CN110064428A - A kind of g-C3N4/ graphene composite material, preparation method and application - Google Patents
A kind of g-C3N4/ graphene composite material, preparation method and application Download PDFInfo
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- CN110064428A CN110064428A CN201910466402.3A CN201910466402A CN110064428A CN 110064428 A CN110064428 A CN 110064428A CN 201910466402 A CN201910466402 A CN 201910466402A CN 110064428 A CN110064428 A CN 110064428A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010439 graphite Substances 0.000 claims abstract description 65
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 61
- 238000011282 treatment Methods 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 17
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 16
- -1 nitrogenous compound Chemical class 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000011229 interlayer Substances 0.000 abstract description 4
- 238000005411 Van der Waals force Methods 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 description 18
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 17
- 229960000907 methylthioninium chloride Drugs 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011812 mixed powder Substances 0.000 description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The embodiment of the present application provides a kind of g-C3N4/ graphene composite material, preparation method and application, belong to technical field of graphene.g-C3N4The preparation method of/graphene composite material, includes the following steps: with g-C3N4The electrode formed after powder and powdered graphite mixing carries out electrochemical treatments, the dry electrode after electrochemical treatments as anode in the electrolytic solution.Electrode after drying is placed under microwave environment and is handled.When carrying out electrochemical treatments, electrolyte can enter g-C3N4In the lamellar structure in graphite, then under microwave treatment, due to the high-energy of microwave, electrolyte can be made to decompose and gasify rapidly, thus make its rapid expanding, the interlaminar separation when pressure at this time is more than piece interlayer Van der Waals force, and remove into nanometer sheet, obtain g-C3N4/ graphene composite material, specific surface area is larger, to improve its redox ability.
Description
Technical field
This application involves technical field of graphene, in particular to a kind of g-C3N4/ graphene composite material, its preparation
Method and application.
Background technique
Existing g-C3N4/ graphene composite material is by g-C under normal conditions3N4Powder and graphene powder mixing, lead to
High energy ball mill progress ball milling is crossed to obtain.The specific surface area of the composite material of acquisition is smaller, can not play each ingredient well
Performance.
Summary of the invention
The application's is designed to provide a kind of g-C3N4/ graphene composite material, preparation method and application, compare table
Area is larger, being capable of effective degradable organic pollutant.
In a first aspect, the embodiment of the present application provides a kind of g-C3N4The preparation method of/graphene composite material, including it is as follows
Step: with g-C3N4The electrode formed after powder and powdered graphite mixing carries out at electrochemistry in the electrolytic solution as anode
Reason, the dry electrode after electrochemical treatments.Electrode after drying is placed in processing under microwave environment and obtains g-C3N4/ graphite
Alkene composite material.
When carrying out electrochemical treatments, electrolyte can enter g-C3N4In the lamellar structure in graphite, then micro-
Under wave processing, due to the high-energy of microwave, electrolyte molecule can be made to decompose and gasify rapidly, thus make its rapid expanding, when
Interlaminar separation when pressure is more than piece interlayer Van der Waals force, and remove into nanometer sheet.g-C3N4It is converted to graphite phase carbon nitride, graphite
It is converted to graphene, obtains g-C3N4/ graphene composite material, specific surface area is larger, and due to the electric conductivity of graphene,
The rate of transform that electronics can be improved is not easy the electron-hole pair generated in graphene carbonitride compound, easily and in external environment
Oxygen gas and water etc. react, to show stronger reproducibility and oxidisability.
With reference to first aspect, in another embodiment, g-C3N4The mass ratio of powder and powdered graphite is 1:(0.5-5).
It can make g-C3N4Powder is uniformly mixed with powdered graphite, and on the basis of photocatalysis performance with higher, can
With excellent electric conductivity, the electronics transfer rate of composite material can be improved, inhibit conduction band electron and valence in graphite-phase titanium nitride
Burying in oblivion with hole keeps the catalytic performance of composite material stronger.
With reference to first aspect, in another embodiment, electrolyte is perchloric acid solution.Optionally, the concentration of perchloric acid is
3-4mol/L。
Use perchloric acid solution as electrolyte, when electrochemical treatments, electrolyte is easily accessible g-C3N4Lamella knot
In structure and graphite platelet structure.
With reference to first aspect, in another embodiment, electrolyte is dilution heat of sulfuric acid.Optionally, dilution heat of sulfuric acid is dense
Degree is 2-5mol/L.
