CN110124719A - A kind of preparation method and application of highly crystalline carbonitride catalysis material - Google Patents
A kind of preparation method and application of highly crystalline carbonitride catalysis material Download PDFInfo
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- CN110124719A CN110124719A CN201910423596.9A CN201910423596A CN110124719A CN 110124719 A CN110124719 A CN 110124719A CN 201910423596 A CN201910423596 A CN 201910423596A CN 110124719 A CN110124719 A CN 110124719A
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 29
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001103 potassium chloride Substances 0.000 claims abstract description 14
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 125000004193 piperazinyl group Chemical group 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000004885 piperazines Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010985 leather Substances 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
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012719 thermal polymerization 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
-
- 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
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method and application of highly crystalline carbonitride catalysis material, belongs to conductor photocatalysis material technical field.It is calcined firstly, melamine is placed in Muffle furnace, obtains seven piperazine presomas；Then, seven piperazine presomas, sylvite and lithium salts ground and mixed is uniform, it is placed in Muffle furnace and is calcined, it is cleaned, dry after taking-up, obtain crystallization carbonitride；Obtained crystallization carbonitride is dispersed in hydrochloric acid, lasting to stir, washing is dry to get the highly crystalline carbonitride catalysis material.The present invention handles crystallization carbonitride in aqueous hydrochloric acid solution, and the crystallinity of the carbonitride made greatly enhances, and the carbonitride of high-crystallinity has very big advantage in migration photo-generated carrier and in terms of inhibiting photo-generate electron-hole pairs.Meanwhile the potassium ion for being embedded in highly crystalline carbonitride middle layer is also that very big contribution has been made in the migration of light induced electron.Have benefited from the two characteristics, the Photocatalyzed Hydrogen Production activity of the highly crystalline carbonitride of the present invention greatly enhances.
Description
Technical field
The invention belongs to conductor photocatalysis material technical fields, specifically, Photocatalyzed Hydrogen Production can be enhanced by being related to one kind
The preparation method and application of active highly crystalline carbonitride catalysis material.
Background technique
With the development of National Highway, environmental problem and energy problem become two hang-ups of current urgent need to resolve.By
In the high-energy density and no pollution characteristic of hydrogen, it is considered to be solve the desirable route of this two large problems.And solar energy conduct
How efficiently, economically a kind of inexhaustible, nexhaustible clean energy resource, become using solar energy to solve environmental problem
The target of researchers' effort for it.Catalysis material is converted into the tie of Hydrogen Energy as solar energy, its development, which receives, grinds
The extensive concern for the person of studying carefully.
From graphite type carbon nitride (g-C in 20093N4) since polymer is successfully applied to photocatalysis field, which makees
For a kind of non-metal optical catalysis material, there is many advantages, such as chemical stability is good, at low cost, nontoxic, cause the wide of people
General concern.But the g-C of traditional thermal polymerization preparation3N4Only semi-crystal or pseudocone structure, cause photocatalytic activity poor.
In order to solve this problem, there has been proposed the methods of various synthesis crystallization carbonitride (CCN), such as molten-salt growth method, microwave-assisted conjunction
At with some other method.In these methods, molten-salt growth method is a kind of easy to operate, powerful green method.However, molten
(002) surface intensity of CCN prepared by salt method is consistently lower than the carbonitride of pseudocone structure, shows the crystallinity of CCN and pays no attention to
Think.In the present invention, we have been put forward for the first time on the basis of molten-salt growth method, further increase carbonitride crystallinity method and its
Application in Photocatalyzed Hydrogen Production.
Summary of the invention
It is an object of the present invention to propose a kind of highly crystalline carbonitride photocatalysis material for defect existing for background technique
The preparation method and application of material.The highly crystalline carbonitride catalysis material that the method for the present invention obtains improves light in terms of two and urges
Change and produce hydrogen activity: firstly, since the raising of crystallinity, the hydrogen bond in HCCN surface texture defect and structure is reduced, and facilitates light
The migration of raw carrier simultaneously reduces the compound of photo-generate electron-hole pairs simultaneously；Secondly, the highly crystalline carbonitride of molten-salt growth method preparation,
Potassium ion is embedded in interlayer structure, these potassium ions can increase electron delocalizationization and extend pi-conjugated system, thus into one
Step increases the transfer of light induced electron.Meanwhile the method for the present invention is low in cost, simple process, easy to operate, green non-pollution.
