CN109590006A - A kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts - Google Patents
A kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts Download PDFInfo
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- CN109590006A CN109590006A CN201811539287.XA CN201811539287A CN109590006A CN 109590006 A CN109590006 A CN 109590006A CN 201811539287 A CN201811539287 A CN 201811539287A CN 109590006 A CN109590006 A CN 109590006A
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- Prior art keywords
- triazine
- piperazine
- homoatomic
- junctions
- hetero
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 51
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 150000001412 amines Chemical class 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 58
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 34
- 235000011164 potassium chloride Nutrition 0.000 claims description 27
- 239000001103 potassium chloride Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000919 ceramic Substances 0.000 claims description 24
- 239000012300 argon atmosphere Substances 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000006104 solid solution Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 238000005374 membrane filtration Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 35
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000013535 sea water Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003918 triazines Chemical class 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—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
Abstract
The present invention relates to catalysis materials, refer in particular to a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts, belong to catalysis material preparation technical field.The present invention does not use high temperature and pressure, energy high efficiency photocatalysis can be produced in batches only by the mode for calcining melamine and Miller amine adduct in fuse salt and decomposes triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts that seawater produces hydrogen, effectively solve current block g-C3N4Material, conductivity is poor, and the high disadvantage of photo-generated carrier recombination rate is obviously improved its Photocatalyzed Hydrogen Production performance and quantum efficiency.
Description
Technical field
The present invention relates to catalysis materials, refer in particular to a kind of preparation of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts
Method belongs to catalysis material preparation technical field.
Background technique
Since the current mankind to the excessive exploitation of fossil fuel and consume, CO in earth atmosphere2Content continue to increase, make
At the greenhouse effects got worse.Therefore, exploitation can replace the energy carrier of fossil fuel to seem especially urgent.Various new
In the energy, Hydrogen Energy becomes optimal selection.However, the preparation of hydrogen is also to rely on the consumption to fossil fuel at present, this is not
CO can be reduced2Discharge.In recent years, emerging photocatalytic hydrogen production by water decomposition technology is that one kind utilizes sunlight as drive
Water is directly decomposed into the technological means of hydrogen and oxygen by dynamic source, this can accomplish CO2Zero-emission becomes the heat studied at present
Point.
Graphite phase carbon nitride (g-C3N4) be one kind emerging in recent years can use sunlight by water decomposition be hydrogen and oxygen
The organic semiconductor photochemical catalyst of gas.The material is stablized with physicochemical properties, and preparation abundant raw material is easy to get, can be in visible light
Irradiation is lower to decompose the characteristics of aquatic products hydrogen produces oxygen.But the block g-C being prepared by conventional methods3N4It is poor that there are conductivities, light
The disadvantages of raw Carrier recombination rate is high, Photocatalyzed Hydrogen Production low efficiency.By to g-C3N4The regulation of inner molecular structure, preparation tool
There is the novel g-C of triazine/seven piperazine homoatomic heterojunction structures3N4Material can construct built in field in material internal, thus significantly
Reduction carrier recombination rate, and then promoted photochemical catalyzing H2-producing capacity.However, preparing this triazine/seven piperazines at present
The g-C of homoatomic heterojunction structure3N4Material is by apparently mixing melamine and Miller amine, then the polycondensation system in fuse salt
It is standby, the novel g-C of the triazine being prepared in this way/seven piperazine homoatomic heterojunction structures3N4Material is simultaneously heterogeneous compound,
Only in the surface construction of material hetero-junctions, material internal still shows no electric field driven state, prepared photocatalysis
Agent performance is not high.Therefore, search operation is simple, and the g-C of the homogeneous compound triazine/seven piperazine homoatomic hetero-junctions of energy3N4Material at
For the focus and emphasis of current carbon nitride material research field.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of easy to operate, and synthesis process green does not use high temperature
High pressure can produce energy efficiency light in batches only by the mode for calcining melamine and Miller amine adduct in fuse salt and urge
Change and decompose triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts that seawater produces hydrogen, effectively solves current block g-C3N4Material,
Conductivity is poor, and the high disadvantage of photo-generated carrier recombination rate is obviously improved its Photocatalyzed Hydrogen Production performance and quantum efficiency.
In order to achieve the object of the present invention, the specific steps are as follows:
(1) preparation of melamine and Miller amine adduct: weighing melamine and be placed in ceramic crucible, and with covering crucible
Lid；Then crucible is put in tube furnace, under high-purity argon gas protection, certain temperature is risen to certain heating rate program,
After being kept for a period of time, cooled to room temperature obtains the melamine and Miller amine adduct of white；
(2) mixture of the melamine and Miller amine adduct and lithium chloride and potassium chloride that obtain step (1) is protected in nitrogen
Grinding is uniformly rear in glove box under shield and pours into ceramic crucible and closes the lid；
(3) ceramic crucible is placed in tube furnace, under the protection of argon atmosphere, is risen to centainly with certain heating rate program
After temperature, kept for a period of time, cooled to room temperature obtains triazine/seven piperazine homoatomic hetero-junctions carbonitrides, lithium chloride and chlorination
The solid solution of potassium.
