CN109160498A - A kind of three-dimensional net structure class graphene carbonitride and its preparation method and application - Google Patents
A kind of three-dimensional net structure class graphene carbonitride and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005057 refrigeration Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 59
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 44
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000725 suspension Substances 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 238000006303 photolysis reaction Methods 0.000 claims description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 3
- 150000002085 enols Chemical class 0.000 claims 1
- 238000007710 freezing Methods 0.000 abstract description 32
- 230000008014 freezing Effects 0.000 abstract description 32
- 239000007787 solid Substances 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000009835 boiling Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 229920000877 Melamine resin Polymers 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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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
Abstract
The present invention provides a kind of three-dimensional net structure class graphene carbonitrides and its preparation method and application, are related to the green syt field of non-metal optical catalytic porous material.The solvent that the present invention uses is water, and with the reduction of pressure, the freezing point variation of water is little, and boiling point is lower and lower, close to freezing point, under the conditions of low-temp low-pressure, aqueous solvent is caused directly to distil, solute is then retained.Vacuum refrigeration and vacuum freeze drying provide the condition of low-temp low-pressure, the water freezed is set directly to distil, and water will not destroy the solid structure freezed during distilling discharge, that is, the solute component remained still keeps its spatial distribution in solution state.But because there is a large amount of gap between the evolution of water between solute, since water shows the lamellar structure being centainly orientated in freezing process, its structure can be remained completely to a certain extent, be evenly distributed conducive to substance, so that product be made to show three-dimensional net structure on a microscopic scale.
Description
Technical field
The invention belongs to the green synthesis techniques field of non-metal optical catalytic porous material more particularly to a kind of three-dimensional networks
Structure class graphene carbonitride and its preparation method and application.
Background technique
Carbonitride (C3N4) as a kind of ancient polymer material, β-C3N4Bulk modulus be 4.27Mbar, with generally acknowledge
Superhard material diamond bulk modulus (4.27Mbar) quite, cube phase carbon nitride (c-C3N4) bulk modulus it is even super
Diamond is crossed, predicts C3N4There are mainly five types of structures, i.e. α-C3N4, β-C3N4, c-C3N4, standard cube carbonitride (p-C3N4) and class stone
Black carbonitride (g-C3N4), wherein four kinds of front belongs to superhard material, and g-C3N4It is a kind of soft phase.
g-C3N4With moderate band gap (2.7eV), high thermal stability (~600 DEG C), biocompatibility and outstanding change
Inertia etc. is learned, and preparation process is relatively easy, abundant raw material is cheap, becomes most potential visible light photocatalysis material
Material.However, the g-C of common thermal polycondensation nitrogen-rich organic object synthesis3N4Specific surface area is small, and light induced electron and hole are easy to polymerize and measure
Sub- low efficiency etc., seriously constrains its actual use and commercialization is expanded.In general, improve catalysis material crystallinity and
Specific surface area can improve its photocatalysis performance, the former is conducive to the separation in light induced electron and hole, and the latter can provide more
Catalytic reaction activity site promotes reactant in more absorption of catalyst surface and more rapidly reacts.In view of class graphite nitrogen
The layer structure for changing carbon, is connected by weak Van der Waals force between layers, can be obtained by simple physics or chemical method
To the carbonitride of two-dimensional nanostructure, i.e. class graphene carbonitride, block is such as removed using ultrasonic wave auxiliary liquid phase in the prior art
Shape class graphitic nitralloy carbon prepares two-dimentional class graphene carbonitride, however, ultrasonic wave is to target product due in ultrasonic stripping process
The class graphene carbonitride size and the number of plies that the unevenness of effect causes are uneven, or even reunite, and oxidation is caused to be lost
It is living, there is a problem of that two-dimentional class graphene carbonitride specific surface area is small.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of three-dimensional net structure class graphene carbonitride and its preparation sides
Method and application.Three-dimensional net structure class graphene carbonitride large specific surface area produced by the present invention, porosity is high, three-dimensional network knot
Structure is evenly distributed.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of three-dimensional net structure class graphene carbonitride, comprising the following steps:
Class graphitic nitralloy carbon is provided；
The class graphitic nitralloy carbon is mixed with polyvinyl alcohol water solution, obtains suspension；
The suspension is subjected to vacuum refrigeration, obtains class graphene carbonitride；
The class graphene carbonitride is subjected to vacuum freeze drying, obtains three-dimensional net structure class graphene carbonitride.