To achieve the above object, the technical solution adopted by the present invention is as follows:
Highly crystalline carbonitride catalysis material provided by the invention, is made of seven piperazine structural units, a small amount of potassium ion insertion
The middle layer of structural unit.
In addition, being specifically included following the present invention also provides a kind of preparation method of highly crystalline carbonitride catalysis material
Step:
The preparation of step 1, seven piperazine presomas: melamine is weighed in semiclosed crucible, is placed in Muffle furnace and carries out
Calcining, after calcining, cooled to room temperature obtains seven piperazine presomas；
The preparation of step 2, crystallization carbonitride: seven piperazine presomas, sylvite and the lithium salts that step 1 is obtained are ground in mortar
Mill is uniformly mixed, and obtained mixture, which is placed in Muffle furnace, to be calcined, after calcining, cooled to room temperature；It obtains
Product uses hot water and ethanol washing, dry, obtains crystallization carbonitride；Wherein, the mass ratio of seven piperazine presomas, sylvite and lithium salts
For 1:(3~10): (3~10)；
The preparation of step 3, highly crystalline carbonitride catalysis material: the crystallization carbonitride that step 2 obtains is dispersed in hydrochloric acid
In, lasting to stir, obtained product water and ethanol washing is dry to get the highly crystalline carbonitride catalysis material.
Further, the concentration of hydrochloric acid described in step 3 is 0.005~0.2mol/L, and the time persistently stirred is 1~4h,
It is preferred that 1h.
Further, in step 3, when crystallization carbonitride is dispersed in hydrochloric acid, the dispersion concentration of crystallization carbonitride is 1~
5mg/mL。
Further, sylvite described in step 2 is potassium chloride, potassium nitrate etc., and the lithium salts is lithium chloride, lithium nitrate etc..
Preferably, the mass ratio of seven piperazine presomas, sylvite and lithium salts described in step 2 is 1:5.5:4.5.
Further, the temperature of calcining described in step 1 is 300~600 DEG C, preferably 500 DEG C；Calcination time is 2~6h, excellent
Select 4h.
Further, the temperature of calcining described in step 2 is 300~600 DEG C, preferably 550 DEG C；Calcination time is 2~6h, excellent
Select 4h；The temperature of the hot water is 50~90 DEG C, preferably 85 DEG C.
Further, temperature dry described in step 2 and step 3 is 60 DEG C, time 12h.
The present invention also provides highly crystalline carbonitride catalysis material answering in Photocatalyzed Hydrogen Production obtained by the above method
With.
Compared with prior art, the invention has the benefit that
1, the present invention provides a kind of preparation methods of highly crystalline carbonitride catalysis material, by crystallization carbonitride in hydrochloric acid
It is handled in aqueous solution, the crystallinity of the carbonitride made greatly enhances, and the carbonitride of high-crystallinity is in migration photo-generated carrier
There is very big advantage in terms of inhibition photo-generate electron-hole pairs.Meanwhile the potassium ion for being embedded in highly crystalline carbonitride middle layer is also
Very big contribution has been made in the migration of light induced electron.Have benefited from the two characteristics, the highly crystalline carbonitride that the present invention is prepared
Photocatalyzed Hydrogen Production activity greatly enhance.Concrete reason is: in general in seven piperazine structures, N (N1) atom pair of bridging is led
Band and the contribution of the edge of valence band less, illustrate that N1 atom will not be excited and generate Photoinduced Electron, photo-generated carrier would not lead to
N1 atom is crossed to shift in seven adjacent piperazine structures；And when K ion is inserted into highly crystalline carbonitride middle layer, seven adjacent piperazine lists
Member forms transmission path, increases electron delocalization, extends pi-conjugated system, be conducive to the transfer of photo-generated carrier between seven piperazine units.
2, the preparation method of a kind of highly crystalline carbonitride catalysis material provided by the invention, mild with process conditions,
Low in cost, green non-pollution is suitble to the features such as large-scale production.