Use dilution heat of sulfuric acid as electrolyte, when electrochemical treatments, electrolyte is easily accessible g-C3N4Lamella knot
In structure and graphite platelet structure, and bisulfate ion molecule can decompose and gasify rapidly, obtain under conditions of microwave treatment
The specific surface area of composite material is bigger.
With reference to first aspect, in another embodiment, the condition of electrochemical treatments are as follows: voltage 1-3V, conduction time is
0.5-1h。
So that electrolyte enters g-C3N4In lamellar structure and graphite platelet structure, intercalation configuration is formed, is convenient for subsequent progress
Microwave treatment.
With reference to first aspect, in another embodiment, the condition of microwave treatment are as follows: power 600-800w, time is
20s-2min。
To make electrolyte molecule decompose and gasify rapidly, the biggish composite material of specific surface area is obtained.
With reference to first aspect, in another embodiment, by g-C3N4The method of powder and powdered graphite mixing, comprising: by g-
C3N4Powder and powdered graphite are put into ball milling 2-4h in ball mill after dispersing in a solvent, be separated by solid-liquid separation, take solid and drying.It can
Selection of land, solvent are water or/and volatilizable solvent.
Ball milling is carried out in a solvent, can make g-C3N4It is more uniform with the mixing of graphite, avoid it from reuniting.Make just
Walking obtained mixed-powder has excellent electric conductivity, convenient for the electrochemical reaction of next step.
With reference to first aspect, in another embodiment, nitrogenous compound is carried out under conditions of temperature is 480-520 DEG C
Calcining 0.8-1.5h for the first time, then carry out second of calcining 1.5-2.5h under conditions of temperature is 530-580 DEG C and obtain g-C3N4
Powder.Optionally, nitrogenous compound includes one of thiocarbamide, dicyanodiamine, melamine or urea or a variety of.Obtained g-
C3N4Powder is easy to be stripped.
Second aspect, the embodiment of the present application provide a kind of g-C3N4/ graphene composite material, by above-mentioned g-C3N4/ graphene
The preparation method of composite material is prepared.
g-C3N4Nanometer sheet has good photocatalysis effect, and graphene nanometer sheet has good electric conductivity, resulting multiple
Condensation material is by g-C3N4Nanometer sheet and graphene nanometer sheet are mutually interspersed, and specific surface area is larger, graphite phase carbon nitride and graphene
Between there are heterojunction structures, g-C can be played3N4With the synergistic effect of graphene, there is very strong photocatalysis effect.
The third aspect, the embodiment of the present application provide a kind of above-mentioned g-C3N4/ graphene composite material is in degradable organic pollutant
In application.It, can effective degradable organic pollutant as photochemical catalyst.
Detailed description of the invention
Technical solution in ord to more clearly illustrate embodiments of the present application, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only some embodiments of the application, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain the protection scope that other relevant attached drawings also belong to the application.
Fig. 1 is the g-C that embodiment 1 provides3N4/ graphene composite material and g-C3N4XRD diagram；
Fig. 2 is the g-C that embodiment 1 provides3N4The TEM of/graphene composite material schemes；
Fig. 3 is the g-C that embodiment 1 provides3N4/ graphene composite material, g-C3N4With the property of graphene degradation of methylene blue
It can comparison diagram.
Specific embodiment
It, below will be in the embodiment of the present application to keep the purposes, technical schemes and advantages of the embodiment of the present application clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the g-C of the embodiment of the present application3N4/ graphene composite material, preparation method and application carry out specifically
It is bright.
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), g-C is prepared3N4Powder:
Nitrogenous compound is carried out to calcining 0.8-1.5h for the first time under conditions of temperature is 480-520 DEG C, then in temperature
Second of calcining 1.5-2.5h is carried out under conditions of being 530-580 DEG C obtains g-C3N4Powder.
Specifically, the melamine for weighing certain mass is put in Muffle furnace, and 1h is kept the temperature at 500 DEG C and forge for the first time
It burns, heat preservation 2h carries out second of calcining at 550 DEG C, obtains g-C3N4Powder.Wherein, it calcines in two times, and the temperature of calcining for the first time
Spend, the g-C of available of a relatively loose structure lower than the temperature of second of calcining3N4Powder, also available more g-C3N4
Powder.