Preferably, the mass ratio of polyvinyl alcohol and water is 1:20~1:10 in the polyvinyl alcohol water solution.
Preferably, the molecular weight of polyvinyl alcohol is 8 × 10 in the polyvinyl alcohol water solution3~2 × 105。
Preferably, the quality of the class graphitic nitralloy carbon and the volume ratio of polyvinyl alcohol water solution are 0.1~1g:100mL.
Preferably, the class graphitic nitralloy carbon is obtained by nitrogen-rich organic object by thermal polycondensation process.
Preferably, the temperature of the vacuum refrigeration is -240~-10 DEG C, and the time of vacuum refrigeration is 3~6h.
Preferably, the temperature of the vacuum freeze drying is -80~0 DEG C, and the time of vacuum freeze drying is 24~72h,
The pressure of vacuum freeze drying is 100~200MPa.
Preferably, the heating rate for being warming up to the vacuum freeze drying temperature is 10~20 DEG C/min.
The present invention also provides three-dimensional net structure class graphenes made from preparation method described in above-mentioned technical proposal to nitrogenize
Carbon, the specific surface area of the three-dimensional net structure class graphene carbonitride are 231~685m2/ g, porosity are 48~92%.
The present invention also provides the three-dimensional net structure class graphene carbonitrides described in above-mentioned technical proposal in organic contamination
Application in object absorption, photocatalytic degradation and photolysis water hydrogen field.
The present invention provides a kind of preparation methods of three-dimensional net structure class graphene carbonitride, comprising the following steps: mentions
For class graphitic nitralloy carbon；The class graphitic nitralloy carbon is mixed with polyvinyl alcohol water solution, obtains suspension；By the suspension
Vacuum refrigeration is carried out, class graphene carbonitride is obtained；The class graphene carbonitride is subjected to vacuum freeze drying, obtains three-dimensional
Network structure class graphene carbonitride.Solvent used in the present invention is water, according to the Phase Equilibrium theory in thermodynamics, with pressure
The freezing point variation of the reduction of power, water is little, and boiling point is lower and lower, close to freezing point, when pressure drops to certain vacuum degree
When, the boiling point and freezing point of water are overlapped, and ice can be without liquid and direct boiling is gas, water three phase point hereinafter, existing
Under the conditions of low-temp low-pressure, aqueous solvent is caused directly to distil, solute is then retained.Vacuum refrigeration and vacuum freeze drying provide
The condition of low-temp low-pressure makes the water freezed directly distil, and water will not destroy the solid freezed during distilling discharge
Structure, that is, the solute component remained still keep its spatial distribution in solution state.But because of water between solute
Occurs a large amount of gap between evolution, since water shows the lamellar structure being centainly orientated in freezing process, structure is certain
It can completely be remained in degree, avoid the unfavorable factor such as layering and sedimentation, be evenly distributed conducive to substance, to make
Product shows three-dimensional net structure on a microscopic scale, is macroscopically shown as spongy feature, so that the structure of product, gap
Uniformly, property is stablized.With powdered or block-like class graphitic nitralloy carbon phase ratio, three-dimensional net structure class graphene carbonitride has
Bigger specific surface area and more loose porous structure, in the absorption of organic pollutant and photocatalytic degradation, photolysis water hydrogen etc.
Aspect shows more outstanding performance and effect.Embodiment statistics indicate that, three-dimensional net structure class stone produced by the present invention
The specific surface area of black alkene carbonitride is 231~685m2/ g, porosity are 48~92%.
Meanwhile preparation method abundant raw material of the invention, being easy to get, it is at low cost；Preparation process is simple, easy to operate, and makes
Standby technique is environmentally protective；By simply changing the ratio of solvent and class graphitic nitralloy carbon, can be obtained porosity it is different three
Tie up the class graphene carbonitride of network structure.
Detailed description of the invention
Fig. 1 is the XRD diagram of 1 class graphitic nitralloy carbon of embodiment；
Fig. 2 is the XRD diagram of class graphene carbonitride after 1 vacuum freeze drying of embodiment；
Fig. 3 is the pictorial diagram of 1 three-dimensional net structure class graphene carbonitride of embodiment.
