CN117065783A - Preparation method and application of precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride - Google Patents
Preparation method and application of precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002243 precursor Substances 0.000 title claims abstract description 47
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 3
- 231100000719 pollutant Toxicity 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 30
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000003607 modifier Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 239000008236 heating water Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 42
- 229910002804 graphite Inorganic materials 0.000 abstract description 42
- 239000010439 graphite Substances 0.000 abstract description 42
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- -1 carbon nitrides Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 88
- 239000000463 material Substances 0.000 description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000003795 desorption Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 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 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
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- 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
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
A preparation method and application of precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride, which relate to a preparation method and application of a photocatalyst. The invention aims to solve the problems of complex process, low efficiency, high cost and harsh conditions existing in the existing technology for preparing graphite-phase carbon nitride with large specific surface area. The method comprises the following steps: 1. preparing a self-assembled rod-shaped precursor; 2. corn-shaped graphite-phase carbon nitrides with different specific surface areas are synthesized by controlling the calcination conditions. A precursor regulated corn-shaped graphite-phase carbon nitride with adjustable specific surface area is used for photocatalytic degradation of serial dye pollutants in water. The invention can obtain the corn-shaped graphite phase carbon nitride with adjustable specific surface area.
Description
Technical Field
The invention relates to a preparation method and application of corn-shaped graphite phase carbon nitride with adjustable specific surface area.
Background
In the rapid development of society, a series of energy and environmental problems caused by the over-exploitation of energy are required to be properly dealt with. The use of solar photocatalytic technology to solve this problem is an environmentally friendly reliable solution.
The graphite phase carbon nitride serving as a photocatalyst has the advantages of good energy band structure, lower preparation cost, nonmetallic element structure, good thermal stability, chemical stability and the like. However, graphite-phase carbon nitride synthesized by the traditional calcination method tends to be in a block state, and the specific surface area is small. In the existing modification method, the secondary calcination method has low efficiency due to the strong decomposition and gasification process, and the improvement of the specific surface area is often not ideal enough; the solvent stripping method often requires a long time of ultrasonic treatment to screen out the thin layer part obtained by stripping, which results in extremely low efficiency, and often requires a strong acid or a highly toxic solvent, which has potential safety hazard. There is therefore a need for a simple and safe method to increase the specific surface area of graphite phase carbon nitride.
Disclosure of Invention
The invention aims to solve the problems of complex method, low efficiency and high risk in the existing process of preparing the graphite-phase carbon nitride material with large specific surface area, and provides a preparation method and application of precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride.
The preparation method of the precursor regulated and controlled corn-shaped graphite-phase carbon nitride with adjustable specific surface area is characterized by comprising the following steps of:
1. preparing an autonomous rod-shaped precursor:
(1) adding raw material melamine into deionized water, and stirring in a heating water bath kettle to completely dissolve the melamine to obtain a solution I;
(2) adding the modifier into deionized water, and stirring in a heating water bath kettle to completely dissolve the modifier to obtain a solution II;
(3) keeping the state of the solution I unchanged, rapidly pouring the solution II into the solution I, continuously stirring for 40-80 min, then stopping stirring, and continuously keeping the water bath heating state for 40-80 min to obtain milky suspension I;
(4) cooling the suspension I in air for 1-10 h, centrifuging, and removing supernatant to obtain a precipitate I;
(5) centrifugal cleaning is carried out on the precipitate I by using deionized water as a cleaning agent, and after repeated cleaning is carried out for 3 times, the precipitate I is dried to obtain a rod-shaped self-assembled precursor I;
2. and (3) placing the precursor I into a corundum crucible with a cover, and calcining in a muffle furnace to prepare the corn-shaped graphite-phase carbon nitride with the adjustable specific surface area.
The invention has the advantages that:
1. compared with the traditional preparation method, the precursor-regulated corn-shaped graphite-phase carbon nitride with adjustable specific surface area has larger specific surface area, smaller size, stronger charge separation and higher activity.
2. Compared with the existing method for preparing the graphite-phase carbon nitride with large specific surface area, the precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride prepared by the method is simpler, more convenient, safer and higher in efficiency, and can regulate and control the specific surface area of the graphite-phase carbon nitride.