Detailed description of the invention
Fig. 1 is blocky carbonitride, crystallization carbonitride and highly crystalline nitrogen prepared by comparative example 1-2 and embodiment 1-4
Change the XRD diffracting spectrum of carbon catalysis material；
(a) in Fig. 2, (b), (c) and (d) is respectively comparative example 1, comparative example 2, embodiment 2, light prepared by embodiment 3
The scanning electron microscope (SEM) photograph of catalysis material；
Fig. 3 is the performance of catalysis material Photocatalyzed Hydrogen Production under full light prepared by comparative example 1-2 and embodiment 1-4
Figure；
Fig. 4 is the principle of catalysis material Photocatalyzed Hydrogen Production under full light prepared by comparative example 1-2 and embodiment 1-4
Figure.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments.It should be understood that institute
Purpose for embodiment is the content that the present invention is further explained, and cannot be construed to protect the present invention in any sense
The limitation of range.
A kind of preparation method of highly crystalline carbonitride catalysis material, specifically includes the following steps:
The preparation of step 1, seven piperazine presomas: a certain amount of melamine is weighed in semiclosed crucible, is placed in Muffle furnace
In calcined, after calcining, cooled to room temperature obtains seven piperazine presomas；
The preparation of step 2, crystallization carbonitride: seven piperazine presomas, potassium chloride and the lithium chloride that step 1 is obtained are in mortar
Grinding is uniformly mixed, and obtained mixture is transferred in semiclosed crucible, is placed in Muffle furnace and is calcined, after calcining,
Cooled to room temperature；Obtained product uses hot water and ethanol washing, dry, obtains crystallization carbonitride；Wherein, seven piperazine forerunner
The mass ratio of body, sylvite and lithium salts is 1:(3~10): (3~10)；
The preparation of step 3, highly crystalline carbonitride catalysis material: the crystallization carbonitride that step 2 obtains is dispersed in hydrochloric acid
In, lasting to stir, obtained product water and ethanol washing is dry to get the highly crystalline carbonitride catalysis material.
Wherein, in step 1, the quality of the melamine is 1-10g, preferably 5g；Calcination temperature is 300-600 DEG C, excellent
Select 500 DEG C；Calcination time is 2-6h, preferably 4h.
Wherein, in step 2, the quality of the seven piperazines presoma is 0.1-1g, preferably 0.6g；Potassium chloride and lithium chloride mixing
The quality of object is 3-12g, preferably 6g (3.3g potassium chloride, 2.7g lithium chloride)；Calcination temperature is 300-600 DEG C, preferably 550 DEG C；
Calcination time is 2-6h, preferably 4h；The hot water temperature is 50-90 DEG C；It is preferred that 85 DEG C.
Wherein, in step 3, the quality of the crystallization carbonitride is 0.05-0.5g, preferably 0.1g；The volume of hydrochloric acid is 20-
60mL, preferably 40mL；The concentration of hydrochloric acid is 0.005-0.2mol/L；Mixing time is 1-4h, preferably 1h.
Wherein, temperature dry described in step 2 and step 3 is 60 DEG C, time 12h.
Comparative example 1:
A kind of preparation method of bulk carbonitride catalysis material, includes the following steps:
Weigh 8g melamine in semiclosed crucible, being placed in 550 DEG C of calcining 4h in Muffle furnace, after calcining, certainly
So it is cooled to room temperature to get blocky carbonitride.
Comparative example 2:
A kind of preparation method of crystallization carbonitride catalysis material, includes the following steps:
The preparation of (1) seven piperazine presoma: 5g melamine is weighed in semiclosed crucible, being placed in Muffle furnace 500 DEG C
4h is calcined, after calcining, cooled to room temperature is to get the seven piperazines presoma；
(2) preparation of crystallization carbonitride: firstly, weighing seven piperazine presomas prepared in 0.6g step (1), 3.3g chlorination
Potassium and 2.7g lithium chloride ground and mixed in mortar are uniform；Then mixture is transferred in semiclosed crucible, is placed in Muffle furnace
In 550 DEG C of calcining 4h, after calcining, cooled to room temperature, take out；Obtained product successively uses 85 DEG C of hot water and ethyl alcohol
Washing, up to the crystallization carbonitride after drying.