Specific embodiment
The present invention provides a kind of preparation methods of three-dimensional net structure class graphene carbonitride, comprising the following steps:
Class graphitic nitralloy carbon is provided；
The class graphitic nitralloy carbon is mixed with polyvinyl alcohol water solution, obtains suspension；
The suspension is subjected to vacuum refrigeration, obtains class graphene carbonitride；
The class graphene carbonitride is subjected to vacuum freeze drying, obtains three-dimensional net structure class graphene carbonitride.
The present invention provides class graphitic nitralloy carbon.In the present invention, the class graphitic nitralloy carbon is preferably led to by nitrogen-rich organic object
Thermal polycondensation process is crossed to obtain.
In the present invention, the nitrogen-rich organic object preferably includes cyanamide, dicyandiamide, melamine, urea, cyanuric acid
One or more of with thiocarbamide.
In the present invention, the temperature of the thermal polycondensation process is preferably 500~560 DEG C, and more preferably 520~550 DEG C, heating
Heating rate to the thermal polycondensation process temperature is preferably 2~10 DEG C/min, and more preferably 5 DEG C/min, soaking time is preferably 2
~8h, more preferably 4~6h.
After obtaining the class graphitic nitralloy carbon, the present invention mixes the class graphitic nitralloy carbon with polyvinyl alcohol water solution,
Obtain suspension.
In the present invention, the mass ratio of polyvinyl alcohol and water is preferably 1:20~1:10 in the polyvinyl alcohol water solution.
In the present invention, the molecular weight of polyvinyl alcohol is preferably 8 × 10 in the polyvinyl alcohol water solution3~2 × 105。
The present invention does not have special restriction to the preparation method of the polyvinyl alcohol water solution, using those skilled in the art
Well known preparation method, specifically, such as polyvinyl alcohol is added to the water in 90 DEG C of stirred in water bath.
In the present invention, the quality of the class graphitic nitralloy carbon and the volume ratio of polyvinyl alcohol water solution be preferably 0.1~
1g:100mL, more preferably 0.2~0.5g:100mL, most preferably 0.3g:100mL.
The present invention does not have special restriction to the hybrid mode, is using mixed method well known to those skilled in the art
Can, it is stirred specifically, such as class graphitic nitralloy carbon is added in polyvinyl alcohol water solution.
After obtaining suspension, the suspension is carried out vacuum refrigeration by the present invention, obtains class graphene carbonitride.In this hair
In bright, the temperature of the vacuum refrigeration is preferably -240~-10 DEG C, more preferably -90~-50 DEG C, most preferably -50 DEG C, very
The time of air-cooled jelly is preferably 3~6h, more preferably 4~5h, and the pressure of the vacuum freeze drying is preferably 100~
200MPa, more preferably 150MPa.In the present invention, the suspension during vacuum refrigeration quick solidification at solid, i.e. class
Graphene carbonitride, the cold expansion process that hydrogen bond causes volume to become larger when being solidified using water, polyvinyl alcohol rapid crystallization, to shell
From obtaining class graphene carbonitride.
After obtaining class graphene carbonitride, the class graphene carbonitride is carried out vacuum freeze drying by the present invention, is obtained
Three-dimensional net structure class graphene carbonitride.In the present invention, water distils completely during the vacuum freeze drying, and water is distilling
The solid structure freezed will not be destroyed during discharge, that is, the solute component remained still keeps it in solution state
Spatial distribution.But because there is a large amount of gap between the evolution of water, since water shows one in freezing process between solute
Surely the lamellar structure being orientated, structure can be remained completely to a certain extent, and it is unfavorable to avoid layering and sedimentation etc.
Factor, be evenly distributed conducive to substance, so that product be made to show three-dimensional net structure on a microscopic scale, be macroscopically shown as
Spongy feature, so that the structure of product, gap are uniform, property is stablized.
In the present invention, preferably -80~0 DEG C of the temperature of the vacuum freeze drying, more preferably -48~-30 DEG C, very
The time of vacuum freecing-dry is preferably 24~72h, more preferably 60h, and the pressure of the vacuum freeze drying is preferably 100~
200MPa, more preferably 150MPa.