Drawings
FIG. 1 is a scanning electron microscope image of a graphite phase carbon nitride material prepared by test one;
FIG. 2 is a graph showing the desorption of nitrogen from a graphite phase carbon nitride material synthesized directly from melamine prepared in test one;
FIG. 3 is a scanning electron microscope image of a graphite phase carbon nitride material prepared in test two;
FIG. 4 is a graph of nitrogen adsorption and desorption for graphite phase carbon nitride materials prepared in test two;
FIG. 5 is an X-ray diffraction pattern of graphite phase carbon nitride materials prepared in test one and test two;
FIG. 6 is a graph of the UV-visible diffuse reflectance spectra of graphite-phase carbon nitride materials prepared in test one and test two;
FIG. 7 is a graph of nitrogen adsorption and desorption for a graphite phase carbon nitride material prepared in test three;
FIG. 8 is a graph of nitrogen adsorption and desorption for graphite phase carbon nitride materials prepared in test four;
FIG. 9 is a graph of nitrogen adsorption and desorption for graphite phase carbon nitride materials prepared in test five;
FIG. 10 is a graph showing the desorption of nitrogen from graphite phase carbon nitride materials prepared in test six;
FIG. 11 is a graph showing the desorption of nitrogen from graphite phase carbon nitride materials prepared in test seven;
FIG. 12 is a photocatalytic degradation methyl orange activity of graphite phase carbon nitride materials prepared in test one and test six;
FIG. 13 is a photocatalytic degradation methylene blue activity of graphite phase carbon nitride materials prepared in test one and test six;
fig. 14 is a photocatalytic degradation rhodamine B activity for the graphite phase carbon nitride materials prepared in test one and test six.
Detailed Description
The examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
The first embodiment is as follows: the embodiment is a preparation method of corn-shaped graphite phase carbon nitride with adjustable specific surface area regulated by a precursor, which is completed according to the following steps:
1. preparing an autonomous rod-shaped precursor:
(1) adding melamine as a raw material into deionized water, and stirring in a heating water bath kettle to completely dissolve the melamine to obtain a solution I.
(2) Adding the modifier into deionized water, and stirring in a heating water bath kettle to completely dissolve the modifier to obtain solution II.
(3) Keeping the state of the solution I unchanged, rapidly pouring the solution II into the solution I, continuously stirring for 40-80 min, then stopping stirring, and continuously keeping the water bath heating state for 40-80 min to obtain milky suspension I;
(4) cooling the suspension I in air for 1-10 h, centrifuging, and removing supernatant to obtain a precipitate I;
(5) centrifugal cleaning is carried out on the precipitate I by using deionized water as a cleaning agent, and after repeated cleaning is carried out for 3 times, the precipitate I is dried to obtain a rod-shaped self-assembled precursor I;
2. and (3) placing the precursor I into a corundum crucible with a cover, and calcining in a muffle furnace to prepare the corn-shaped graphite-phase carbon nitride with the adjustable specific surface area.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the volume ratio of the melamine raw material to the deionized water in the step one (1) is (3-10 g): (400-1000 mL); the water bath temperature in the step one (1) is 60-80 ℃; the stirring speed in the step one (1) is 300-500 r/min; the stirring time in the step one (1) is 40-80 min. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the modifier in the step one (2) is cyanuric acid; the volume ratio of the mass of the modifier to the deionized water in the step one (2) is (3-10 g): (400-1000 mL); the water bath temperature in the step one (2) is 60-80 ℃; the stirring speed in the step one (2) is 300-500 r/min; the stirring time in the step one (2) is 40-80 min. Other steps are the same as those of the first to second embodiments.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the stirring time in the step one (3) is 40-80 min; the heating time in the step one (3) is 40-80 min. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the cooling time in the step one (4) is 1-10 h; the centrifugal speed in the step one (4) is 2000-6000 rpm. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the centrifugal speed in the step one (5) is 2000-6000 rpm; the drying temperature in the step one (5) is 60-90 ℃; the drying time in the step one (5) is 5-24 h. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the precursor in the second step has the mass of 0.5-100 g; the volume of the crucible in the second step is 5-500 mL; the calcining temperature in the second step is 400-700 ℃; the temperature rising rate in the second step is 0.5-10 ℃/min; the constant temperature time in the second step is 2-8 h. Other steps are the same as those of embodiments one to six.
Eighth embodiment: the embodiment is a precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride for photocatalytic degradation of dye pollutants in water.