Optionally, nitrogenous compound includes one of thiocarbamide, dicyanodiamine, melamine or urea or a variety of.Equal energy
It is enough that g-C is obtained by calcining3N4Powder.Wherein, the calcining of nitrogenous compound can be in air atmosphere, nitrogen atmosphere or argon atmospher
Middle progress is enclosed, the embodiment of the present application is with no restrictions.
In another embodiment, g-C3N4The preparation method of powder can also be prepared by chemical vapour deposition technique.
(2), material mixes:
By g-C3N4Powder and powdered graphite are put into ball milling 2-4h in ball mill after dispersing in a solvent, be separated by solid-liquid separation, and take solid
Body is simultaneously dried to obtain mixed-powder.
Ball milling dispersion, g-C are carried out under conditions of with solvent3N4It is more uniform with the dispersion of graphite, obtained g-
C3N4The dispersion effect of/graphene composite material is more preferable, g-C3N4It can preferably be brought into play with the functional characteristic of graphene,
And it is complementary effect it is stronger.
Optionally, solvent is water or/and volatilizable solvent.Such as: solvent can be individual water, be also possible to individually
The mixture of volatilizable solvent or water and volatilizable solvent.In the embodiment of the present application, volatilizable solvent can be ethyl alcohol, propyl alcohol
With the one of which of isopropanol.It is illustrated and is illustrated using ethanol water as solvent below, g-C3N4Powder and powdered graphite are in ethyl alcohol
It is more easier to disperse in water, and ethyl alcohol is volatile, the time of subsequent drying is shorter.In ethanol water, the volume of ethyl alcohol and water
Than can be arbitrary proportion, for example, 1:(0.5-1.5), so as to g-C3N4The dispersion of powder and powdered graphite and can quickly into
Row drying.
In another embodiment, g-C3N4Powder and powdered graphite can also disperse in a solvent and carry out ultrasonic mixing, Gu
Liquid separation, takes solid and drying.
Wherein, the mode of separation of solid and liquid can be filtering, centrifuge separation etc., and the embodiment of the present application is without limitation.
In other embodiments, g-C3N4Powder and powdered graphite can also directly carry out ball milling mixing.
(3), mixed-powder is formed to obtain electrode, wherein can be formed by way of pressure-like, such as using tablet press machine into
Row pressure-like obtains electrode slice.
Wherein, the concrete mode of pressure-like is: weighing the above-mentioned mixed g-C of certain mass3N4Powder and powdered graphite are put into mould
Tool finally takes out in addition certain pressure is 10-20MPa, dwell time 1-2min and is pressed molding mixture electrode slice,
Electrode slice is that diameter is 1cm, with a thickness of the disk of 0.5cm.
It is, of course, also possible to electrode bar be obtained by way of pressure-like, as long as using mixed g-C3N4Powder and graphite powder
It is used as anode after the molding of end, is the protection scope of the embodiment of the present application.
(4), using electrode as anode, electrochemical treatments, the dry electricity after electrochemical treatments are carried out in the electrolytic solution
Pole.When carrying out electrochemical treatments, electrolyte can enter g-C3N4In the lamellar structure in graphite, be dried with
Afterwards, electrolyte molecule is located at g-C3N4It, can be by g-C in the lamellar structure in graphite3N4It is partially stripped with graphite.
Specifically, using electrode as anode, platinum filament as cathode, use dilution heat of sulfuric acid as electrolyte, be in voltage
1-3V, conduction time to carry out electrochemical treatments under conditions of 0.5-1h, make the inside of bisulfate ion molecule insertion electrode, also
It is g-C3N4Inside graphite, make g-C3N4Become larger with the molecular gap of graphite, intercalation configuration is formed, after electrochemical treatments
Electrode collects, and is dried.Optionally, the voltage of electrochemical treatments can be 1V or 2V or 3V, when energization
Between can be 0.5h or 1h or 0.8h etc..
Wherein, voltage is bigger, and conduction time is longer, and bisulfate ion molecule can be made more to enter nitridation carbon molecules and stone
It is more abundant to be stripped carbonitride and graphite between black lamellar structure, obtain graphite phase carbon nitride nanometer sheet and stone
Black alkene nanometer sheet.
Optionally, the concentration of dilution heat of sulfuric acid is 2-5mol/L, such as: concentration can be 2mol/L or 2.5mol/L, or
3mol/L or 3.5mol/L or 4mol/L or 5mol/L.Dilute sulfuric acid electrolyte under this concentration conditions, can be in microwave treatment
When, so that bisulfate ion molecule is decomposed and is gasified rapidly, makes g-C3N4The pressure being subject to graphite is more than the Van der Waals of piece interlayer
Power makes g-C3N4Lamella and graphite flake layer are peeling-off, obtain g-C3N4Nanometer sheet and Nano graphite chip architecture, the g- made
C3N4The specific surface area of/graphene composite material is bigger.