Embodiment 1:
A kind of preparation method of high crystallization carbonitride catalysis material, includes the following steps:
The preparation of (1) seven piperazine presoma: 5g melamine is weighed in semiclosed crucible, being placed in Muffle furnace 500 DEG C
4h is calcined, after calcining, cooled to room temperature is to get the seven piperazines presoma；
(2) preparation of crystallization carbonitride: firstly, weighing seven piperazine presomas prepared in 0.6g step (1), 3.3g chlorination
Potassium and 2.7g lithium chloride ground and mixed in mortar are uniform；Then mixture is transferred in semiclosed crucible, is placed in Muffle furnace
In 550 DEG C of calcining 4h, after calcining, cooled to room temperature, take out；Obtained product successively uses 85 DEG C of hot water and ethyl alcohol
Washing, up to the crystallization carbonitride after drying；
(3) preparation of Gao Jinghua carbonitride catalysis material: crystallization carbonitride prepared in 0.1g step (2) is dispersed
In 40mL aqueous hydrochloric acid solution (0.005mol/L), 1h is persistently stirred, obtained product water and ethanol washing, after drying to obtain the final product
The high crystallization carbonitride.
Embodiment 2:
Compared with Example 1, difference is the present embodiment: the concentration of aqueous hydrochloric acid solution is 0.01mol/L in step (3)；
Remaining step is same as Example 1.
Embodiment 3:
Compared with Example 1, difference is the present embodiment: the concentration of aqueous hydrochloric acid solution is 0.1mol/L in step (3)；Its
Remaining step is same as Example 1.
Embodiment 4:
Compared with Example 1, difference is the present embodiment: the concentration of aqueous hydrochloric acid solution is 0.2mol/L in step (3)；Its
Remaining step is same as Example 1.
Embodiment 5:
To above-described embodiment 1-4, gained catalysis material carries out Photocatalyzed Hydrogen Production activity experiment in comparative example 1-2, specifically
Experimental technique is as follows:
(1) the triethanolamine aqueous solution that dose volume concentration is 10%；
(2) by embodiment 1-4, material respectively weighs 20mg in 100mL three-necked flask in comparative example 1-2, and 80mL step is added
Suddenly the triethanolamine aqueous solution prepared in (1), is sealed three-necked flask using rubber stopper and rubber tube；
(3) it is passed through nitrogen while stirring to remove the gas dissolved in air and water in flask, after 30 minutes, clamps rubber
Leather hose is to prevent gas leakage；
(4) the three-necked flask reactor handled well is placed under 300W xenon lamp and irradiates a hour (still in magnetic when illumination
Under power stirring, so that photochemical catalyst and solution come into full contact with), it utilizes and generates in gas chromatograph measurement three-necked flask
Hydrogen；
Fig. 1 is blocky carbonitride, crystallization carbonitride and highly crystalline nitrogen prepared by comparative example 1-2 and embodiment 1-4
Change the XRD diffracting spectrum of carbon catalysis material；As shown in Figure 1, the crystallinity of embodiment 3 is all higher than the crystallinity of other samples,
Show that embodiment 3 has best concentration of hydrochloric acid.
(a) in Fig. 2, (b), (c) and (d) is respectively comparative example 1, comparative example 2, embodiment 2, light prepared by embodiment 3
The scanning electron microscope (SEM) photograph of catalysis material；As shown in Figure 2, comparative example 1 is blocky carbonitride, and main pattern is bulk, and comparative example 2 is in fact
Example 3 is applied, the structure of sample increasingly rule is unified, this has also further demonstrated that the crystallinity of embodiment 3 is best.
Fig. 3 is the performance of catalysis material Photocatalyzed Hydrogen Production under full light prepared by comparative example 1-2 and embodiment 1-4
Figure；Experiment condition are as follows: sample size 20mg, the triethanolamine that sacrifice agent is 10%, using 3% platinum as co-catalyst, light
It is 1 hour according to the time, light source is 300W xenon lamp.From the figure 3, it may be seen that highly crystalline carbonitride catalysis material tool made from embodiment
There is excellent photocatalytic activity, wherein the Photocatalyzed Hydrogen Production rate highest of 3 material of embodiment.
Fig. 4 is the principle of catalysis material Photocatalyzed Hydrogen Production under full light prepared by comparative example 1-2 and embodiment 1-4
Figure.The presence of hydrogen bond inhibits the separation of photo-generate electron-hole pairs in comparative example 1, to influence photocatalytic activity；In comparative example 2
Excessive potassium concentration reduces the crystallinity of carbonitride, is also suppressed the migration of light induced electron, urges to influence light
Change activity；Since preferable crystallinity and suitable potassium concentration promote the migration and transfer of light induced electron in embodiment 1-4,
Making their photocatalytic activity enhances, and wherein embodiment 3 is since with best crystallinity, its photocatalytic activity is best.