(4) dispersed with the solid solution that boiling water obtains step (3), after being washed using the membrane filtration that diameter is 0.22 μm
Obtain triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts.
Preferably, step (1) heating rate is 2-10 DEG C/min.
Preferably, the temperature of step (1) described heating is 360-430 DEG C, retention time 4-24h.
Preferably, the flow of step (1) described argon gas is 50-400mL/min.
Preferably, the quality of the mixture of the adduct of step (2) melamine and Miller amine and lithium chloride and potassium chloride
Than for 1:30-1:6；In the mixture of lithium chloride and potassium chloride, the mass ratio of lithium chloride and potassium chloride is 9:11.
Preferably, step (3) heating rate is 10-20 DEG C/min.
Preferably, the temperature of step (3) described heating is 550-600 DEG C, retention time 4-6h.
Preferably, the flow of step (3) described argon gas is 50-400mL/min.
Preferably, step (4) boiling water is the deionized water that normal atmosphere depresses 100 DEG C, and washing times are 6-20 times.
The utility model has the advantages that
The present invention is compared with the technology of existing synthesis carbonitride, and have apparent advantage: preparation process is simple to operation, passes through
Just obtainable energy efficient-decomposition seawater produces the three of hydrogen to the mode of the adduct of polycondensation melamine and Miller amine in fuse salt
Piperazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials.The triazine that method of the invention is prepared/seven piperazine homoatomic hetero-junctions nitrogen
Change carbon photocatalyst material and show very high photochemical catalyzing H2-producing capacity, under visible light illumination photocatalysis point
Solution aquatic products hydrogen activity may be up to 32885 μm of ol/gh, and quantum efficiency may be up to 57%.Its activity is the nitridation of common process preparation
70 times of carbon.Present invention process is simple, favorable reproducibility, and raw materials are very cheap and easy to get, convenient for batch production.
Detailed description of the invention
Fig. 1 is prepared block g-C3N4And the triazine obtained under different temperatures/seven piperazine homoatomic hetero-junctions carbonitride samples
XRD spectra.
Triazine prepared by Fig. 2/seven piperazine homoatomic hetero-junctions carbonitrides SEM figure.
The ultraviolet-visible light diffusing reflection of sample prepared by Fig. 3 absorbs (DRS) map.
G-C under Fig. 4 radiation of visible light3N4And synthesized triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts production hydrogen is living
Property schematic diagram.
Specific embodiment
It is several embodiments of the present invention below, further illustrates the present invention, but protection scope of the present invention not only limits
In this.
Embodiment 1
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 1.0g melamine and be placed in 20mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 100mL/min argon atmosphere under with 2 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 4h to 370 DEG C
With the adduct of Miller amine.The adduct material for then weighing melamine and Miller amine that 0.2g is calcined is placed in nitrogen guarantor
It is fully ground after mixing in the agate mortar in glove box under shield and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be above-mentioned
Mixture after grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tube furnace again
In, and in the case where flow is the argon atmosphere of 50mL/min with the heating rate temperature programming of 10 DEG C/min to 550 DEG C, and keep 4h
Allow its cooled to room temperature that the solid solution of triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared afterwards
Body.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, recycles diameter after fully dispersed
It is washed for 0.22 μm of membrane filtration, which is repeated 6 times.The solid finally collected simultaneously is dried just at 60 DEG C
To a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials.
Embodiment 2
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 4.0g melamine and be placed in 80mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 200mL/min argon atmosphere under with 5 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 10h to 390 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 0.4g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 200mL/min with the heating rate temperature programming of 15 DEG C/min to 560 DEG C, and protect
It holds and allows after 4h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 15 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained.
Embodiment 3
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 8.0g melamine and be placed in 100mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 350mL/min argon atmosphere under with 5 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 20h to 430 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 1.0g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 400mL/min with the heating rate temperature programming of 20 DEG C/min to 600 DEG C, and protect
It holds and allows after 6h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 20 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained.
Embodiment 4
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 6.0g melamine and be placed in 100mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 100mL/min argon atmosphere under with 8 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 16h to 370 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 0.8g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 100mL/min with the heating rate temperature programming of 15 DEG C/min to 580 DEG C, and protect
It holds and allows after 4h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 18 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained, 370-T/H-CN is named as.