The present invention will be described in detail with reference to the accompanying drawings and examples.
Test one: the preparation method of the graphite phase carbon nitride with unregulated precursor is specifically completed by the following steps:
10g of melamine is put into a corundum crucible with a cover, the volume of which is 100mL, the crucible is put into a muffle furnace, the temperature in the muffle furnace is increased to 550 ℃ at a heating rate of 2 ℃/min, the temperature is kept at the constant temperature of 550 ℃ for 4 hours, and then the crucible is naturally cooled to room temperature. Obtaining the graphite phase carbon nitride material directly prepared by melamine.
FIG. 1 is a scanning electron microscope image of a graphite phase carbon nitride material prepared by test one;
as can be seen from fig. 1, the graphite phase carbon nitride material directly prepared from melamine exhibits a bulk morphology.
Fig. 2 is a graph showing the desorption of nitrogen from graphite phase carbon nitride materials synthesized directly from melamine prepared in test one. The results showed that the specific surface area of the sample was 16.74m 2 /g。
And (2) testing II: the preparation method of the precursor regulated and controlled corn-shaped graphite-phase carbon nitride with adjustable specific surface area is specifically completed according to the following steps:
1. preparing an autonomous rod-shaped precursor:
(1) adding 5g of raw material melamine into 500mL of deionized water, heating the mixture in a water bath kettle at 80 ℃ and stirring the mixture at 400r/min for 60min to completely dissolve the melamine to obtain a solution I;
(2) adding 5g of modifier into 500mL of deionized water, heating the mixture in a water bath kettle at 80 ℃ and stirring the mixture at 400r/min for 60min to completely dissolve the modifier, thereby obtaining solution II;
(3) keeping the state of the solution I unchanged, rapidly pouring the solution II into the solution I, continuously stirring for 60min, then stopping stirring, and continuously keeping the water bath heating state for 60min to obtain milky suspension I;
(4) cooling the suspension I in air for 4 hours, centrifuging at 4000rpm, and removing the supernatant to obtain a precipitate I;
(5) washing the precipitate I by using deionized water as a cleaning agent, centrifuging at 4000rpm, removing supernatant, repeatedly cleaning for 3 times, and putting the precipitate I into an oven at 80 ℃ for drying treatment for 12 hours to obtain a rod-shaped self-assembled precursor I;
2. 20g of the precursor I is placed into a corundum crucible with a cover, the volume of which is 100mL, the crucible is placed into a muffle furnace, the temperature in the muffle furnace is increased to 550 ℃ at a heating rate of 2 ℃/min, the temperature is kept at the constant temperature of 550 ℃ for 4 hours, and then the crucible is naturally cooled to room temperature. Obtaining the corn-shaped graphite phase carbon nitride material.
FIG. 3 is a scanning electron microscope image of a graphite phase carbon nitride material prepared in test two;
as can be seen from fig. 3, the graphite phase carbon nitride material prepared in the test two exhibited a corn-like structure, and it was found by comparing with the test sample that the sample prepared in the test two had a smaller size.
FIG. 4 is a graph showing the desorption of nitrogen from graphite phase carbon nitride material prepared in test II, showing that the specific surface area of the sample prepared in test II is 97.71m 2 And/g, the precursor regulation can provide larger specific surface area for the prepared sample.
FIG. 5 is an X-ray diffraction chart, wherein 1 is a graphite-phase carbon nitride material directly synthesized by melamine prepared in test one, and 2 is a corn-shaped graphite-phase carbon nitride material prepared in test two;
as can be seen from fig. 5, the diffraction peak of 2 is lower than 1, and the highest peak of 2 is slightly shifted to a high angle compared to 1, indicating that the overall size of 2 is smaller than 1.
FIG. 6 is an ultraviolet-visible diffuse reflectance spectrum, wherein 1 is a graphite-phase carbon nitride material directly synthesized from melamine prepared in test one, and 2 is a corn-shaped graphite-phase carbon nitride material prepared in test two;
as can be seen from fig. 6, the spectrum of 2 is significantly blue shifted compared to 1, again demonstrating that the overall size of 2 is less than 1.
And (3) test III: the difference between the test and the test II is that: in the second step, the mass of the precursor I is 25g. Other steps and parameters were the same as those of test two.