It should be pointed out that specific embodiment described above can make those skilled in the art that this hair be more fully understood
It is bright, but do not limit the invention in any way.Therefore, it will be appreciated by those skilled in the art that still can be carried out to the present invention
Modification or equivalent replacement；And all do not depart from the technical solution and its improvement of spirit and technical spirit of the invention, it should all
Cover in the scope of protection of the patent of the present invention.
Claims (6)
1. a kind of preparation method of highly crystalline carbonitride catalysis material, comprising the following steps:
The preparation of step 1, seven piperazine presomas: melamine being placed in Muffle furnace and is calcined, after calcining, natural cooling
To room temperature, seven piperazine presomas are obtained；
The preparation of step 2, crystallization carbonitride: seven piperazine presomas, sylvite and the lithium salts ground and mixed that step 1 is obtained are uniform, obtain
To mixture be placed in Muffle furnace and calcined, after calcining, cooled to room temperature；Obtained product using hot water and
Ethanol washing, it is dry, obtain crystallization carbonitride；Wherein, the mass ratio of seven piperazine presomas, sylvite and lithium salts is 1:(3~10): (3
~10)；
The preparation of step 3, highly crystalline carbonitride catalysis material: the crystallization carbonitride that step 2 obtains is dispersed in hydrochloric acid, is held
Continuous stirring, obtained product water and ethanol washing are dry to get the highly crystalline carbonitride catalysis material.
2. the preparation method of highly crystalline carbonitride catalysis material according to claim 1, which is characterized in that step 3 institute
The concentration for stating hydrochloric acid is 0.005~0.2mol/L, and the time persistently stirred is 1~4h.
3. the preparation method of highly crystalline carbonitride catalysis material according to claim 1, which is characterized in that in step 3,
When crystallization carbonitride is dispersed in hydrochloric acid, the dispersion concentration of crystallization carbonitride is 1~5mg/mL.
4. the preparation method of highly crystalline carbonitride catalysis material according to claim 1, which is characterized in that step 2 institute
Stating sylvite is potassium chloride or potassium nitrate, and the lithium salts is lithium chloride or lithium nitrate.
5. the preparation method of highly crystalline carbonitride catalysis material according to claim 1, which is characterized in that step 1 and
The temperature of calcining described in step 2 is 300~600 DEG C, and calcination time is 2~6h.
6. the highly crystalline carbonitride catalysis material that any one of claim 1 to 5 the method obtains is in Photocatalyzed Hydrogen Production
Using.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215109A (en) * | 2019-11-27 | 2020-06-02 | 西安交通大学 | N, S co-doped high-crystalline carbon photocatalytic total-hydrolysis material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395771A (en) * | 2016-08-31 | 2017-02-15 | 东华理工大学 | Preparation method of graphite-phase carbon nitride quantum dots |
| CN106824247A (en) * | 2017-02-28 | 2017-06-13 | 陕西科技大学 | A kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst and its preparation method and application |
| CN107986247A (en) * | 2017-12-26 | 2018-05-04 | 佛山科学技术学院 | A kind of preparation method of graphite phase carbon nitride nanotube |
| CN109590006A (en) * | 2018-12-17 | 2019-04-09 | 江苏大学 | A kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts |
-
2019
- 2019-05-21 CN CN201910423596.9A patent/CN110124719A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395771A (en) * | 2016-08-31 | 2017-02-15 | 东华理工大学 | Preparation method of graphite-phase carbon nitride quantum dots |
| CN106824247A (en) * | 2017-02-28 | 2017-06-13 | 陕西科技大学 | A kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst and its preparation method and application |
| CN107986247A (en) * | 2017-12-26 | 2018-05-04 | 佛山科学技术学院 | A kind of preparation method of graphite phase carbon nitride nanotube |
| CN109590006A (en) * | 2018-12-17 | 2019-04-09 | 江苏大学 | A kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts |
Non-Patent Citations (2)
| Title |
|---|
| HAO YIN ET AL.: "Acid-induced crystallinity enhancement of graphite-like C3N3+xHy synthesized through a facile one-pot approach", 《CHEMICAL PHYSICS LETTERS》 * |
| LIHUA LIN ET AL.: "Crystalline carbon nitride semiconductors prepared at different temperatures for photocatalytic hydrogen production", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
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