. Placing 2g of tungsten chloride (Dow Akkoda chemical reagent Co., Ltd.) and 3.789g of thioacetamide (Dow Akkoda chemical reagent Co., Ltd.) in a beaker, pouring 60ml of deionized water, performing ultrasonic treatment for 1h, transferring the solution to a reaction kettle, reacting for 24h at 220 ℃, filtering and washing the obtained precipitate, and drying for 24h at 80 ℃ to obtain tungsten disulfide. 3.5mg of tungsten disulfide, 25mg of titanium dioxide and 471.5mg of carbon nitride are poured into a beaker, 30ml of absolute alcohol is added, the mixture is stirred for 12 hours after 2 hours of ultrasonic treatment, then the mixture is dried for 24 hours at 80 ℃, and the temperature is kept for 2 hours at 250 ℃ under the argon atmosphere, so that the graphite-phase carbon nitride-based photocatalyst is prepared.
As shown in fig. 1, mainly diffraction peaks of carbon nitride and titanium dioxide are detected, and since the doping amount of tungsten disulfide is small, no corresponding diffraction peak is detected, which can indicate that carbon nitride co-modified by titanium dioxide and tungsten disulfide is successfully synthesized.
As shown in fig. 2, it can be seen that tungsten disulfide, titanium dioxide and carbon nitride are tightly bound.
As shown in fig. 3, the performance test of hydrogen production by photolysis of water with the graphite-phase carbon nitride-based photocatalyst and pure carbon nitride is as follows: a 300 watt xenon lamp was used as the light source, 50mg of catalyst material, 8 ml of triethanolamine, 4 ml of chloroplatinic acid (1 mg per ml), 68 ml of water, with a five hour hydrogen production of 4.9 mmol per gram and 1.6 mmol per gram of pure carbon nitride.
Example 2
30 g of urea (Tianjin Kaiton chemical reagent Co., Ltd.) was put into an alumina porcelain ark, and then the porcelain ark was put into a muffle furnace to be heat-treated, and the temperature was raised from room temperature to 500 ℃ at a rate of 10 ℃ per minute, and the heat was preserved for 2 hours, and then the carbon nitride was synthesized by furnace cooling. Taking 0.3g of titanium carbide (Shanghai field nanometer materials Co., Ltd.) and putting into a porcelain ark, carrying out heat treatment in a muffle furnace, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, and keeping the temperature for 1h to synthesize titanium dioxide; weighing 1g of titanium dioxide and 60ml of sodium hydroxide with the concentration of 10mol/L, pouring the titanium dioxide into a polytetrafluoroethylene inner container, carrying out ultrasonic treatment for 30min to fully disperse the titanium dioxide, then placing a reaction kettle in an oven with the temperature of 130 ℃ for heat preservation for 24h, then dropwise adding concentrated hydrochloric acid into the obtained reaction solution until the pH is 3, then washing the reaction solution with deionized water for several times to enable the pH to be 7, drying the obtained precipitate at the temperature of 80 ℃ for 24h, and then carrying out heat treatment on the obtained dry powder in a muffle furnace with the temperature of 350 ℃ for 2 h. 25mg of titanium dioxide and 475mg of carbon nitride are poured into a beaker, 30ml of absolute alcohol is added, and the mixture is stirred for 12 hours after 2 hours of ultrasonic treatment. And then drying the graphite phase carbon nitride photocatalyst at the temperature of 80 ℃ for 24 hours, and then preserving heat at the temperature of 250 ℃ for 2 hours in the argon atmosphere to obtain the graphite phase carbon nitride photocatalyst.
The performance test of hydrogen production by photocatalytic decomposition of water by the graphite-phase carbon nitride-based photocatalyst comprises the following steps: a 300 watt xenon lamp was used as the light source, 50mg of catalyst material, 8 ml of triethanolamine, 4 ml of chloroplatinic acid (1 mg per ml), 68 ml of water, a five hour hydrogen production of 2.0 mmol per gram and 1.6 mmol per gram of pure carbon nitride.
