CN108607595A - The preparation method and applications of carbonitride homotype hetero-junctions with ordered mesopore structure - Google Patents
The preparation method and applications of carbonitride homotype hetero-junctions with ordered mesopore structure Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 claims abstract description 9
- 229940012189 methyl orange Drugs 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000010865 sewage Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009510 drug design Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 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 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910003256 NaTaO3 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 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
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to domain of inorganic chemistry, it is related to a kind of with dicyandiamide, urea and hard template silica SBA 15 being that raw material prepares the carbonitride homotype heterojunction structure for having ordered mesopore structure, and applies it in the sewage disposal of methyl orange.Preparation process is divided into two steps：First, silica hard template SBA 15 is prepared；Then, the carbonitride homotype heterojunction material with ordered mesopore structure is prepared.The introducing of ordered mesopore structure brings the specific surface area of superelevation, enhances the utilization ratio of visible light；The rational design of homotype hetero-junctions and structure accelerate the separation of photo-generate electron-hole pair, improve the quantum efficiency of catalyst.The present invention substantially improves the photocatalytic activity of carbonitride, has good degradation effect to methyl orange.
Description
Technical field
The invention belongs to domain of inorganic chemistry, be related to one kind is with urea, dicyandiamide and hard template silica SBA-15
Raw material prepares the carbonitride homotype heterojunction structure material for having ordered mesopore structure, and applies it at methyl orange sewage
In reason.
Background technology
As organic semiconducting materials, graphite phase carbon nitride purposes is very extensive, can be used as preparing mesoporous material, metal nitrogen
The nitrogen source of compound or high-performance abrasion-proof material etc..In 2006, the report about g-C3N4 as nonmetallic heterogeneous catalysis
Occur.G-C3N4 has been started after this as Novel non-metal semiconductor catalysis material, in the research heat of catalytic field application
Tide.
According to the characteristic and light-catalysed reaction mechanism of semiconductor structure and valence band conduction band, we can be directed to nitridation
The characteristic of carbon is modified accordingly, it is expected to obtain higher catalytic activity.In existing documents and materials and related journals
In report, the modification of carbonitride improves the service life of photo-generate electron-hole pair from light absorbing region, enhancing efficiency of light absorption is widened
It sets out, metal ion mixing, nonmetallic ion-doped, template preparation, stripping nano piece and semiconductor has been carried out to carbonitride
It is compound, etc. modified methods, obtain a large amount of novel carbon nitride photocatalyst, be widely used in photodegradation elutriation hydrogen, light drop
Pollutant etc. is solved, has superior photocatalysis performance compared to other catalyst.
Photocatalysis technology is still difficult to realize Cheap highly effective conversion and utilizes solar energy at present.Main cause is reported at present
Semiconductor light-catalyst such as TiO2、NaTaO3Deng only in ultraviolet region could showing catalytic activity, but ultraviolet light only accounts for sunlight
Gross energy 7%, and 400~760nm visible lights account for sunshine gross energy 50%.In recent years, it by existing Photocatalyst or opens
It sends out and responds and have the novel photocatalysis material of relatively narrow energy gap in visible-range, become the hot spot of photocatalysis research field.
Currently, the research of novel visible responsive photocatalyst, which is concentrated mainly on, improves the visible light-responded of photochemical catalyst：To traditional light
Catalyst TiO2It is modified modification；Prepare the compound catalysis material with heterojunction structure；Exploitation can directly absorb can
Light-exposed novel semi-conductor catalysis material.Ti systems, Ta systems, Nb systems, Bi systems, W systems, Ag systems, Mo systems, Co systems etc. are proven to have
It is visible light-responded and there is preferable photocatalytic activity in terms of decomposing water and organic matter.
