CN106914268A - A kind of graphene composite nano material and its preparation method and application - Google Patents
A kind of graphene composite nano material and its preparation method and application Download PDFInfo
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- CN106914268A CN106914268A CN201710237672.8A CN201710237672A CN106914268A CN 106914268 A CN106914268 A CN 106914268A CN 201710237672 A CN201710237672 A CN 201710237672A CN 106914268 A CN106914268 A CN 106914268A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052796 boron Inorganic materials 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 41
- 239000006185 dispersion Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 26
- 238000002604 ultrasonography Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 239000012467 final product Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical class CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000006303 photolysis reaction Methods 0.000 claims description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 231100000719 pollutant Toxicity 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004408 titanium dioxide Substances 0.000 abstract description 7
- 230000009977 dual effect Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/55—Photoelectrolysis
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- C02F2305/00—Use of specific compounds during water treatment
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Abstract
The invention provides a kind of graphene composite nano material and preparation method thereof, the invention is on the one hand by the dual modified effect of B, N, there is electric conductivity higher, bigger area load free charge density compared to the Graphene of undoped p and effectively can be repaired the fault of construction of graphene oxide while doping, so as to form optical property and the doped graphene having good stability；On the other hand, the present invention is coupled by by titanium dioxide with both Graphenes of doping, produce cooperative compensating effect, and light induced electron will be transmitted to taking for Graphene, so as to reduce the recombination rate in hole and electronics, also cause that the forbidden band of titanium dioxide narrows, and extends photoresponse scope, so as to greatly improve photocatalysis performance, prepared composite property is very excellent.
Description
Technical field
The invention belongs to applications to nanostructures technical field, and in particular to a kind of graphene composite nano material and its system
Preparation Method and application.
Background technology
It is a Disciplinary Frontiers in current scientific research to the research of nano material, is also many scientific workers in the whole world
The focus of research.In place of the mystery of nano material and also the extensive concern for causing people is not even more by the aspect that people know；
The research being prepared to nano material and application even more current focus and difficult point, are also the high-tech emphasis of development.
Photocatalysis technology is the focus of current scientific research, and its range of application is quite varied, and such as sewage disposal, air are net
Change, Solar use, antibacterial, antifog and self-cleaning function etc..And the development of photocatalysis technology depends on catalysis material
Innovation and development, development high activity, the catalysis material of high stability are the keys of photocatalysis technology, and should by nanometer technology
For being one of important symbol of photocatalysis technology progress in recent years in the research and development of catalysis material, excellent preferable nanometer is developed
Catalysis material will be the important directions of photocatalysis technology research in a period from now on.
TiO2It is a kind of wide bandgap semiconductor, can only be by the shorter ultraviolet excitation of wavelength, this is for using only 4%
The sunshine of ultraviolet light content is totally unfavorable；Other light excites TiO2Produced photo-generate electron-hole recombination rate is high, causes light
Quantum efficiency is low, and photocatalysis performance is not protruded, this be also semiconductor type photochemical catalyst be restricted in actual applications it is main
Reason.Graphene, due to its very good photoelectric characteristic, has received extensive research and has applied since being found, special
It is not that the hydrophobicity for having important application, Graphene synusia conjugation aromatic structure surface in photocatalysis field is conducive to it to adsorb
Foreign surfaces reduce surface free energy, and to construct surface heterogeneous medium junction structure using the process of self-organization can improve composite photocatalyst
The photocatalytic activity of agent, while Graphene is conducive to improving its adsorbance.Therefore, by Graphene and conductor photocatalysis material
Compound graphene composite photocatalyst powder is a kind of novel photocatalysis material with high adsorption capacity and high catalytic activity.Its
In, boron doped graphene has electric conductivity higher, bigger area load free charge density compared to last doping Graphene
And stronger nitrogen oxides pernicious gas absorption (chemisorbed)；And N element doping can also improve its electric property, this be by
There is the atomic radius approximate with C atoms in N atoms, it is possible to as electron donor, the nitrogen generated after being adulterated with Graphene
Doped graphene shows electric conductivity higher.But also carry out dual chemical without being adulterated with B, N simultaneously in the prior art and change
Property Graphene improves the report of its performance with collective effect.
The content of the invention
It is an object of the invention to provide a kind of graphene composite nano material, the composite nano materials are on the one hand with B, N unit
Element carries out the common modified optical property to improve Graphene to Graphene；On the other hand modified Graphene is urged with TiO2 light
Agent carries out being compounded to form composite, so as to increase the absorption of light and widen the scope of light absorbs to obtain high performance being combined
Catalysis material.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of preparation method of graphene composite nano material, the composite nano materials are TiO2The nitrogen co-doped stone of/boron
Black alkene material, the preparation method of the material specifically includes following steps：
(1) preparation of the nitrogen co-doped Graphene of boron：10~20g graphene oxides are weighed, the deionization of 20~40mL is added
Water, ultrasonic disperse obtains graphene oxide dispersion, then constantly stirring under, toward above-mentioned dispersion liquid addition 0.5~
1.5g sodium borohydrides and 1~3g urea, and the mixed liquor that will be obtained is transferred in hydrothermal reaction kettle in 150~200 DEG C of reactions
12-18h, obtains sediment, washs, is drying to obtain the nitrogen co-doped Graphene of boron；
(2)TiO2The preparation of the nitrogen co-doped grapheme material of/boron：Taking 3-5g cetylamines, to be added to 1~2mL potassium chloride water-soluble
In liquid and 120-240mL absolute ethyl alcohols, ultrasound is then slowly added into 5-10mL isopropyl titanates and reacts 15-20 hours, filtering,
Washing, dry acquisition TiO2Presoma；Then take in step (1) the nitrogen co-doped 10~20g of Graphene of boron and add 60-100mL
Ethanol, ultrasound about 1h formed dispersion liquid, afterwards by above-mentioned TiO2Presoma is added to reactor simultaneously with the dispersion liquid of gained
In, 6-12h is reacted in 120-200 DEG C, finally centrifugation, washing are dried, roasting obtains final product the TiO2The nitrogen co-doped Graphene material of/boron
Material.
