CN108906121B - C6N7Cl3Preparation method of-DAAB polymer photocatalytic hydrogen production catalyst - Google Patents
C6N7Cl3Preparation method of-DAAB polymer photocatalytic hydrogen production catalyst Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 39
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 claims 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims 3
- 239000003599 detergent Substances 0.000 claims 1
- 241000219112 Cucumis Species 0.000 abstract description 17
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 abstract description 17
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
本发明提供一种C6N7Cl3‑DAAB聚合物光催化制氢催化剂的制备方法，以三聚氰胺为原料合成Melon，然后Melon和KOH反应制备得到C6N7(OK)3，再用固相反应法将C6N7(OK)3和PCl5合成中间体C6N7Cl3，最后将中间体C6N7Cl3和DAAB在甲苯中反应得到C6N7Cl3‑DAAB聚合物。然后对C6N7Cl3‑DAAB聚合物进行光催化制氢性能的研究。研究结果表明C6N7Cl3‑DAAB聚合物的产氢速率为9.05μmol g‑1 h‑1，是Melon 5.79μmol g‑1 h‑1产氢速率的1.5倍。
The invention provides a preparation method of a C 6 N 7 Cl 3 -DAAB polymer photocatalytic hydrogen production catalyst. Melon is synthesized by using melamine as a raw material, and then Melon is reacted with KOH to prepare C 6 N 7 (OK) 3 . C 6 N 7 (OK) 3 and PCl 5 were synthesized into intermediate C 6 N 7 Cl 3 by reverse reaction method, and finally intermediate C 6 N 7 Cl 3 and DAAB were reacted in toluene to obtain C 6 N 7 Cl 3 -DAAB polymer. Then the photocatalytic hydrogen production performance of C 6 N 7 Cl 3 ‑DAAB polymer was studied. The results show that the hydrogen production rate of C 6 N 7 Cl 3 -DAAB polymer is 9.05μmol g -1 h -1 , which is 1.5 times that of Melon's 5.79 μmol g -1 h -1 .
Description
Technical Field
The invention relates to a preparation method of a catalyst for producing hydrogen by decomposing water by sunlight. Belongs to the technical field of energy materials.
Background
The energy is an indispensable material basis for human survival and also an important material guarantee for the sustainable development of the society and the economy. After the 20 th century, the science and technology developed rapidly, the economy developed, people's life had changed greatly, the human society entered the unprecedented prosperity period. However, with the rapid development of society, there is a serious worsening of a series of problems such as resource shortage, environmental pollution, and ecological imbalance. No doubt, environmental pollution and energy depletion are two major challenges facing human survival and development. People have noticed that the thorough solution of the above problems is free from worries of people, and the most fundamental approach is to accelerate the development of clean energy and realize the large-scale development and utilization of clean energy. At present, the development and utilization of renewable clean energy sources are widely accepted by countries around the world. The hydrogen energy has the characteristics of high energy density, storage, transportability, no pollution and the like, and is used as a low-carbon and zero-carbon energy source, so that more and more hydrogen energy is developed and researched in recent years. At present, the photocatalytic hydrogen production technology has become one of the most valuable research directions for producing hydrogen by utilizing solar energy and decomposing water. On one hand, the water resource is very abundant, the distribution is extensive, the cost is low, it is easy to obtain. On the other hand, the hydrogen has high energy density and high heat value, only water is a combustion product, and little pressure can not be caused to the environment, thereby realizing virtuous cycle of energy utilization. Polymer semiconductor graphite phase carbon nitride (Melon) has attracted much attention because of its excellent chemical stability and unique semiconductor band structure. Although it has been widely studied, the development of the Melon material is still limited due to the shortcomings of insufficient sunlight utilization rate, small specific surface area, high recombination rate of photo-generated electrons and holes, and the like.