Example 3
30 g of urea (Tianjin Kaiton chemical reagent Co., Ltd.) was put into an alumina porcelain ark, and then the porcelain ark was put into a muffle furnace to be heat-treated, and the temperature was raised from room temperature to 500 ℃ at a rate of 10 ℃ per minute, and the heat was preserved for 2 hours, and then the carbon nitride was synthesized by furnace cooling. Taking 0.3g of titanium carbide (Shanghai field nanometer materials Co., Ltd.) and putting into a porcelain ark, carrying out heat treatment in a muffle furnace, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, and keeping the temperature for 1h to synthesize titanium dioxide; weighing 1g of titanium dioxide and 60ml of sodium hydroxide with the concentration of 10mol/L, pouring the titanium dioxide into a polytetrafluoroethylene inner container, carrying out ultrasonic treatment for 30min to fully disperse the titanium dioxide, then placing a reaction kettle in an oven with the temperature of 130 ℃ for heat preservation for 24h, then dropwise adding concentrated hydrochloric acid into the obtained reaction solution until the pH is 3, then washing the reaction solution with deionized water for several times to enable the pH to be 7, drying the obtained precipitate at the temperature of 80 ℃ for 24h, and then carrying out heat treatment on the obtained dry powder in a muffle furnace with the temperature of 350 ℃ for 2 h. 2g of tungsten chloride (Dow Elkoda Chemicals Co., Ltd.) and 3.789g of thioacetamide (Dow Elkoda Chemicals Co., Ltd.) were placed in a beaker, poured with 60ml of deionized water, and sonicated for 1 hour. The solution was transferred to a reaction kettle and reacted at 220 ℃ for 24 h. And filtering and washing the obtained precipitate, and drying the precipitate for 24 hours at the temperature of 80 ℃ to obtain the tungsten disulfide. And (2) pouring 5mg of tungsten disulfide, 25mg of titanium dioxide and 470mg of carbon nitride into a beaker, adding 30ml of absolute alcohol, carrying out ultrasonic treatment for 2 hours, stirring for 12 hours, drying for 24 hours at 80 ℃, and then carrying out heat preservation for 2 hours at 250 ℃ under an argon atmosphere to obtain the graphite-phase carbon nitride-based photocatalyst.
As shown in fig. 3, the performance test of hydrogen production by photolysis of water with the graphite-phase carbon nitride-based photocatalyst and pure carbon nitride is as follows: a 300 watt xenon lamp was used as the light source, 50mg of catalyst material, 8 ml of triethanolamine, 4 ml of chloroplatinic acid (1 mg per ml), 68 ml of water, a five hour hydrogen production of 2.3 mmol per gram and 1.6 mmol per gram of pure carbon nitride.
Example 4
30 g of urea (Tianjin Kaiton chemical reagent Co., Ltd.) was put into an alumina porcelain ark, and then the porcelain ark was put into a muffle furnace to be heat-treated, and the temperature was raised from room temperature to 500 ℃ at a rate of 10 ℃ per minute, and the heat was preserved for 2 hours, and then the carbon nitride was synthesized by furnace cooling. Placing 2g of tungsten chloride (Dow Akkoda chemical reagent Co., Ltd.) and 3.789g of thioacetamide (Dow Akkoda chemical reagent Co., Ltd.) in a beaker, pouring 60ml of deionized water, performing ultrasonic treatment for 1h, transferring the solution to a reaction kettle, reacting for 24h at 220 ℃, filtering and washing the obtained precipitate, and drying for 24h at 80 ℃ to obtain tungsten disulfide. And 3.5mg of tungsten disulfide and 496.5mg of carbon nitride are poured into a beaker, 30ml of absolute alcohol is added, the mixture is stirred for 12 hours after being subjected to ultrasonic treatment for 2 hours, and then the mixture is dried for 24 hours at the temperature of 80 ℃ and is kept warm for 2 hours at the temperature of 250 ℃ under the atmosphere of argon, so that the graphite-phase carbon nitride-based photocatalyst is prepared.
The performance test of hydrogen production by photocatalytic decomposition of water by the graphite-phase carbon nitride-based photocatalyst comprises the following steps: a 300 watt xenon lamp was used as the light source, 50mg of catalyst material, 8 ml of triethanolamine, 4 ml of chloroplatinic acid (1 mg per ml), 68 ml of water, with a five hour hydrogen production of 1.9 mmol per gram and 1.6 mmol per gram of pure carbon nitride.