Embodiment 5
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 6.0g melamine and be placed in 100mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 100mL/min argon atmosphere under with 8 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 16h to 390 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 0.8g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 100mL/min with the heating rate temperature programming of 15 DEG C/min to 580 DEG C, and protect
It holds and allows after 4h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 18 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained, 390-T/H-CN is named as.
Embodiment 6
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 6.0g melamine and be placed in 100mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 100mL/min argon atmosphere under with 8 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 16h to 410 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 0.8g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 100mL/min with the heating rate temperature programming of 15 DEG C/min to 580 DEG C, and protect
It holds and allows after 4h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 18 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained, 410-T/H-CN is named as.
Embodiment 7
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 6.0g melamine and be placed in 100mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 100mL/min argon atmosphere under with 8 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 16h to 420 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 0.8g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 100mL/min with the heating rate temperature programming of 15 DEG C/min to 580 DEG C, and protect
It holds and allows after 4h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 18 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained, 420-T/H-CN is named as.
Embodiment 8
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 6.0g melamine and be placed in 100mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 100mL/min argon atmosphere under with 8 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 16h to 430 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 0.8g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 100mL/min with the heating rate temperature programming of 15 DEG C/min to 580 DEG C, and protect
It holds and allows after 4h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 18 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained, 430-T/H-CN is named as.
Embodiment 9
The preparation of the adduct of melamine and Miller amine, concrete operations are as follows: weighing 6.0g melamine and be placed in 100mL ceramics
In crucible and cover crucible cover.Then crucible is put in tube furnace, flow be 100mL/min argon atmosphere under with 8 DEG C/
The heating rate temperature programming of min keeps the melamine for allowing its cooled to room temperature that white is prepared after 16h to 450 DEG C
The adduct of amine and Miller amine.The adduct material for then weighing melamine and Miller amine that 0.8g is calcined is placed in nitrogen
It is fully ground after mixing in the agate mortar in glove box under protection and with 2.7g lithium chloride and 3.3g potassium chloride.It then will be upper
Mixture after stating grinding pours into ceramic crucible and covers lid.Later, the crucible equipped with mixture is put into tubular type again
In furnace, and in the case where flow is the argon atmosphere of 100mL/min with the heating rate temperature programming of 15 DEG C/min to 580 DEG C, and protect
It holds and allows after 4h its cooled to room temperature that consolidating for triazine/seven piperazine homoatomic hetero-junctions carbonitrides and lithium chloride and potassium chloride is prepared
Solution.Then obtained solid solution is distributed in 100 DEG C of deionized waters of normal atmosphere pressure, is recycled after fully dispersed straight
The membrane filtration that diameter is 0.22 μm washs, which is repeated 18 times.The solid finally collected simultaneously is dried at 60 DEG C
Just a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst materials are obtained, 450-T/H-CN is named as.
XRD, TEM, DRS characterization of catalyst are as shown in Figure 1, 2, 3.
Fig. 1: being had found by XRD analysis, and there are two types of crystal structures for carbonitride, and as the temperature rises, the peak of triazine crystal form is gradually
It disappears.When the temperature in step (1) is up to 450 DEG C, triazine crystal form is completely disappeared.
Fig. 2: being had found by sem analysis, and prepared triazine/seven piperazine homoatomic hetero-junctions carbonitrides are rodlike cluster structure.
Fig. 3: being had found by DRS analysis, and as the temperature rises, to the absorption of light certain red shift occurs for carbonitride.
Fig. 4: it for triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalyst photocatalysis Decomposition aquatic products hydrogen activity figures, can be sent out in figure
It is existing, compared to block g-C3N4, the production hydrogen activity of nitride porous carbon is obviously improved, wherein g-C3N4、370-T/H-CN、390-T/
The hydrogen output of H-CN, 410-T/H-CN, 430-T/H-CN and 450-T/H-CN be respectively 9.3 μm of ol/h, 342.4 μm of ol/h,
382.9 μm of ol/h, 657.7 μm of ol/h, 607.2 μm of ol/h and 486.1 μm of ol/h.The triazine obtained at 410 DEG C/seven piperazine homoatomics are different
Matter knot carbonitride has highest production hydrogen activity, and when catalyst amount is 0.02g, it, which produces hydrogen activity, may be up to 657.7 μm of ol/
H, about 32885 μm of ol/gh, quantum efficiency may be up to 57%.