Disclosure of Invention
The invention aims to provide a C with a novel structure6N7Cl3A preparation method of a catalyst for photocatalytic hydrogen production of DAAB polymer. A compound of the invention6N7Cl3The preparation method of the-DAAB polymer photocatalytic hydrogen production catalyst is completed according to the following steps:
step one, melamine (C)3H6N6) Placing into a ceramic crucible, calcining in a muffle furnace at 520 ℃ for 8h, naturally cooling to room temperature, and grinding to obtain Melon (C)6N7(NH2)3) Weighing a proper amount of Melon, placing the Melon in KOH solution, heating, stirring, refluxing and reacting for 4 hours, and then cooling and crystallizing to obtain white acicular crystals C6N7(OK)3Weighing appropriate amount of C6N7(OK)3Adding an excess of PCl5Fully grinding the mixture in a mortar, putting the ground mixture into a hydrothermal kettle, putting the hydrothermal kettle into an oven, heating the hydrothermal kettle for 24 hours at 220 ℃ to obtain an intermediate C6N7Cl3；
Step two, the intermediate C obtained in the step one6N7Cl3And 4, 4-azodiphenylamine (DAAB) are respectively weighed, and the proper amount of the mixture is sequentially added into toluene, stirred in a shading mode at room temperature and then reacted for a period of time under the condition of oil bath heating and reflux. After the reaction is finished, filtering the mixture at normal pressure to obtain a solid, sequentially washing the solid with toluene, acetone and an acetone-water mixture (v: v ═ 1:1) for 3-5 times, and drying the washed solid at 80 ℃ to obtain C6N7Cl3-a DAAB polymer;
c in step two6N7Cl3The mass to volume ratio of the toluene to the toluene is 1g: 15-20 mL;
c in step two6N7Cl3And the mass ratio of the dosage of DAAB is 1g: 1-2 g;
and the reaction condition in the step two is that stirring is carried out for 12-36 h in a shading mode at room temperature, and then the reaction is carried out for 1-3 h under the condition of oil bath heating reflux at the temperature of 100-135 ℃.
Photocatalytic decomposition test for hydrogen production
To investigate C6N7Cl3The effect of the DAAB polymer photocatalytic hydrogen production catalyst on hydrogen production by water decomposition is tested according to the following method. The test procedure was as follows: the photocatalytic hydrogen production experiment is carried out in a photocatalytic activity evaluation online analysis system, before the reaction starts, a condensation system is started, and air in the system is exhausted through a vacuum pump. The xenon lamp of 300W is used as a light source (more than or equal to 320 nm).
The photocatalytic hydrogen production test process is as follows: c is to be6N7Cl3The DAAB polymer hydrogen production photocatalyst material was weighed at 30mg with an analytical balance and added to a mixed solution of 90mL of distilled water and 10mL of triethanolamine. In order to uniformly disperse the photocatalyst in the reaction process, ultrasonic treatment is carried out for 30min before the solution is added into the reactor, 1 wt% of Pt is added as a cocatalyst, then the mixed solution is transferred into a hydrogen generating device and is continuously stirred in the reaction process, the system is vacuumized for 40min before the reaction, a light source is startedThen, sampling is carried out every 1h under the illumination condition, and analysis is carried out by a gas chromatograph, wherein the reaction time is 5h in total.
The invention has the advantages of
Melon is synthesized by taking melamine as raw material, and then the Melon reacts with KOH to prepare C6N7(OK)3Then using a solid phase reaction method to react C6N7(OK)3And PCl5Synthesis of intermediate C6N7Cl3Finally, intermediate C is added6N7Cl3Stirring the mixture and DAAB in toluene at normal temperature for 24 hours, and heating and refluxing the mixture in an oil bath at the temperature of 125-135 ℃ for 2 hours to obtain C6N7Cl3DAAB polymer was then subjected to a study of the photocatalytic hydrogen generation properties. The results of the study demonstrate that C6N7Cl3The hydrogen production rate of the-DAAB polymer was 9.05. mu. mol g-1h-1Is Melon 5.79. mu. mol g-1h-1The hydrogen production rate is 1.5 times.