Example 5
30 g of urea (Tianjin Kaiton chemical reagent Co., Ltd.) was put into an alumina porcelain ark, and then the porcelain ark was put into a muffle furnace to be heat-treated, and the temperature was raised from room temperature to 500 ℃ at a rate of 10 ℃ per minute, and the heat was preserved for 2 hours, and then the carbon nitride was synthesized by furnace cooling. Taking 0.3g of titanium carbide (Shanghai field nanometer materials Co., Ltd.) and putting into a porcelain ark, carrying out heat treatment in a muffle furnace, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, and keeping the temperature for 1h to synthesize titanium dioxide; weighing 1g of titanium dioxide and 60ml of sodium hydroxide with the concentration of 10mol/L, pouring the titanium dioxide into a polytetrafluoroethylene inner container, carrying out ultrasonic treatment for 30min to fully disperse the titanium dioxide, then placing a reaction kettle in an oven with the temperature of 130 ℃ for heat preservation for 24h, then dropwise adding concentrated hydrochloric acid into the obtained reaction solution until the pH is 3, then washing the reaction solution with deionized water for several times to enable the pH to be 7, drying the obtained precipitate at the temperature of 80 ℃ for 24h, and then carrying out heat treatment on the obtained dry powder in a muffle furnace with the temperature of 350 ℃ for 2 h. Placing 2g of tungsten chloride (Chengdu Aikoda chemical reagent Co., Ltd.) and 3.789g of thioacetamide (Chengdu Aikoda chemical reagent Co., Ltd.) in a beaker, pouring 60ml of deionized water, performing ultrasonic treatment for 1h, transferring the solution to a reaction kettle, reacting for 24h at 220 ℃, filtering and washing the obtained precipitate, and drying for 24h at 80 ℃ to obtain tungsten disulfide. 3.5mg of tungsten disulfide, 35mg of titanium dioxide and 471.5mg of carbon nitride are poured into a beaker, 30ml of absolute alcohol is added, the mixture is stirred for 12 hours after 2 hours of ultrasonic treatment, then the mixture is dried for 24 hours at 80 ℃, and the temperature is kept for 2 hours at 250 ℃ under the argon atmosphere, so that the graphite-phase carbon nitride-based photocatalyst is prepared.
As shown in fig. 3, the performance test of hydrogen production by photolysis of water with the graphite-phase carbon nitride-based photocatalyst and pure carbon nitride is as follows: a 300 watt xenon lamp was used as the light source, 50mg of catalyst material, 8 ml of triethanolamine, 4 ml of chloroplatinic acid (1 mg per ml), 68 ml of water, with a five hour hydrogen production of 4.4 mmol per gram and 1.6 mmol per gram of pure carbon nitride.