In another embodiment, electrolyte is perchloric acid solution, and the concentration of perchloric acid solution is 3-4mol/L, such as:
Concentration can be 3mol/L or 3.2mol/L or 3.5mol/L or 3.8mol/L or 4mol/L.Perchloric acid molecule enters g-
C3N4Lamella and graphite lamellar structure in after, by subsequent microwave treatment, also can fast decoupled and volatilization, so as to g-
C3N4The removing of lamella and graphite flake layer.
(5) electrode after drying is placed under microwave environment and is handled.Due to the high-energy of microwave, electrolyte molecule can be made
It decomposes rapidly and gasification, to make its rapid expanding, the interlaminar separation when pressure is more than piece interlayer Van der Waals force, and remove at receiving
Rice piece.At this point, g-C3N4It is converted to graphite phase carbon nitride, graphite is converted to graphene, obtains g-C3N4/ graphene composite material,
Its specific surface area is larger, and due to the electric conductivity of graphene, the rate of transform of electronics can be improved, and makes to produce in graphene carbonitride
Raw electron-hole pair is not easy compound, easily reacts with the oxygen gas and water etc. in external environment, thus show it is stronger also
Originality and oxidisability.
Optionally, the condition of microwave treatment is as follows: power 600-800w, time 20s-2min.Such as: microwave power
For 600w, the microwave time is 2min or microwave power is 700w, and the microwave time is 1min or microwave power is 800w, when microwave
Between be 20s, the electrode rapid expanding after capable of making electrochemical treatments obtains the biggish g-C of specific surface area3N4/ graphene is multiple
Condensation material.
In the present embodiment, g-C3N4The mass ratio of powder and powdered graphite is 1:(0.5-5).Such as: g-C3N4Powder and stone
The mass ratio at ink powder end is 1:0.5 or 1:1 or 1:2 or 1:3 or 1:4 or 1:5.Use the g-C of above-mentioned mass ratio3N4Powder
G-C is carried out with powdered graphite3N4The preparation of/graphene composite material keeps its photocatalysis performance stronger, and electric conductivity is higher, so as to
Improve its catalytic performance.
The embodiment of the present application provides a kind of g-C3N4/ graphene composite material, by above-mentioned g-C3N4/ graphene composite material
Preparation method be prepared.g-C3N4Nanometer sheet has good photocatalysis effect, and graphene nanometer sheet has conductive well
Property, resulting composite material is by g-C3N4Nanometer sheet and graphene nanometer sheet are mutually interspersed, and specific surface area is larger, graphite-phase nitrogen
There are heterojunction structures between change carbon and graphene, can play g-C3N4With the synergistic effect of graphene, there is very strong photocatalysis
Effect.
The embodiment of the present application provides a kind of above-mentioned g-C3N4Application of/the graphene composite material in degradable organic pollutant.
It, can effective degradable organic pollutant as photochemical catalyst.Such as: formaldehyde, methylene blue etc..
Embodiment 1
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), melamine is placed in Muffle furnace, carries out calcining 1h for the first time under conditions of temperature is 500 DEG C, then
Temperature carries out second of calcining 2h and obtains g-C under conditions of being 550 DEG C3N4Powder.
(2), by g-C3N4Powder and powdered graphite are put into ball milling 3h in ball mill, centrifuge separation after dispersing in ethanol water,
It takes solid and is dried to obtain mixed-powder.Wherein, g-C3N4The mass ratio of powder and powdered graphite is 1:1.
(3), the above-mentioned mixed g-C of certain mass is weighed3N4Powder and powdered graphite are put into mold, in addition certain pressure is
15MPa, dwell time are pressure-like under conditions of 1.5min, and obtaining diameter is 1cm, the electrode slice of thickness 0.5cm.
(4), using electrode slice as anode, platinum filament is as cathode, and concentration is the dilute sulfuric acid of 4mol/L as electrolyte, in electricity
Pressure is 2V, and conduction time to carry out electrochemical treatments under conditions of 0.8h, dries the electrode slice Jing Guo electrochemical treatments.