Drawings
FIG. 1 is C6N7Cl3And C6N7Cl3-DAAB polymer FT-IR spectrum;
FIG. 2 is C6N7Cl3-DAAB polymer SEM picture;
FIG. 3 shows Melon and C6N7Cl3-DAAB polymer photocatalytic decomposition water hydrogen production rate contrast diagram.
Detailed Description
Example 1: one kind of C of the present embodiment6N7Cl3The preparation method of the-DAAB polymer photocatalytic hydrogen production catalyst is completed according to the following steps:
step one, placing 30g of melamine into a ceramic crucible, placing the ceramic crucible into a muffle furnace, calcining for 8 hours at 520 ℃, naturally cooling to room temperature, and grinding to obtain Melon; weighing 10g of Melon, placing the Melon in 200mL of 2.5M KOH solution, heating, stirring, refluxing, reacting for 4h, standing overnight, cooling, crystallizing to obtain white needle-like crystals, filtering to obtain crystals, washing the crystals with absolute ethyl alcohol for 2-3 times, and placing the crystals in a vacuum drying oven for drying at 70 ℃ for 8h to obtain C6N7(OK)3(ii) a Weighing appropriate amount of 2.5g C6N7(OK)38g of PCl are added5Fully grinding in a mortar, putting into a hydrothermal kettle, heating in an oven at 220 ℃ for 24 hours, naturally cooling to room temperature, transferring the solid in the kettle into cold distilled water at a temperature lower than 4 ℃ under the condition of a salt bath, stirring and dispersing, and drying the solid obtained after suction filtration in a allochroic silica gel dryer to obtain C6N7Cl3Sealing and storing in refrigerator;
step two, the C obtained in the step one6N7Cl3And DAAB, 2g and 2.303g of each component are weighed and added into 30mL of toluene, stirred at room temperature in a shade mode for 24 hours and then heated and refluxed in an oil bath at 125-135 ℃ for 2 hours. After the reaction is finished, filtering the mixture at normal pressure, washing the mixture for 3 to 5 times by using toluene, acetone and an acetone-water mixture (v: v ═ 1:1) in turn with 20mL of each, and drying the mixture at 80 ℃ to obtain C6N7Cl3-DAAB polymer.
C6N7Cl3Characterization and performance detection of the DAAB polymer hydrogen production photocatalyst material:
FIG. 1 shows the results of example 1 for C6N7Cl3And C6N7Cl3FT-IR detection of the-DAAB polymer gave the following results as shown in FIG. 1:1 is C6N7Cl32 is C6N7Cl3-DAAB polymer. 3200cm was obtained by analysis on 1-1The absorption peak at (A) is an asymmetric stretching vibration peak of-C-N bond, 1637cm-1、1500cm-1And 1400cm-1The left and right absorption peaks are the absorption peaks of vibration of skeleton with N-C ═ N, 1350cm-1Then is the C-N telescopic vibration absorption, 850cm-1The absorption peak of (A) is the deduced synthesized product C generated by the stretching vibration of C-Cl6N7Cl3. 3500cm can be estimated by 2 analysis-1The absorption peak is generated by the asymmetric stretching vibration of N-H of secondary amine, 3200cm-1The absorption peak of (1) is the asymmetric stretching vibration absorption peak of C-H on the benzene ring, and is 1600cm-1And 1500 cm-1The four absorption peaks are caused by the vibration of the skeleton of the benzene ring, the stretching vibration of the-N-bond, and the stretching vibration of-C-NThe peak of stretching vibration of-C-N appears at 1300cm-1Bending vibration of-C-H at 1250cm-1、1150cm-1And 1100cm-1Generates an absorption peak at 850cm-1The absorption peak at (a) is evidence of para-disubstituted. From the figure, C can be deduced6N7Cl3Reaction with DAAB to form C6N7Cl3-DAAB polymer.