In the present invention, the vacuum refrigeration and vacuum freeze drying carry out preferably in vacuum freeze drier, described
Vacuum refrigeration preferably carries out in the freezing chamber of vacuum freeze drier, and the vacuum freeze drying is preferably in vacuum freeze drying
The drying position of machine carries out.In the present invention, it is preferred to control the temperature of vacuum freeze drying by the temperature of freezing chamber.
In the present invention, it is preferred to be up to the pressure of required vacuum freeze drying using vacuum pump.
In the present invention, the heating rate for being warming up to the vacuum freeze drying temperature is preferably 10~20 DEG C/min.
The present invention also provides three-dimensional net structure class graphenes made from preparation method described in above-mentioned technical proposal to nitrogenize
Carbon, the specific surface area of the three-dimensional net structure class graphene carbonitride are 231~685m2/ g, porosity are 48~92%.
The present invention also provides the three-dimensional net structure class graphene carbonitrides described in above-mentioned technical proposal in organic contamination
Application in object absorption, photocatalytic degradation and photolysis water hydrogen field.
Below with reference to embodiment to three-dimensional net structure class graphene carbonitride provided by the invention and preparation method thereof and
Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
It is 8 × 10 by molecular weight3Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
20, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Melamine is put into
In alumina crucible and lid is added, is placed in Muffle furnace and is calcined, is that 5 DEG C/min is heated to 560 DEG C simultaneously with heating rate
Heat preservation 4h obtains yellow powder sample, i.e. class graphitic nitralloy carbon.0.1g product is added in the polyvinyl alcohol water solution prepared
It is sufficiently stirred, obtains uniform suspension.- 80 DEG C are quickly cooled to using freeze drier, the suspension made is put into cold
Freeze chamber, so that solution is quickly cooled to solid, and keep low temperature 3h.The solid freezed is transferred to vacuum drying position again and is made
The temperature of freezing chamber is maintained at -48 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 200MPa, the pumpdown time is
72h makes solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.
It is 605m using the specific surface area that nitrogen adsorption methods measure product2/ g, porosity 89%.Fig. 1 is class graphite nitrogen
Change the XRD diagram of carbon, (100) diffraction maximum occur in 13 ° of left-right positions in figure, are attributed in carbonitride and repeat in the same plane
Seven piperazine structures, corresponding interplanar distance be 0.68nm.There is sharp (002) diffraction maximum 27 ° of positions, it is corresponding
It is interlayer stacking characteristic peak, corresponding interlamellar spacing is 0.33nm, it was demonstrated that product is the layer structure carbonitride with similar graphite,
That is class graphitic nitralloy carbon.Fig. 2 is the XRD diagram of class graphene carbonitride after vacuum freeze drying, and is occurred in the XRD diagram in Fig. 1
The position at peak is almost the same, but the intensity at peak obviously weakens, and it is less to show that class graphitic nitralloy carbon has successfully been stripped into the number of plies
Class graphene carbonitride.Fig. 3 is the pictorial diagram of three-dimensional net structure class graphene carbonitride.
Embodiment 2
It is 8 × 10 by molecular weight3Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
20, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Melamine is put into
In alumina crucible and lid is added, is placed in Muffle furnace and is calcined, is that 5 DEG C/min is heated to 550 DEG C simultaneously with heating rate
Heat preservation 2h obtains yellow powder sample, i.e. class graphitic nitralloy carbon.0.2g product is added in the polyvinyl alcohol water solution prepared
It is sufficiently stirred, obtains uniform suspension.- 80 DEG C are quickly cooled to using freeze drier, the suspension made is put into cold
Freeze chamber, so that solution is quickly cooled to solid, and keep low temperature 3h.The solid freezed is transferred to vacuum drying position again and is made
The temperature of freezing chamber is maintained at -48 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 150MPa, the pumpdown time is
72h makes solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.The ratio of product is measured using nitrogen adsorption methods
Surface area is 483m2/ g, porosity 85%.