(5) electrode slice after drying is placed in power is that processing 1min obtains g-C under 700w microwave environment3N4/ graphene is multiple
Condensation material.
Embodiment 2
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), melamine is placed in Muffle furnace, carries out calcining 1h for the first time under conditions of temperature is 500 DEG C, then
Temperature carries out second of calcining 2h and obtains g-C under conditions of being 550 DEG C3N4Powder.
(2), by g-C3N4Powder and powdered graphite are put into ball milling 3h in ball mill and obtain mixed-powder.Wherein, g-C3N4Powder
The mass ratio of end and powdered graphite is 1:1.
(3), the above-mentioned mixed g-C of certain mass is weighed3N4Powder and powdered graphite are put into mold, in addition certain pressure is
15MPa, dwell time are pressure-like under conditions of 1.5min, and obtaining diameter is 1cm, the electrode slice of thickness 0.5cm.
(4), using electrode slice as anode, platinum filament is as cathode, and concentration is the dilute sulfuric acid of 4mol/L as electrolyte, in electricity
Pressure is 2V, and conduction time to carry out electrochemical treatments under conditions of 0.8h, dries the electrode slice Jing Guo electrochemical treatments.
(5) electrode slice after drying is placed in power is that processing 1min obtains g-C under 700w microwave environment3N4/ graphene is multiple
Condensation material.
Embodiment 3
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), melamine is placed in Muffle furnace, carries out calcining 1h for the first time under conditions of temperature is 550 DEG C, then
Temperature carries out second of calcining 2h and obtains g-C under conditions of being 500 DEG C3N4Powder.
(2), by g-C3N4Powder and powdered graphite are put into ball milling 3h in ball mill, centrifuge separation after dispersing in ethanol water,
It takes solid and is dried to obtain mixed-powder.Wherein, g-C3N4The mass ratio of powder and powdered graphite is 1:1.
(3), the above-mentioned mixed g-C of certain mass is weighed3N4Powder and powdered graphite are put into mold, in addition certain pressure is
15MPa, dwell time are pressure-like under conditions of 1.5min, and obtaining diameter is 1cm, the electrode slice of thickness 0.5cm.
(4), using electrode slice as anode, platinum filament is as cathode, and concentration is the dilute sulfuric acid of 4mol/L as electrolyte, in electricity
Pressure is 2V, and conduction time to carry out electrochemical treatments under conditions of 0.8h, dries the electrode slice Jing Guo electrochemical treatments.
(5) electrode slice after drying is placed in power is that processing 1min obtains g-C under 700w microwave environment3N4/ graphene is multiple
Condensation material.
Embodiment 4
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), melamine is placed in Muffle furnace, carries out calcining 2h for the first time under conditions of temperature is 500 DEG C, then
Temperature carries out second of calcining 1h and obtains g-C under conditions of being 550 DEG C3N4Powder.
(2), by g-C3N4Powder and powdered graphite are put into ball milling 3h in ball mill, centrifuge separation after dispersing in ethanol water,
It takes solid and is dried to obtain mixed-powder.Wherein, g-C3N4The mass ratio of powder and powdered graphite is 3:1.
(3), the above-mentioned mixed g-C of certain mass is weighed3N4Powder and powdered graphite are put into mold, in addition certain pressure is
15MPa, dwell time are pressure-like under conditions of 1.5min, and obtaining diameter is 1cm, the electrode slice of thickness 0.5cm.
(4), using electrode slice as anode, platinum filament is as cathode, and concentration is the dilute sulfuric acid of 4mol/L as electrolyte, in electricity
Pressure is 2V, and conduction time to carry out electrochemical treatments under conditions of 0.8h, dries the electrode slice Jing Guo electrochemical treatments.
(5) electrode slice after drying is placed in power is that processing 1min obtains g-C under 700w microwave environment3N4/ graphene is multiple
Condensation material.
Comparative example 1
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), melamine is placed in Muffle furnace, carries out calcining 1h for the first time under conditions of temperature is 500 DEG C, then
Temperature carries out second of calcining 2h and obtains g-C under conditions of being 550 DEG C3N4Powder.
(2), by g-C3N4Powder and graphene are put into ball milling 3h in ball mill, centrifuge separation after dispersing in ethanol water, take
Solid is simultaneously dried to obtain g-C3N4/ graphene composite material.