FIG. 2 for C obtained in example 16N7Cl3SEM analysis of the-DAAB polymer gave the following results as shown in FIG. 2: the product is in the shape of regular round particles, and the particle size is 200-400 nm.
FIG. 3 for C obtained in example 16N7Cl3Comparison of hydrogen production rates by photocatalytic decomposition of DAAB polymers is shown in FIG. 3; 1 is Melon and 2 is C6N7Cl3-DAAB. From the figure, C can be known6N7Cl3The hydrogen production rate of the-DAAB polymer was 9.05. mu. mol g-1h-1Is Melon 5.79. mu. mol g-1h-1The hydrogen production rate is 1.5 times.
Claims (4)
1. C6N7Cl3A preparation method of the catalyst for photocatalytic hydrogen production of-DAAB polymer, which is characterized in that C6N7Cl3The preparation method of the-DAAB polymer photocatalytic hydrogen production catalyst is completed according to the following steps:
step one, melamine is C3H6N6Placing into a ceramic crucible, calcining in a muffle furnace at 520 deg.C for 8 hr, naturally cooling to room temperature, grinding to obtain melem with chemical formula C6N7(NH2)3Weighing a proper amount of melem, placing the melem in KOH solution, heating, stirring, refluxing and reacting for 4 hours, and then cooling and crystallizing to obtain white acicular crystals C6N7(OK)3Weighing appropriate amount of C6N7(OK)3Adding an excess of PCl5Fully grinding the mixture in a mortar, putting the ground mixture into a hydrothermal kettle, putting the hydrothermal kettle into an oven, heating the hydrothermal kettle for 24 hours at 220 ℃ to obtain an intermediate C6N7Cl3；
Step two, the intermediate C obtained in the step one6N7Cl3And 4, 4' -azodiphenylamine, namely DAAB for short, are weighed and sequentially added into toluene, and are stirred in a shading mode at room temperature, and then the mixture reacts for a period of time under the condition of oil bath heating reflux; after the reaction is finished, filtering at normal pressure to obtain a solid, sequentially washing with toluene, acetone and an acetone-water mixture in a volume ratio of 1:1 for 3-5 times, and drying at 80 ℃ to obtain C6N7Cl3-a DAAB polymer;
c in step two6N7Cl3The mass to volume ratio of the toluene to the toluene is 1g: 15-20 mL;
c in step two6N7Cl3The mass ratio of the dosage of the DAAB to the dosage of the DAAB is 1g: 1-2 g;
and the reaction condition in the step two is that stirring is carried out for 12-36 h in a shading mode at room temperature, and then the reaction is carried out for 1-3 h under the condition of oil bath heating reflux at the temperature of 100-135 ℃.
2. A compound C according to claim 16N7Cl3The preparation method of the-DAAB polymer photocatalytic hydrogen production catalyst is characterized by comprising the following steps: c in step two6N7Cl3And the mass ratio of the dosage of the 4, 4' -azodiphenylamine is 1g: 1-1.5 g.
3. A compound C according to claim 16N7Cl3The preparation method of the-DAAB polymer photocatalytic hydrogen production catalyst is characterized by comprising the following steps: and the reaction condition in the step two is that stirring is carried out for 20-24 h under shading at room temperature, and then the reaction is carried out for 2h under the condition of oil bath heating reflux at 125-135 ℃.
4. A compound C according to claim 16N7Cl3The preparation method of the-DAAB polymer photocatalytic hydrogen production catalyst is characterized by comprising the following steps: c in step two6N7Cl3The mass and the volume of each detergent of the acetone-water mixture with the volume ratio of 1:1 to toluene and acetone used in washingThe volume ratio is 1g: 10-20 mL.
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| CN1788841A (en) * | 2005-12-21 | 2006-06-21 | 华东师范大学 | Hydrogen production catalyst, preparation and its uses |
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| CN105772056A (en) * | 2016-04-28 | 2016-07-20 | 成都理工大学 | Preparation method and application of graphite-phase carbon nitride photocatalysis material |
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