The research of current developed novel photocatalyst, light-catalyzed reaction mechanism also in imagination and speculates the stage,
Up for continuing to deepen.Although having developed a variety of visible light responsive photocatalysts, most of photo-quantum efficiency is not high, can
The catalytic capability in light-exposed area is very low, easy in inactivation, some easy to produce photochemical corrosion as photochemical catalyst.Major part needs to find
Suitable carrier and process for fixation had both overcome suspended phase photochemical catalyst easily to agglomerate, difficult the shortcomings of recycling using carrier.Graphite-phase
Carbonitride has received widespread attention in novel visible response semiconductor field of photocatalytic material.In the research to carbonitride
In, porous structure can increase the utilization ratio of light, and hetero-junctions can extend the service life of photo-generate electron-hole pair.Cong et al. will
Melamine and urea are calcined together by different proportion is made nitride porous carbon homotype hetero-junctions, almost can be complete in two hours
Degradation of methylene blue and rhodamine B (Cong, L., H.Mu, S.Zhang, et al., Nano, 2017.12 (04):1750042).
Consult data of literatures, the research of carbonitride homotype hetero-junctions is relatively fewer at present, and about order mesoporous and
The research that homotype hetero-junctions is combined rarely has people to be related to.
Invention content
Based on existing photocatalysis technology, the present invention is using urea and dicyandiamide as presoma, using silica SBA-15 as mould
Plate agent is that solvent handles three with deionized water, is calcined under certain condition after crossing rate drying while hot, hydrofluoric acid is used in combination
After etching away template, carbonitride homotype hetero-junctions is successfully made, and it is different that ordered mesopore structure introduced carbonitride homotype
Matter knot, Will it are applied in the sewage disposal of methyl orange.
Technical scheme is as follows：
The preparation method of carbonitride homotype hetero-junctions with ordered mesopore structure, includes the following steps：
Step 1 prepares silicon dioxide hard template SBA-15：
4g P123 are weighed at room temperature is dissolved in 150mL, 1.6molL-1HCl solution in, stirring in water bath 4h is extremely at 30 DEG C
The homogeneous solution of water white transparency；It reuses pipette and is added at one time 9.6mL tetraethyl orthosilicates (Tetraethyl
Orthosilicate, TEOS), heating water bath is then warming up to 40 DEG C of constant temperature stirrings for 24 hours, obtains milky white liquid mixture；Again will
The liner that mixture is transferred to 150mL is to be placed in baking oven, 100 DEG C of hydrothermal crystallizings in the stainless steel cauldron of polytetrafluoroethylene (PTFE)
48h；Mixed liquor filtering after hydrothermal crystallizing, is used in combination appropriate amount of deionized water to wash, obtains white foam solid；Filter cake is placed in
60 DEG C of thermostatic drying chambers dry 12h；Finally, with 5 DEG C of min in Muffle furnace-1Heating rate rise to 550 DEG C, roast 5h, remove
Go template, as mesoporous molecular sieve SBA-15 material；
Step 2, the carbonitride homotype heterojunction material for preparing ordered mesopore structure：
Urea and dicyandiamide are weighed in proportion, and ultrasonic agitation in 50-70 DEG C of deionized water is added after grinding and is uniformly mixed,
Obtain mixed liquor A；It weighs SBA-15 made from step 1 to be added in mixed liquor A, be filtered while hot after constant temperature stirring, in nitrogen after drying
Under atmosphere, temperature programming to heating temperature, heat preservation is cooled to room temperature, with hydrofluoric acid dips, centrifugation, with deionized water and anhydrous
Ethyl alcohol is washed to neutrality, dry to get to the carbonitride homotype heterojunction material DUPG with ordered mesopore structure.
In step 2, urea and dicyandiamide is selected to be used as presoma, the mass ratio of the urea and dicyandiamide is 5~10：
1, wherein in mixed liquor A, dicyandiamide is saturation state.
In step 2, the time that constant temperature stirring in mixed liquor A is added in the hard template silica SBA-15 is 2h, while hot mistake
Filter can effectively prevent the hydrolysis of urea, improve the solubility of urea and dicyandiamide in aqueous solution.
In step 2, the heating rate of temperature programming is 2~5 DEG C/min, and the heating temperature after heating is 480~580 DEG C,
Soaking time is 4h.
In step 2, the mass percentage concentration of hydrofluoric acid is 5%, and soaking time is for 24 hours；Drying temperature is 60 DEG C, when dry
Between be 8h.
Carbonitride homotype heterojunction material produced by the present invention with ordered mesopore structure is used for photocatalytic degradation first
Base orange, 2h degradation rates are up to 90%.