Embodiment 3
It is 8 × 10 by molecular weight3Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
10, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Melamine is put into
In alumina crucible and lid is added, is placed in Muffle furnace and is calcined, is that 5 DEG C/min is heated to 520 DEG C simultaneously with heating rate
Heat preservation 4h obtains yellow powder sample, i.e. class graphitic nitralloy carbon.0.3g product is added in the polyvinyl alcohol water solution prepared
It is sufficiently stirred, obtains uniform suspension.- 50 DEG C are quickly cooled to using freeze drier, the suspension made is put into cold
Freeze chamber, so that solution is quickly cooled to solid, and keep low temperature 3h.The solid freezed is transferred to vacuum drying position again and is made
The temperature of freezing chamber is maintained at -80 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 150MPa, the pumpdown time is
60h makes solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.The ratio of product is measured using nitrogen adsorption methods
Surface area is 423m2/ g, porosity 73%.
Embodiment 4
It is 8 × 10 by molecular weight3Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
10, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Melamine is put into
In alumina crucible and lid is added, is placed in Muffle furnace and is calcined, is that 5 DEG C/min is heated to 500 DEG C simultaneously with heating rate
Heat preservation 4h obtains yellow powder sample, i.e. class graphitic nitralloy carbon.0.5g product is added in the polyvinyl alcohol water solution prepared
It is sufficiently stirred, obtains uniform suspension.- 50 DEG C are quickly cooled to using freeze drier, the suspension made is put into cold
Freeze chamber, so that solution is quickly cooled to solid, and keep low temperature 3h.The solid freezed is transferred to vacuum drying position again and is made
The temperature of freezing chamber is maintained at -30 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 150MPa, the pumpdown time is
60h makes solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.The ratio of product is measured using nitrogen adsorption methods
Surface area is 343m2/ g, porosity 70%.
Embodiment 5
It is 2 × 10 by molecular weight5Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
10, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Melamine is put into
In alumina crucible and lid is added, is placed in Muffle furnace and is calcined, is that 5 DEG C/min is heated to 500 DEG C simultaneously with heating rate
Heat preservation 2h obtains yellow powder sample, i.e. class graphitic nitralloy carbon.1g product is added in the polyvinyl alcohol water solution prepared and is filled
Divide stirring, obtains uniform suspension.- 50 DEG C are quickly cooled to using freeze drier, the suspension made is put into freezing
Chamber makes solution quickly be cooled to solid, and keeps low temperature 3h.The solid freezed is transferred to vacuum drying position again and is made cold
The temperature for freezing chamber is maintained at -30 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 100MPa, the pumpdown time is
For 24 hours, make solvent distillation completely, obtain three-dimensional net structure class graphene carbonitride.The ratio of product is measured using nitrogen adsorption methods
Surface area is 231m2/ g, porosity 48%.
Embodiment 6
It is 2 × 10 by molecular weight5Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
20, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Melamine is put into
In alumina crucible and lid is added, is placed in Muffle furnace and is calcined, is that 5 DEG C/min is heated to 550 DEG C simultaneously with heating rate
Heat preservation 6h obtains yellow powder sample, i.e. class graphitic nitralloy carbon.0.2g product is added in the polyvinyl alcohol water solution prepared
It is sufficiently stirred, obtains uniform suspension.- 240 DEG C are quickly cooled to using freeze drier, the suspension made is put into cold
Freeze chamber, so that solution is quickly cooled to solid, and keep low temperature 3h.The solid freezed is transferred to vacuum drying position again and is made
The temperature of freezing chamber is maintained at -10 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 100MPa, the pumpdown time is
60h makes solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.The ratio of product is measured using nitrogen adsorption methods
Surface area is 451m2/ g, porosity 76%.
Embodiment 7
It is 8 × 10 by molecular weight3Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
20, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Urea is put into oxidation
In aluminium crucible and lid is added, is placed in Muffle furnace and is calcined, be heated to 520 DEG C with heating rate for 2 DEG C/min and keep the temperature
8h obtains pale yellow powder sample, i.e. class graphitic nitralloy carbon.0.1g product is added in the polyvinyl alcohol water solution prepared and is filled
Divide stirring, obtains uniform suspension.- 50 DEG C are quickly cooled to using freeze drier, the suspension made is put into freezing
Chamber makes solution quickly be cooled to solid, and keeps low temperature 6h.The solid freezed is transferred to vacuum drying position again and is made cold
The temperature for freezing chamber is maintained at -80 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 200MPa, the pumpdown time is
72h makes solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.The ratio of product is measured using nitrogen adsorption methods
Surface area is 685m2/ g, porosity 92%.
