CN109772419A - The preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material is constructed in confinement space - Google Patents
The preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material is constructed in confinement space Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010455 vermiculite Substances 0.000 claims abstract description 25
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 25
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 25
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000009830 intercalation Methods 0.000 claims description 4
- 230000002687 intercalation Effects 0.000 claims description 4
- 241000545744 Hirudinea Species 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 26
- 238000012423 maintenance Methods 0.000 description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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Abstract
The invention belongs to photocatalysis fields, more particularly to a kind of the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material is constructed in confinement space, implement as follows: (1) mixing cyanamide with vermiculite, temperature programming is to 300~400 DEG C, it is slowly cooled to room temperature again, obtain cyanamide intercalated vermiculite precursor: the cyanamide intercalated vermiculite precursor is stirred to react by (2) with organic solution, is dried after filtering and washing；It is heated to 500~650 DEG C in air, then is slowly cooled to room temperature；(3) products therefrom is reacted with strong acid, is dried after filtering and washing filter cake.The present invention it is at low cost, it is easy to industrialized production, purpose product good dispersion and have excellent photocatalysis performance.
Description
Technical field
The invention belongs to photocatalysis field, more particularly to a kind of in confinement space to construct the carbon-based ultrathin nanometer piece of nitridation compound
The preparation method of material.
Background technique
The energy, information and material are three kinds of pillars of contemporary society's development, recently as the continuous hair of social economy
An important factor for exhibition, energy shortage has become limitation economic development.In order to further push sustainable development, it is necessary to send out energetically
All kinds of new green energy resources are opened up, Photocatalitic Technique of Semiconductor is that one kind is efficient, cleans, is environmentally friendly, renewable energy new
Emerging technology can utilize the natural a series of chemical reaction of sun optical drive, convert solar energy into chemical energy (such as hydrogen
Can), and in the depollution of environment and tap a new source of energy and go up it and show huge potentiality, therefore Photocatalitic Technique of Semiconductor becomes
The focus on research direction of current science.
In document Nature, 1972,238:37-38, Japanese Scientists Fujishma and Honda discovery
TiO2 can decompose water as photochemical catalyst and prepare hydrogen and oxygen, and titanium dioxide (TiO2) is a kind of photocatalysis of comparative maturity
Agent has many advantages, such as that inexpensively nontoxic, high stability, ultraviolet catalytic are high-efficient.However, the broad-band gap of TiO2 and being not responding to
The shortcomings that visible light, limits it in the application in visible light photocatalysis field to a certain extent.In document Nature
Materials, 2009, in 8:76-80, Wang et al. take the lead in finding graphite phase carbon nitride (g-C3N4) under visible light having compared with
For good response and catalytic performance.But graphite phase carbon nitride (g-C3N4) semiconductor light-catalyst material of conventional method preparation
Material, is stacked by the sheet irregularly stacked, the extremely serious shadow of sheet pattern that the particle and accordion that stratiform is reunited stack
Its photocatalysis performance is rung.In addition, graphite phase carbon nitride (g-C3N4) material is only capable of purple of the absorbing wavelength range in sunlight
Outer optical band, and ultraviolet band accounts for the ratio of very little in sunlight.Therefore these semiconductor materials are in visible light catalytic
Using being above limited by very large.In order to solve this problem, it adulterates existing semiconductor and effectively helps noble metal
Catalyst is that the optical range that two kinds of effective modes absorb it expands to visible light portion in conjunction with the surface of photocatalyst material
Point.However for the sample less stable after doping, dopant can become new Carrier recombination center, lead to photo-generated carrier
Pair reduction.And by noble metal in conjunction with photocatalyst material surface higher cost.Therefore a kind of novel photocatalyst is developed
Material replaces traditional graphite phase carbon nitride (g-C3N4) conductor photocatalysis material to be particularly important.