Description of the drawings
Fig. 1 is the XRD spectrum of the invention；
Fig. 2 is the N of the invention2Adsorption/desorption isotherms；
Fig. 3 is the graph of pore diameter distribution of the invention；
Fig. 4 is that methyl orange drop degradation rate changes over time relationship；
Fig. 5 is the degradation rate Transformation Graphs at any time of the invention cycle down solution methyl orange.
Specific embodiment
Below by specific embodiment and Figure of description, the present invention will be further described.
Embodiment 1：
Step 1 weighs 4g P123 and is dissolved in 150mL, 1.6molL at room temperature-1HCl solution in, at 30 DEG C water-bath stir
4h is mixed to the homogeneous solution of water white transparency.It reuses pipette and is added at one time 9.6mL tetraethyl orthosilicates (Tetraethyl
Orthosilicate, TEOS), heating water bath is then warming up to 40 DEG C of constant temperature stirrings for 24 hours, obtains milky white liquid mixture.Again will
The liner that mixture is transferred to 150mL is to be placed in baking oven, 100 DEG C of hydrothermal crystallizings in the stainless steel cauldron of polytetrafluoroethylene (PTFE)
48h.Mixed liquor filtering after hydrothermal crystallizing, is used in combination appropriate amount of deionized water to wash, obtains white foam solid.Filter cake is placed in
60 DEG C of thermostatic drying chambers dry 12h.Finally, with 5 DEG C of min in Muffle furnace-1Heating rate rise to 550 DEG C, roast 5h, remove
Go template, as mesoporous molecular sieve SBA-15 material；
Step 2,
It is 15 in mass ratio:2 weigh be added after urea and dicyandiamide grinding a certain amount of 10mL60 DEG C deionized water it is super
Sound stirs, it is made to be uniformly mixed, and the SBA-15 for weighing step 2g is added in above-mentioned mixed liquor, the constant temperature stirring and while hot at 60 DEG C
Filtering is heated to 550 DEG C with the heating rate of 2.5 DEG C/min, keeps the temperature 4h, be cooled to room temperature, use in a nitrogen atmosphere
The hydrofluoric acid dips of 100mL5% 24 hours, centrifugation, are washed with deionized water and absolute ethyl alcohol, the dry 8h at 60 DEG C, both
To sample DUPG.
Photocatalysis effect is tested：
Using the GHX-2 type photochemical reactors of city Science and Technology Ltd. of Yangzhou University.15mg catalyst is weighed to be added to
In the methyl orange solution of the 10mg/L of 50Ml, after dark reaction half an hour, opens light source and sample 3-4ml every 10min, make after suction filtration
With the real-time concentration with measurement of ultraviolet-visible spectrophotometer methyl orange.UV, visible light spectrophotometric used is UV-3100 types.
Embodiment 2：
Step 1, with the step 1 of embodiment 1；
Step 2,
It is 15 in mass ratio:1.5 weigh urea and dicyandiamide grinding after a certain amount of 10mL50 DEG C of deionized water is added
Ultrasonic agitation makes it be uniformly mixed, and the SBA-15 for weighing step 2g is added in above-mentioned mixed liquor, and constant temperature is stirred and taken advantage of at 50 DEG C
Heat filtering is heated to 500 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 4h, be cooled to room temperature, use in a nitrogen atmosphere
The hydrofluoric acid dips of 100mL5% 24 hours, centrifugation, are washed with deionized water and absolute ethyl alcohol, the dry 8h at 60 DEG C, both
To sample DUPG2.
Embodiment 3：
Step 1 of the step 1 with embodiment 1；
Step 2
It is 15 in mass ratio:3 weigh be added after urea and dicyandiamide grinding a certain amount of 10mL65 DEG C deionized water it is super
Sound stirs, it is made to be uniformly mixed, and the SBA-15 for weighing step 2g is added in above-mentioned mixed liquor, the constant temperature stirring and while hot at 65 DEG C
Filtering is heated to 580 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 4h, be cooled to room temperature, use 100mL5% in a nitrogen atmosphere
Hydrofluoric acid dips 24 hours, centrifugation wash with deionized water and absolute ethyl alcohol, 8h dried at 60 DEG C, both obtains sample
DUPG3。
Embodiment 4：
Step 1 of the step 1 with embodiment 1；
Step 2
It is 15 in mass ratio:3 weigh be added after urea and dicyandiamide grinding a certain amount of 10mL70 DEG C deionized water it is super
Sound stirs, it is made to be uniformly mixed, and the SBA-15 for weighing step 2g is added in above-mentioned mixed liquor, the constant temperature stirring and while hot at 70 DEG C
Filtering is heated to 480 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 4h, be cooled to room temperature, use 100mL5% in a nitrogen atmosphere
Hydrofluoric acid dips 24 hours, centrifugation wash with deionized water and absolute ethyl alcohol, 8h dried at 60 DEG C, both obtains sample
DUPG3。
As shown in Fig. 1, the invention completely remains the original structure of carbonitride, and reduces the crystallization of former carbonitride
Degree.