FIG. 7 is a graph showing the desorption of nitrogen from the graphite phase carbon nitride material prepared in test III, showing that the specific surface area of the sample prepared in test III is 78.70m 2 /g。
And (3) testing four: the difference between the test and the test II is that: in the second step, the mass of the precursor I is 15g. Other steps and parameters were the same as those of test two.
FIG. 8 is a graph showing the desorption of nitrogen from graphite phase carbon nitride material prepared in test four, showing that the specific surface area of the sample prepared in test four is 124.25m 2 /g。
Test five: the difference between the test and the test II is that: in the second step, the mass of the precursor I is 10g. Other steps and parameters were the same as those of test two.
FIG. 9 is a graph showing the desorption of nitrogen from a graphite phase carbon nitride material prepared in test five, showing that the specific surface area of the sample prepared in test five is 142.18m 2 /g。
Test six: the difference between the test and the test II is that: in the second step, the mass of the precursor I is 5g. Other steps and parameters were the same as those of test two.
FIG. 10 is a graph showing the desorption of nitrogen from a graphite phase carbon nitride material prepared in test six, showing that the specific surface area of the sample prepared in test six is 224.11m 2 /g。
The comparison of the specific surface area results of the graphite-phase carbon nitride materials prepared by the tests II, III, four, five and six shows that the specific surface area of the prepared graphite-phase carbon nitride material and the mass of the precursor in the crucible are in a negative correlation relationship under the condition of unchanged fixed crucible volume, namely, the smaller the feeding amount of the precursor into the crucible is, the larger the specific surface area of the prepared graphite-phase carbon nitride material is.
Test seven: the difference between the test and the test V is that: the volume of the corundum crucible with the cover in the second step is 50mL. Other steps and parameters were the same as in test five.
FIG. 11 is a graph showing the desorption of nitrogen from a graphite phase carbon nitride material prepared in test seven, showing that the specific surface area of the sample prepared in test seven is 98.96m 2 /g。
Comparing the specific surface area results of the graphite-phase carbon nitride material prepared by the test seven with the specific surface area results of the graphite-phase carbon nitride material prepared by the test five, the specific surface area of the prepared graphite-phase carbon nitride material and the volume of the crucible are in positive correlation under the condition that the mass of the precursor put into the crucible is unchanged, namely, the larger the volume of the crucible is, the larger the specific surface area of the prepared graphite-phase carbon nitride material is.
In addition, by comparison, the graphite phase carbon nitride material prepared in test six has the highest specific surface area in the series of tests.
The graphite-phase carbon nitride materials prepared in test one and test six were placed in two 250mL beakers, 100mL of methyl orange solution with a concentration of 15mg/L was added thereto, stirring was continued for 30min at 400r/min under dark conditions, and then the mixture was irradiated with a 300W xenon lamp for 1h, after which the liquid was centrifuged at 8000rpm, the supernatant was taken and the degradation rate was measured by a spectrophotometer model UV-3600 Plus, and the measurement results were shown in fig. 12, wherein 1 and 6 were the activities of the graphite-phase carbon nitride materials prepared in test one and test six, respectively.
As can be seen from fig. 12, the graphite phase carbon nitride material prepared in test six has higher methyl orange degrading activity than the graphite phase carbon nitride material prepared in test one. The comparison result proves that the photocatalytic degradation methyl orange performance of the material can be improved by adjusting and controlling the precursor to improve the specific surface area of the corn-shaped graphite phase carbon nitride.
The graphite-phase carbon nitride materials prepared in test one and test six were placed in two 250mL beakers, respectively, 100mL of methylene blue solution having a concentration of 15mg/L was added thereto, stirred at 400r/min for 30min under dark conditions, then stirring was continued and irradiated with a 300W xenon lamp for 1h, and after the liquid was centrifuged at 8000rpm, the supernatant was taken and the degradation rate thereof was tested by a spectrophotometer model UV-3600 Plus, and the test results were shown in fig. 13, wherein 1 and 6 were the activities of the graphite-phase carbon nitride materials prepared in test one and test six, respectively.
As can be seen from fig. 13, the graphite phase carbon nitride material prepared in test six has a higher methylene blue degradation activity than the graphite phase carbon nitride material prepared in test one. The comparison result proves that the photocatalytic degradation methylene blue performance of the material can be improved by adjusting and controlling the precursor to improve the specific surface area of the corn-shaped graphite phase carbon nitride.