Compared with graphite phase carbon nitride (g-C3N4) semiconductor light-catalyst material of conventional method preparation, in confinement space
Constructing the nanometer sheet that the carbon-based ultrathin nanometer piece composite material of nitridation not only shows has size smaller, transparent, smooth gauze-like
Tile structure, partial sheet is laminated on together, and has good dispersibility.The electronic state of semiconductor nano thin slice is by body
The energy band of phase material is transitioned into the energy level with separate structure with size reduction, shows on absorption spectrum to be exactly never to tie
The broad absorption band of structure is transitioned into the structured absorption characteristic of tool.In addition, compared to graphite phase carbon nitride (g-C3N4) semiconductor light
Catalyst is constructed the carbon-based ultrathin nanometer piece composite material forbidden bandwidth of nitridation in confinement space and is obviously reduced, illustrates the material pair
The absorbability and utilization rate of light are stronger.And in nitrogenizing carbon-based ultrathin nanometer sheet material, carbocyclic ring and carbonitride formation plane are heterogeneous
Structure can promote conductor photocatalysis material surface photo-generate electron-hole since carbon has good conduction to electronics
Pair separation, inhibit the compound again of internal electronics and hole, effectively improve photocatalysis performance.It is carbon-based compound about nitrogenizing at present
The primary synthetic methods of material reported both at home and abroad are to utilize the high organic compound mixing melamines of phosphorus content such as glucose
Material is prepared by hydro-thermal or solvent-thermal method.But the material that this method obtains still is presented without regular slab-like pattern.And
Confinement space is constructed the carbon-based ultrathin nanometer piece composite material of nitridation and is had not been reported applied to the research of photocatalysis hydrogen production system.
Summary of the invention
The present invention is directed to a kind of at low cost, easy to industrialized production, purpose is provided in place of overcome the deficiencies in the prior art
Product good dispersion and the carbon-based ultrathin nanometer piece composite material of nitridation is constructed in confinement space with excellent photocatalysis performance
Preparation method.
In order to solve the above technical problems, the present invention is implemented as follows:
It is a kind of to construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space, it can implement as follows:
(1) cyanamide is mixed with vermiculite, temperature programming is to 300~400 DEG C, then is slowly cooled to room temperature, and obtains cyanamide intercalation leech
Stone precursor:
(2) step (1) the cyanamide intercalated vermiculite precursor is stirred to react with organic solution, is dried after filtering and washing；In air
In be heated to 500~650 DEG C, then be slowly cooled to room temperature；
(3) step (2) products therefrom is reacted with strong acid, is dried after filtering and washing filter cake.
As a preferred embodiment, in the step (1) of the present invention, cyanamide is uniformly mixed with vermiculite is placed on aluminium oxide earthenware
In crucible, 300~400 DEG C are heated to 1~10 DEG C/min in air, after maintaining 1~4h, then is slowly cooled to room temperature.
Further, in step (2) of the present invention, by cyanamide intercalated vermiculite precursor and 1~40mL organic solution 40
2~60h, 40~80 DEG C of drying after filtering and washing are stirred to react at~90 DEG C；It is heated to 500~650 DEG C in air, maintains 1
After~4h, then it is slowly cooled to room temperature.
Further, in step (3) of the present invention, products therefrom and strong acid are stirred to react 2 at 40~90 DEG C~
60 h are filtered and 40~80 DEG C of drying after filter cake are washed with deionized.
Further, in the step (1) of the present invention, the cyanamide is in cyanamide, dihydro diamino or melamine
One or more kinds of mixtures.
Further, the mass ratio of cyanamide and vermiculite of the present invention is 1:1~20.
Further, in step (2) of the present invention, organic solution is aldehyde solvent.
Further, aldehyde solvent of the present invention is one or both of formaldehyde solvent, acetaldehyde solvent or butyraldehyde solvent
Above mixture.
Further, heating ramp rate is 1~10 DEG C/min to the present invention in air.
Further, in step (3) of the present invention, strong acid be one or both of hydrochloric acid, sulfuric acid or hydrofluoric acid with
On mixture.
The advantage of the invention is that cyanamide intercalation, between vermiculite laminate, the physical limit effect of laminate can control interlayer visitor
The shape size and object phase of body substance, the polycondensation reaction that cyanamide molecule carries out in corresponding interface are different from the body of conventional open
System, the carbon-based ultrathin nanometer piece composite material of nitridation of formation are the ultrathin nanometer pieces of regular appearance, and size is smaller, has good
Dispersibility.Present invention process is simple, and cost of material is low, is easy to industrial scale production.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and specific embodiments.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 is the XRD diagram for the composite material that embodiment 1 obtains.