Comparative example 2
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), melamine is placed in Muffle furnace, carries out calcining 1h for the first time under conditions of temperature is 500 DEG C, then
Temperature carries out second of calcining 2h and obtains g-C under conditions of being 550 DEG C3N4Powder.
(2), by g-C3N4Powder and powdered graphite are put into ball milling 3h in ball mill, centrifuge separation after dispersing in ethanol water,
It takes solid and is dried to obtain mixed-powder.Wherein, g-C3N4The mass ratio of powder and powdered graphite is 1:1.
(3), the above-mentioned mixed g-C of certain mass is weighed3N4Powder and powdered graphite are put into mold, in addition certain pressure is
15MPa, dwell time are pressure-like under conditions of 1.5min, and obtaining diameter is 1cm, the electrode slice of thickness 0.5cm.
(4), using electrode slice as anode, platinum filament is as cathode, and concentration is the dilute sulfuric acid of 4mol/L as electrolyte, in electricity
Pressure is 2V, and conduction time, the dry electrode slice Jing Guo electrochemical treatments obtained g- to carry out electrochemical treatments under conditions of 0.8h
C3N4/ graphene composite material.
Comparative example 3
g-C3N4The preparation method of/graphene composite material, includes the following steps:
(1), melamine is placed in Muffle furnace, carries out calcining 1h for the first time under conditions of temperature is 500 DEG C, then
Temperature carries out second of calcining 2h and obtains g-C under conditions of being 550 DEG C3N4Powder.
(2), by g-C3N4Powder and powdered graphite are put into ball milling 3h in ball mill, centrifuge separation after dispersing in ethanol water,
It takes solid and is dried to obtain mixed-powder.Wherein, g-C3N4The mass ratio of powder and powdered graphite is 1:1.
(3), the above-mentioned mixed g-C of certain mass is weighed3N4Powder and powdered graphite are put into mold, in addition certain pressure is
15MPa, dwell time are pressure-like under conditions of 1.5min, and obtaining diameter is 1cm, the electrode slice of thickness 0.5cm.
(4) electrode slice is placed in power is that processing 1min obtains g-C under 700w microwave environment3N4/ graphene composite material.
Experimental example 1
Fig. 1 is the g-C that embodiment 1 provides3N4/ graphene composite material and g-C3N4XRD diagram, it will be seen from figure 1 that
Wherein, top curve is pure g-C3N4XRD diffraction curve, lower curve g-C3N4The XRD diffraction of/graphene composite material
Curve declines and increases respectively with 13 ° of diffraction peak for 27 ° in figure, and the method for illustrating to provide by embodiment 1 can be prepared
Obtain g-C3N4/ graphene composite material.
Fig. 2 is the g-C that embodiment 1 provides3N4The TEM of/graphene composite material schemes, figure it is seen that there is piece in figure
Layer structure and hole, the size of lamellar structure reach nanoscale, and the method for illustrating to provide by embodiment 1 can be prepared
With g-C3N4The g-C of nanometer sheet and graphene nanometer sheet3N4/ graphene composite material, and there are many holes in the composite material
Hole, specific surface area are larger.
Fig. 3 is the g-C that embodiment 1 provides3N4/ graphene composite material, g-C3N4With the property of graphene degradation of methylene blue
It can comparison diagram, wherein the detection mode of degradation of methylene blue is: photochemical catalyst is dispersed in methylene blue solution to (concentration is
20mg/L), stirring and adsorbing in the dark is placed extremely to balance.Solution after adsorption equilibrium is poured into light degradation pond, opens ultraviolet xenon lamp
(having filtered ultraviolet light, light intensity 18) and recirculated water carry out radiation of visible light, detect the degradation rate of methylene blue, evaluate material pair
The photocatalytic activity of methylene blue.In Fig. 3, leftmost information drawing indicates individual g-C3N4Degradation rate to methylene blue is
41%；Intermediate bar chart indicates g-C3N4/ graphene composite material is 84% to the degradation rate of methylene blue；The bar shaped on the right
Figure indicates that individual graphene is 5% to the degradation rate of methylene blue.It can release, g-C3N4/ graphene composite material is to methylene
The degradation effect of base indigo plant is best, catalytic activity highest, and its degradation rate is greater than individual g-C3N4With individual graphene to methylene
The sum of the degradation rate of base indigo plant.