The graphite-phase carbon nitride materials prepared in test one and test six were placed in two 250mL beakers, 100mL of rhodamine B solution having a concentration of 15mg/L was added thereto, stirring was continued for 30min at 400r/min under dark conditions, stirring was continued and irradiated with a 300W xenon lamp for 30min, and after the liquid was centrifuged at 8000rpm, the supernatant was taken and the degradation rate thereof was tested by a spectrophotometer of model UV-3600 Plus, and the test results were shown in fig. 14, wherein 1 and 6 were the activities of the graphite-phase carbon nitride materials prepared in test one and test six, respectively.
As can be seen from fig. 14, the graphite phase carbon nitride material prepared in test six has higher rhodamine B degrading activity than the graphite phase carbon nitride material prepared in test one. The comparison result proves that the photocatalytic degradation rhodamine B performance of the material can be improved by adjusting and controlling the precursor to improve the specific surface area of the corn-shaped graphite phase carbon nitride.
Claims (8)
1. The preparation method of the precursor regulated and controlled corn-shaped graphite-phase carbon nitride with adjustable specific surface area is characterized by comprising the following steps of:
1. preparing an autonomous rod-shaped precursor:
(1) adding raw material melamine into deionized water, and stirring in a heating water bath kettle to completely dissolve the melamine to obtain a solution I;
(2) adding the modifier into deionized water, and stirring in a heating water bath kettle to completely dissolve the modifier to obtain a solution II;
(3) keeping the state of the solution I unchanged, rapidly pouring the solution II into the solution I, continuously stirring for 40-80 min, then stopping stirring, and continuously keeping the water bath heating state for 40-80 min to obtain milky suspension I;
(4) cooling the suspension I in air for 1-10 h, centrifuging, and removing supernatant to obtain a precipitate I;
(5) centrifugal cleaning is carried out on the precipitate I by using deionized water as a cleaning agent, and after repeated cleaning is carried out for 3 times, the precipitate I is dried to obtain a rod-shaped self-assembled precursor I;
2. and (3) placing the precursor I into a corundum crucible with a cover, and calcining in a muffle furnace to prepare the corn-shaped graphite-phase carbon nitride with the adjustable specific surface area.
2. The preparation method of the precursor-regulated corn-shaped graphite-phase carbon nitride with the adjustable specific surface area, which is disclosed in claim 1, is characterized in that the volume ratio of the melamine raw material to deionized water in the step one (1) is (3-10 g): (400-1000 mL); the water bath temperature in the step one (1) is 60-80 ℃; the stirring speed in the step one (1) is 300-500 r/min; the stirring time in the step one (1) is 40-80 min.
3. The method for preparing precursor-controlled corn-shaped graphite-phase carbon nitride with adjustable specific surface area according to claim 1, wherein the modifier in the step one (2) is cyanuric acid; the volume ratio of the mass of the modifier to the deionized water in the step one (2) is (3-10 g): (400-1000 mL); the water bath temperature in the step one (2) is 60-80 ℃; the stirring speed in the step one (2) is 300-500 r/min; the stirring time in the step one (2) is 40-80 min.
4. The method for preparing the precursor-controlled corn-shaped graphite-phase carbon nitride with adjustable specific surface area according to claim 1, wherein the stirring time in the step one (3) is 40-80 min; the heating time in the step one (3) is 40-80 min.
5. The method for preparing the precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride according to claim 1, wherein the cooling time in the step one (4) is 1-10 h; the centrifugal speed in the step one (4) is 2000-6000 rpm.
6. The method for preparing precursor-controlled corn-shaped graphite-phase carbon nitride with adjustable specific surface area according to claim 1, wherein the centrifugal speed in the step one (5) is 2000-6000 rpm; the drying temperature in the step one (5) is 60-90 ℃; the drying time in the step one (5) is 5-24 h.
7. The method for preparing the precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride according to claim 1, wherein the precursor mass in the second step is 0.5-100 g; the volume of the crucible in the second step is 5-500 mL; the calcining temperature in the second step is 400-700 ℃; the temperature rising rate in the second step is 0.5-10 ℃/min; the constant temperature time in the second step is 2-8 h.
8. The preparation method of the precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride is characterized in that the precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride is used for photocatalytic degradation of dye pollutants in water.
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