Fig. 2 is that the TEM of the resulting composite material of embodiment 2 schemes.
Fig. 3-a and Fig. 3-b is to scheme outside the solid violet of the resulting composite material of embodiment 3.
Fig. 4 is the photocatalysis performance figure of the resulting composite material of embodiment 4.
Specific embodiment
Embodiment 1.
(1) 3g dicyandiamide and vermiculite are weighed, is 1:6 according to dicyandiamide and vermiculite mass ratio, mixed sample is put into
It is slowly cooled to room temperature after being heated to 400 DEG C of maintenance 3h in air in crucible with 5 DEG C/min.Before dicyandiamide intercalated vermiculite
Body with 40 DEG C of 20mL formalin at be stirred to react 8h, 80 DEG C of drying after filtering and washing.It is heated in air with 5 DEG C/min
It is slowly cooled to room temperature after 560 DEG C of maintenance 2h.
(2) by burn after sample and 40 DEG C of mixed solution of hydrofluoric acid and hydrochloric acid at be stirred to react 4 h, filter and spend
It obtains nitrogenizing carbon-based ultrathin nanometer piece composite material after 80 DEG C of drying after ion water washing filter cake.
(3) it weighs 3g dicyandiamide and is put into after program in Muffle furnace is warming up to 560 DEG C of maintenance 2h and be slowly cooled to room temperature, obtain
G-C3N4 material.As shown in Figure 1, XRD diagram proves that the material is different from traditional g-C3N4 material, which is that nitridation is carbon-based
Composite material.
Embodiment 2.
(1) 2g cyanamide and vermiculite are weighed, is 1:6 according to cyanamide and vermiculite mass ratio, mixed sample is put into
It is slowly cooled to room temperature after being heated to 320 DEG C of maintenance 3h in air in crucible with 5 DEG C/min.Before cyanamide intercalated vermiculite
Body with 40 DEG C of 20mL acetaldehyde solution at be stirred to react 12 h, 80 DEG C of drying after filtering and washing.In air with 5 DEG C/min heating
It is slowly cooled to room temperature after to 620 DEG C of maintenance 2h.
(2) by burn after sample and 40 DEG C of mixed solution of hydrofluoric acid and sulfuric acid at be stirred to react 6 h, filter and spend
It obtains nitrogenizing carbon-based ultra-thin carbon nanosheet composite material after 80 DEG C of drying after ion water washing filter cake.As shown in Fig. 2, tem observation
There is the pattern of ultrathin nanometer piece to the carbon-based ultrathin nanometer piece composite material of nitridation of synthesis.
Embodiment 3.
(1) 4g melamine and vermiculite are weighed, is 1:8 according to melamine and vermiculite mass ratio, by mixed sample
It is put into crucible after being heated to 320 DEG C of maintenance 3h in air with 5 DEG C/min and is slowly cooled to room temperature.By melamine intercalation leech
The precursor of stone with 40 DEG C of 20mL acetaldehyde solution at be stirred to react 8 h, 80 DEG C of drying after filtering and washing.In air with 5 DEG C/min
It is slowly cooled to room temperature after being heated to 600 DEG C of maintenance 4h.
(2) by burn after sample and 40 DEG C of mixed solution of hydrofluoric acid and sulfuric acid at be stirred to react 4 h, filter and spend
It obtains nitrogenizing carbon-based ultrathin nanometer piece composite material after 80 DEG C of drying after ion water washing filter cake.
(3) it weighs 4g melamine and is put into after program in Muffle furnace is warming up to 600 DEG C of maintenance 4h and be slowly cooled to room temperature, obtain
G-C3N4 material is arrived.As shown in figure 3, uv-spectrogram shows compared to g-C3N4 material, which absorbs with broader spectrum
Performance.
Embodiment 4.