Experimental example 2
The g-C that embodiment 1- embodiment 4 and comparative example 1- comparative example 3 provide is detected respectively using BET test3N4/ graphite
Alkene composite material and individual g-C3N4And the individually specific surface area of graphene, and the method detection provided by experimental example 1
The g-C that embodiment 1- embodiment 4, comparative example 1- comparative example 3 provide3N4/ graphene composite material and individual g-C3N4And list
Only graphene obtains table 1 to the degradation rate of methylene blue.
1 g-C of table3N4The performance of/graphene composite material
As it can be seen from table 1 the g-C that embodiment 1- embodiment 4 provides3N4The specific surface area of/graphene composite material and right
The degradation rate of methylene blue is all larger than the g-C of the offer of comparative example 1- comparative example 33N4/ graphene composite material.
Embodiment 1 and embodiment 2 compare it is found that by g-C3N4Powder and powdered graphite are put into dry bulb in ball mill and grind, and obtain
G-C3N4The specific surface area of/graphene composite material is smaller, lower to the degradation rate of methylene blue.
Embodiment 3 and embodiment 1 compare it is found that preparing g-C3N4When powder, the temperature of calcining is greater than and forges for the second time for the first time
The temperature of burning, obtained g-C3N4The specific surface area of/graphene composite material is smaller, lower to the degradation rate of methylene blue.
Embodiment 4 and embodiment 1 compare it is found that g-C3N4When the mass ratio of powder and powdered graphite is 3:1, obtained g-
C3N4The specific surface area of/graphene composite material is smaller, lower to the degradation rate of methylene blue.
In embodiment 1, embodiment 3 and embodiment 4, with individual g-C3N4It is compared with individual graphene, methylene blue
Degradation rate is greater than individual g-C3N4With individual graphene to the sum of the degradation rate of methylene blue.
Embodiments described above is some embodiments of the present application, instead of all the embodiments.The reality of the application
The detailed description for applying example is not intended to limit claimed scope of the present application, but is merely representative of the selected implementation of the application
Example.Based on the embodiment in the application, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall in the protection scope of this application.
Claims (10)
1. a kind of g-C3N4The preparation method of/graphene composite material, which comprises the steps of:
With g-C3N4The electrode formed after powder and powdered graphite mixing carries out at electrochemistry in the electrolytic solution as anode
Reason, the dry electrode after electrochemical treatments；
The electrode after drying is placed in processing under microwave environment and obtains the g-C3N4/ graphene composite material.
2. g-C according to claim 13N4The preparation method of/graphene composite material, which is characterized in that the g-C3N4
The mass ratio of powder and the powdered graphite is 1:(0.5-5).
3. g-C according to claim 13N4The preparation method of/graphene composite material, which is characterized in that the electrolyte
For perchloric acid solution；
Optionally, the concentration of the perchloric acid solution is 3-4mol/L.
4. g-C according to claim 13N4The preparation method of/graphene composite material, which is characterized in that the electrolyte
For dilution heat of sulfuric acid；
Optionally, the concentration of the dilution heat of sulfuric acid is 2-5mol/L.
5. g-C described in any one of -4 according to claim 13N4The preparation method of/graphene composite material, which is characterized in that
The condition of the electrochemical treatments are as follows: voltage 1-3V, conduction time 0.5-1h.
6. g-C according to claim 13N4The preparation method of/graphene composite material, which is characterized in that at the microwave
The condition of reason are as follows: power 600-800w, time 20s-2min.
7. g-C according to claim 13N4The preparation method of/graphene composite material, which is characterized in that by the g-
C3N4The method of powder and powdered graphite mixing, comprising:
By the g-C3N4Powder and the powdered graphite are put into ball milling 2-4h in ball mill after dispersing in a solvent, be separated by solid-liquid separation,
Take solid and drying；
Optionally, the solvent is water or/and volatilizable solvent.
8. g-C according to claim 13N4The preparation method of/graphene composite material, which is characterized in that by nitrogenous chemical combination
Object carries out calcining 0.8-1.5h for the first time under conditions of temperature is 480-520 DEG C, then under conditions of temperature is 530-580 DEG C
It carries out second of calcining 1.5-2.5h and obtains the g-C3N4Powder；
Optionally, the nitrogenous compound includes one of thiocarbamide, dicyanodiamine, melamine or urea or a variety of.
9. a kind of g-C3N4/ graphene composite material, which is characterized in that by the described in any item g-C of claim 1-83N4/ graphite
The preparation method of alkene composite material is prepared.
10. a kind of g-C as claimed in claim 93N4Application of/the graphene composite material in degradable organic pollutant.
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