Claims (9)
1. a kind of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts preparation method, which is characterized in that specific preparation step
It is as follows:
(1) preparation of melamine and Miller amine adduct: weighing melamine and be placed in ceramic crucible, and with covering crucible
Lid；Then crucible is put in tube furnace, under high-purity argon gas protection, certain temperature is risen to certain heating rate program,
After being kept for a period of time, cooled to room temperature obtains the melamine and Miller amine adduct of white；
(2) mixture of the melamine and Miller amine adduct and lithium chloride and potassium chloride that obtain step (1) is protected in nitrogen
Grinding is uniformly rear in glove box under shield and pours into ceramic crucible and closes the lid；
(3) ceramic crucible is placed in tube furnace, under the protection of argon atmosphere, is risen to centainly with certain heating rate program
After temperature, kept for a period of time, cooled to room temperature obtains triazine/seven piperazine homoatomic hetero-junctions carbonitrides, lithium chloride and chlorination
The solid solution of potassium；
(4) dispersed with the solid solution that boiling water obtains step (3), can be obtained triazine/seven piperazine homoatomic hetero-junctions after filtration washing
Carbon nitride photocatalyst.
2. a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts as described in claim 1, feature
It is, in step (1), the heating rate is 2-10 DEG C/min；The temperature of the heating is 360-430 DEG C, and the retention time is
4-24h；The flow of the argon gas is 50-400mL/min.
3. a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts as described in claim 1, feature
It is, in step (2), the mass ratio of the adduct and lithium chloride and the mixture of potassium chloride of the melamine and Miller amine is
1:30-1:6；In the mixture of lithium chloride and potassium chloride, the mass ratio of lithium chloride and potassium chloride is 9:11.
4. a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts as described in claim 1, feature
It is, in step (3), the heating rate is 10-20 DEG C/min；The temperature of the heating is 550-600 DEG C, and the retention time is
4-6h；The flow of the argon gas is 50-400mL/min.
5. a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts as described in claim 1, feature
It is, in step (4), the boiling water is the deionized water that normal atmosphere depresses 100 DEG C；The filtration washing is to be by diameter
0.22 μm of membrane filtration washing；Washing times are 6-20 times.
6. a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts as claimed in claim 2, feature
It is, in step (1), in step (1), the heating rate is 8 DEG C/min；The temperature of the heating is 410 DEG C, the retention time
For 16h；The flow of the argon gas is 100mL/min.
7. a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts as claimed in claim 3, feature
It is, the mass ratio of the mixture of the adduct and lithium chloride and potassium chloride of the melamine and Miller amine is 1:7.5.
8. a kind of preparation method of triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts as claimed in claim 4, feature
It is, in step (3), the heating rate is 15 DEG C/min；The temperature of the heating is 580 DEG C, retention time 4h；It is described
The flow of argon gas is 100mL/min.
9. triazine/seven piperazine homoatomic hetero-junctions carbon nitride photocatalysts use of method preparation a method as claimed in any one of claims 1-8
On the way, which is characterized in that photocatalysis Decomposition aquatic products hydrogen under visible light illumination.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110124719A (en) * | 2019-05-21 | 2019-08-16 | 电子科技大学 | A kind of preparation method and application of highly crystalline carbonitride catalysis material |
| CN110170332A (en) * | 2019-06-20 | 2019-08-27 | 中国石油大学(华东) | A kind of carbonitride and preparation method thereof can be used for photocatalysis seawater liberation of hydrogen |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992282A (en) * | 2012-11-08 | 2013-03-27 | 南京大学 | Mesoporous C3N4 photocatalytic material prepared by using molten salt method and application thereof in photocatalysis field |
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN105772056A (en) * | 2016-04-28 | 2016-07-20 | 成都理工大学 | Preparation method and application of graphite-phase carbon nitride photocatalysis material |
| CN108686690A (en) * | 2017-04-12 | 2018-10-23 | 中国科学院福建物质结构研究所 | One kind being based on graphite phase carbon nitride g-C3N4Photochemical catalyst and its preparation method and application |
-
2018
- 2018-12-17 CN CN201811539287.XA patent/CN109590006B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992282A (en) * | 2012-11-08 | 2013-03-27 | 南京大学 | Mesoporous C3N4 photocatalytic material prepared by using molten salt method and application thereof in photocatalysis field |
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN105772056A (en) * | 2016-04-28 | 2016-07-20 | 成都理工大学 | Preparation method and application of graphite-phase carbon nitride photocatalysis material |
| CN108686690A (en) * | 2017-04-12 | 2018-10-23 | 中国科学院福建物质结构研究所 | One kind being based on graphite phase carbon nitride g-C3N4Photochemical catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| HUANHUAN LIUA等: "Microwave-assisted molten-salt rapid synthesis of isotypetriazine-/heptazine based g-C3N4heterojunctions with highlyenhanced photocatalytic hydrogen evolution performance", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
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