(1) 2g dicyandiamide and vermiculite are weighed, is 1:8 according to dicyandiamide and vermiculite mass ratio, mixed sample is put into
It is slowly cooled to room temperature after being heated to 320 DEG C of maintenance 3h in air in crucible with 5 DEG C/min.Before dicyandiamide intercalated vermiculite
8 h, 80 DEG C of drying after filtering and washing are stirred to react at 40 DEG C of body and 20mL butyraldehyde solution.It is heated in air with 5 DEG C/min
It is slowly cooled to room temperature after 580 DEG C of maintenance 2h.
(2) by burn after sample and 70 DEG C of mixed solution of hydrofluoric acid and hydrochloric acid at be stirred to react 4 h, filter and spend
It obtains nitrogenizing carbon-based ultrathin nanometer piece composite material after 80 DEG C of drying after ion water washing filter cake.2g dicyandiamide is weighed again is put into horse
Not program is slowly cooled to room temperature after being warming up to 580 DEG C of maintenance 2h in furnace, has obtained g-C3N4 material.
(3) sample and 80mL for weighing 50mg are put into photo catalysis reactor, and the aqueous solution conduct of 10mL triethanolamine is added
Sacrifice agent carries out photocatalysis hydrogen production experiment under conditions of the atmosphere lamp used (optical filter equipped with λ >=420n).As shown in figure 4, light
Catalytic performance chart is bright compared to g-C3N4, which has better photocatalysis performance.
It is understood that for those of ordinary skill in the art, can do in accordance with the technical idea of the present invention
Various other changes and modifications out, and all these changes and deformation all should belong to the protection model of the claims in the present invention
It encloses.
Claims (10)
1. a kind of construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space, which is characterized in that by such as
Lower step is implemented:
(1) cyanamide is mixed with vermiculite, temperature programming is to 300~400 DEG C, then is slowly cooled to room temperature, and obtains cyanamide intercalation leech
Stone precursor；
(2) step (1) the cyanamide intercalated vermiculite precursor is stirred to react with organic solution, is dried after filtering and washing；In air
In be heated to 500~650 DEG C, then be slowly cooled to room temperature；
(3) step (2) products therefrom is reacted with strong acid, is dried after filtering and washing filter cake.
2. according to claim 1 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: cyanamide is uniformly mixed with vermiculite and is placed in alumina crucible, in air with 1~10 in the step (1)
DEG C/min is heated to 300~400 DEG C, after maintaining 1~4h, then it is slowly cooled to room temperature.
3. according to claim 2 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: cyanamide intercalated vermiculite precursor is stirred at 40~90 DEG C with 1~40mL organic solution in the step (2)
React 2~60h, 40~80 DEG C of drying after filtering and washing；It is heated to 500~650 DEG C in air, after maintaining 1~4h, then slowly
It is cooled to room temperature.
4. according to claim 3 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: products therefrom and strong acid are stirred to react 2~60 h at 40~90 DEG C, suction filtration is used in combination in the step (3)
Deionized water washs 40~80 DEG C of drying after filter cake.
5. according to claim 4 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: in the step (1), the cyanamide be one or both of cyanamide, dihydro diamino or melamine with
On mixture.
6. according to claim 5 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: the mass ratio of the cyanamide and vermiculite is 1:1~20.
7. according to claim 6 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: organic solution is aldehyde solvent in the step (2).
8. according to claim 7 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: the aldehyde solvent is the mixture of one or more of formaldehyde solvent, acetaldehyde solvent or butyraldehyde solvent.
9. according to claim 8 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: heating ramp rate is 1~10 DEG C/min in air.
10. according to claim 9 construct the preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material in confinement space,
It is characterized by: strong acid is the mixture of one or more of hydrochloric acid, sulfuric acid or hydrofluoric acid in the step (3).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697228A (en) * | 2020-05-07 | 2020-09-22 | 辽宁石油化工大学 | Preparation method of fluorine intercalation graphitized carbon material |
| CN116586098A (en) * | 2023-05-26 | 2023-08-15 | 郑州大学 | Vermiculite/graphite phase carbon nitride/bismuth oxybromide composite photocatalytic material and preparation method and application thereof |
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