Claims (2)
1. A graphite-phase carbon nitride-based catalyst, characterized in that: the catalyst is a catalyst in which titanium dioxide nanorods are distributed on the surface and the edge of a carbon nitride nanosheet or are inserted into the interlayer of the nanosheet and tungsten disulfide is distributed on the surface of the carbon nitride nanosheet, and the catalyst comprises the following chemical components in percentage by weight: the tungsten disulfide is 0-1, the titanium dioxide is 0-7, and the balance is graphite phase carbon nitride, and the method comprises the following steps:
(1) putting raw material urea into an alumina porcelain ark, then putting the porcelain ark into a muffle furnace for heat treatment, raising the temperature from room temperature to 500 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 2 hours, then cooling along with the furnace, and synthesizing carbon nitride;
(2) according to the mass ratio of the titanium carbide to the urea of 1:100, putting the titanium carbide raw material into another porcelain ark, carrying out heat treatment in a muffle furnace, heating to 350 ℃ from room temperature at the heating rate of 10 ℃/min, and preserving heat for 1h to synthesize titanium dioxide; according to the proportion of adding 60mL of sodium hydroxide into 1g of titanium dioxide, pouring the titanium dioxide and the sodium hydroxide with the concentration of 10mol/L into a polytetrafluoroethylene inner container, and carrying out ultrasonic treatment for 30min to fully disperse the titanium dioxide; then placing the reaction kettle in an oven at 130 ℃ for heat preservation for 24h, then dropwise adding concentrated hydrochloric acid into the obtained reaction solution until the PH is 3, then washing the reaction solution for several times by deionized water to enable the PH to be 7, drying the obtained precipitate at 80 ℃ for 24h, and then carrying out heat treatment on the obtained dried powder in a muffle furnace at 350 ℃ for 2 h;
(3) according to the mass ratio of tungsten chloride to thioacetamide of 1: 1.9, putting tungsten chloride and thioacetamide into a beaker, adding 10mL of deionized water into a mixture of tungsten chloride and thioacetamide per gram, pouring the mixture into deionized water, carrying out ultrasonic treatment for 1h, transferring the solution into a reaction kettle, reacting for 24h at 220 ℃, filtering and washing the obtained precipitate, and drying for 24h at 80 ℃ to obtain tungsten disulfide;
(4) and (3) pouring the tungsten disulfide in the step (3), the titanium dioxide in the step (2) and the carbon nitride in the step (1) into a container, wherein the total mass of three phases is 500mg, the tungsten disulfide is 2.5-5mg, the titanium dioxide is 25-35mg and the balance is the carbon nitride, adding 3mL of anhydrous alcohol into each 50mg of the mixture, carrying out ultrasonic treatment on the mixture for 2h, stirring the mixture for 12h, and drying the mixture for 24h at 80 ℃.
2. A method for preparing the graphite-phase carbon nitride-based catalyst according to claim 1, characterized in that:
(1) putting raw material urea into an alumina porcelain ark, then putting the porcelain ark into a muffle furnace for heat treatment, raising the temperature from room temperature to 500 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 2 hours, then cooling along with the furnace, and synthesizing carbon nitride;
(2) according to the mass ratio of the titanium carbide to the urea of 1:100, putting the titanium carbide raw material into another porcelain ark, carrying out heat treatment in a muffle furnace, heating to 350 ℃ from room temperature at the heating rate of 10 ℃/min, and preserving heat for 1h to synthesize titanium dioxide; according to the proportion of adding 60mL of sodium hydroxide into 1g of titanium dioxide, pouring the titanium dioxide and the sodium hydroxide with the concentration of 10mol/L into a polytetrafluoroethylene inner container, and carrying out ultrasonic treatment for 30min to fully disperse the titanium dioxide; then placing the reaction kettle in an oven at 130 ℃ for heat preservation for 24h, then dropwise adding concentrated hydrochloric acid into the obtained reaction solution until the PH is 3, then washing the reaction solution for several times by deionized water to enable the PH to be 7, drying the obtained precipitate at 80 ℃ for 24h, and then carrying out heat treatment on the obtained dried powder in a muffle furnace at 350 ℃ for 2 h;
(3) according to the mass ratio of tungsten chloride to thioacetamide of 1: 1.9, putting tungsten chloride and thioacetamide into a beaker, adding 10mL of deionized water into a mixture of tungsten chloride and thioacetamide per gram, pouring the mixture into deionized water, carrying out ultrasonic treatment for 1h, transferring the solution into a reaction kettle, reacting for 24h at 220 ℃, filtering and washing the obtained precipitate, and drying for 24h at 80 ℃ to obtain tungsten disulfide;
(4) and (3) pouring the tungsten disulfide in the step (3), the titanium dioxide in the step (2) and the carbon nitride in the step (1) into a container, wherein the total mass of three phases is 500mg, the tungsten disulfide is 2.5-5mg, the titanium dioxide is 25-35mg and the balance is the carbon nitride, adding 3mL of anhydrous alcohol into each 50mg of the mixture, carrying out ultrasonic treatment on the mixture for 2h, stirring the mixture for 12h, and drying the mixture for 24h at 80 ℃.
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| CN105817253A (en) * | 2016-04-12 | 2016-08-03 | 中国计量大学 | Method for preparing graphite phase carbon nitride nanosheet/titania nanotube array photocatalysis material |
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