As shown in attached drawing 2 and attached drawing 3, which has been successfully, reproduced the orderly pore passage structure of template SBA-15, successfully makes
The carbonitride homotype heterojunction material with ordered mesopore structure was obtained, specific surface area reaches 169.1m2/ g, average pore size are only
5.95nm。
Such as attached drawing 4, which has reached 90% to the degradation efficiency of methyl orange, and the invention is by recycling and repeating first of degrading
The degradation rate of base orange such as attached drawing 5, the invention material still have good catalytic activity, the surface invention material after reuse
Expect with good stability.
Claims (7)
1. the preparation method of the carbonitride homotype hetero-junctions with ordered mesopore structure, which is characterized in that include the following steps：
Step 1 prepares silicon dioxide hard template SBA-15, spare；
Step 2, the carbonitride homotype heterojunction material for preparing ordered mesopore structure：
Urea and dicyandiamide are weighed in proportion, and ultrasonic agitation in 50-70 DEG C of deionized water is added after grinding and is uniformly mixed, obtains mixed
Close liquid A；It weighs SBA-15 made from step 1 to be added in mixed liquor A, be filtered while hot after constant temperature stirring, in nitrogen atmosphere after drying
Under, temperature programming to heating temperature, heat preservation is cooled to room temperature, with hydrofluoric acid dips, centrifugation, with deionized water and absolute ethyl alcohol
Washing is dry to get to the carbonitride homotype heterojunction material DUPG with ordered mesopore structure to neutrality.
2. the preparation method of the carbonitride homotype hetero-junctions according to claim 2 with ordered mesopore structure, feature
It is, in step 2, the mass ratio of the urea and dicyandiamide is 5~10：1, wherein in mixed liquor A, dicyandiamide is saturation
State.
3. the preparation method of the carbonitride homotype hetero-junctions according to claim 2 with ordered mesopore structure, feature
It is, in step 2, the time that constant temperature stirs in mixed liquor A is added as 2h in the hard template silica SBA-15.
4. the preparation method of the carbonitride homotype hetero-junctions according to claim 2 with ordered mesopore structure, feature
It is, in step 2, the heating rate of temperature programming is 2~5 DEG C/min, and the heating temperature after heating is 480~580 DEG C, heat preservation
Time is 4h.
5. the preparation method of the carbonitride homotype hetero-junctions according to claim 2 with ordered mesopore structure, feature
It is, in step 2, the mass percentage concentration of hydrofluoric acid is 5%, and soaking time is for 24 hours.
6. the preparation method of the carbonitride homotype hetero-junctions according to claim 2 with ordered mesopore structure, feature
It is, in step 2, drying temperature is 60 DEG C, drying time 8h.
7. the carbonitride homotype with ordered mesopore structure made from any one of claim 1~6 preparation method is heterogeneous
Knot is used for photo-catalytic degradation of methyl-orange, and 2h degradation rates are up to 90%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680371A (en) * | 2021-09-10 | 2021-11-23 | 润泰化学（泰兴）有限公司 | Application and preparation method of bimetallic catalyst for synthesizing 1, 2-cyclohexane dimethyl phthalate from dimethyl phthalate |
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| CN114700103A (en) * | 2022-04-12 | 2022-07-05 | 广州大学 | Immobilized preparation method of metal-free carbon-based catalyst, product and application thereof |
| CN114700103B (en) * | 2022-04-12 | 2023-10-27 | 广州大学 | Immobilization preparation method of metal-free carbon-based catalyst, product and application of product |
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