Embodiment 8
It is 8 × 10 by molecular weight3Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
10, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Urea is put into oxidation
In aluminium crucible and lid is added, is placed in Muffle furnace and is calcined, be heated to 520 DEG C with heating rate for 5 DEG C/min and keep the temperature
2h obtains pale yellow powder sample, i.e. class graphitic nitralloy carbon.0.2g product is added in the polyvinyl alcohol water solution prepared and is filled
Divide stirring, obtains uniform suspension.- 240 DEG C are quickly cooled to using freeze drier, the suspension made is put into freezing
Chamber makes solution quickly be cooled to solid, and keeps low temperature 4h.The solid freezed is transferred to vacuum drying position again and and is made
The temperature of freezing chamber is maintained at -80 DEG C, and using vacuum pump by the intracorporal air pressure reduction of freezing chamber in 200MPa, the pumpdown time is
72h makes solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.The ratio of product is measured using nitrogen adsorption methods
Surface area is 441m2/ g, porosity 74%.
Embodiment 9
It is 8 × 10 by molecular weight3Polyvinyl alcohol be added in aqueous solution, wherein polyvinyl alcohol and water in mass ratio 1:
20, a period of time is stirred under 90 DEG C of water bath conditions, obtains transparent polyvinyl alcohol water solution, for use.Urea is put into oxidation
In aluminium crucible and lid is added, is placed in Muffle furnace and is calcined, be heated to 520 DEG C with heating rate for 5 DEG C/min and keep the temperature
8h obtains pale yellow powder sample, i.e. class graphitic nitralloy carbon.0.2g product is added in the polyvinyl alcohol water solution prepared and is filled
Divide stirring, obtains uniform suspension.- 90 DEG C are quickly cooled to using freeze drier, the suspension made is put into freezing
Chamber makes solution quickly be cooled to solid, and keeps low temperature 6h.The solid freezed is transferred to vacuum drying position again and is made cold
The temperature for freezing chamber is maintained at 0 DEG C, is reduced the intracorporal air pressure of freezing chamber in 200MPa, pumpdown time 72h using vacuum pump,
Make solvent distillation completely, obtains three-dimensional net structure class graphene carbonitride.The specific surface of product is measured using nitrogen adsorption methods
Product is 554m2/ g, porosity 87%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of three-dimensional net structure class graphene carbonitride, comprising the following steps:
Class graphitic nitralloy carbon is provided；
The class graphitic nitralloy carbon is mixed with polyvinyl alcohol water solution, obtains suspension；
The suspension is subjected to vacuum refrigeration, obtains class graphene carbonitride；
The class graphene carbonitride is subjected to vacuum freeze drying, obtains three-dimensional net structure class graphene carbonitride.
2. preparation method according to claim 1, which is characterized in that polyvinyl alcohol and water in the polyvinyl alcohol water solution
Mass ratio be 1:20~1:10.
3. preparation method according to claim 1 or 2, which is characterized in that polyvinyl alcohol in the polyvinyl alcohol water solution
Molecular weight be 8 × 103~2 × 105。
4. preparation method according to claim 1 or 2, which is characterized in that the quality and poly- second of the class graphitic nitralloy carbon
The volume ratio of enol aqueous solution is 0.1~1g:100mL.
5. preparation method according to claim 1, which is characterized in that the class graphitic nitralloy carbon is passed through by nitrogen-rich organic object
Thermal polycondensation process obtains.
6. preparation method according to claim 1, which is characterized in that the temperature of the vacuum refrigeration is -240~-10 DEG C,
The time of vacuum refrigeration is 3~6h.
7. preparation method according to claim 1, which is characterized in that the temperature of the vacuum freeze drying is -80~0
DEG C, the time of vacuum freeze drying is 24~72h, and the pressure of vacuum freeze drying is 100~200MPa.
8. preparation method according to claim 1 or claim 7, which is characterized in that be warming up to the vacuum freeze drying temperature
Heating rate is 10~20 DEG C/min.
9. three-dimensional net structure class graphene carbonitride, feature made from preparation method described in claim 1~8 any one
It is, the specific surface area of the three-dimensional net structure class graphene carbonitride is 231~685m2/ g, porosity are 48~92%.
10. three-dimensional net structure class graphene carbonitride as claimed in claim 9 Adsorption of Organic, photocatalytic degradation and
Application in photolysis water hydrogen field.
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