Wherein, the preparation method of the graphene oxide is：2~4g graphite powders are added to containing 2~4g sodium nitrate and
In the ice-water bath of 40~80mL concentrated sulfuric acids, then magnetic stirring about 30min, under stirring, adds 6~12g potassium permanganate,
And in stir about 1h under room temperature environment, afterwards to 180~240mL deionized waters are added in above-mentioned solution, in 90~95 DEG C of backflows
15~30min, is diluted, and add 30mLH after being cooled to room temperature with deionized water2O2, now solution be changed into yellowish-brown, will obtain
Solution suction filtration, and be washed with deionized to neutrality, finally by product in 60 DEG C of vacuum drying ovens drying graphite oxide
Alkene.
The mass concentration of the concentrated sulfuric acid is 98%, the H2O2Mass concentration be 30%.
The hydro-thermal reaction is carried out in homogeneous reactor.
The concentration of the potassium chloride is 0.05-0.15mol/L.
The roasting is to be calcined 3-5h at 350-450 DEG C.
In addition, the present invention is also claimed the preparation-obtained TiO of preparation method of the composite nano materials2/ boron nitrogen
Codope graphene composite nano material.
The present invention is also claimed the TiO2The application of the nitrogen co-doped graphene composite nano material of/boron, the material
It is applied to the fields such as photocatalytic degradation pollution dirt, photolysis water hydrogen.
Technique effect of the invention is：(1) preparation method of the present invention realizes the controlledly synthesis of composite, and the present invention is first
First under hydrothermal conditions using urea as nitrogen source, with sodium borohydride as boron source and reducing agent, by the reduction of graphene oxide and mix
It is miscellaneous at the same realize；Secondly, the complex method of titanium dioxide of the present invention and doped graphene effectively prevent Graphene and titanium dioxide
The shortcoming that titanium is easily reunited, increased effective contact area of titanium dioxide and graphene nanometer sheet.
(2) the dual modified effect that one aspect of the present invention passes through B, N, has conduction higher compared to the Graphene of undoped p
Property, bigger area load free charge density and doping while can effectively by the fault of construction of graphene oxide
Repaired, so as to form optical property and the doped graphene having good stability；On the other hand, the present invention is by by titanium dioxide
Coupled with both Graphenes of doping, produced cooperative compensating effect, and light induced electron will be transmitted to the energy band of Graphene
On, so as to reduce the recombination rate of hole and electronics, also cause that the forbidden band of titanium dioxide narrows, photoresponse scope is extended, so that
Photocatalysis performance greatly is improved, prepared composite property is very excellent.
Brief description of the drawings
Fig. 1 schemes for the SEM of the composite nano materials of the embodiment of the present invention 1.
Fig. 2 be the embodiment of the present invention 1 and composite nano materials prepared by comparative example 1-2 under light application time to methyl orange
Photocatalytic degradation curve comparison figure.
Specific embodiment
Technical scheme is further elaborated with reference to embodiment：
Embodiment 1
A kind of preparation method of graphene composite nano material, specifically includes following steps：
(1) preparation of the nitrogen co-doped Graphene of boron：15g graphene oxides are weighed, the deionized water of 30mL, ultrasound point is added
Dissipate obtain graphene oxide dispersion, then constantly stirring under, toward above-mentioned dispersion liquid addition 1.0g sodium borohydrides and
2g urea, and the mixed liquor that will be obtained is transferred in hydrothermal reaction kettle and reacts 16h in 180 DEG C, obtains sediment, washing, drying are
Obtain the nitrogen co-doped Graphene of boron；
(2)TiO2The preparation of the nitrogen co-doped grapheme material of/boron：Take 4g cetylamines and be added to 1.5mL concentration for 0.1mol/
In L potassium chloride solutions and 160mL absolute ethyl alcohols, ultrasound is then slowly added into 8mL isopropyl titanates and reacts 18 hours, filtering,
Washing, dry acquisition TiO2Presoma；Then take the nitrogen co-doped Graphene 16g of boron in step (1) and add the ethanol of 80mL, surpass
Sound about 1h forms dispersion liquid, afterwards by above-mentioned TiO2Presoma is added in reactor simultaneously with the dispersion liquid of gained, in 170 DEG C
Reaction 8h, is finally centrifuged, washing is dried, 4h is calcined at 400 DEG C obtains final product the TiO2The nitrogen co-doped grapheme material of/boron.
Embodiment 2
A kind of preparation method of graphene composite nano material, specifically includes following steps：
(1) preparation of the nitrogen co-doped Graphene of boron：10g graphene oxides are weighed, the deionized water of 20mL, ultrasound point is added
Dissipate obtain graphene oxide dispersion, then constantly stirring under, toward above-mentioned dispersion liquid addition 0.5g sodium borohydrides and
1g urea, and the mixed liquor that will be obtained is transferred in hydrothermal reaction kettle and reacts 18h in 150 DEG C, obtains sediment, washing, drying are
Obtain the nitrogen co-doped Graphene of boron；
(2)TiO2The preparation of the nitrogen co-doped grapheme material of/boron：Take 3g cetylamines and be added to 1mL concentration for 0.15mol/L
In potassium chloride solution and 120mL absolute ethyl alcohols, ultrasound is then slowly added into 5mL isopropyl titanates and reacts 15 hours, filtering,
Washing, dry acquisition TiO2Presoma；Then take the nitrogen co-doped Graphene 10g of boron in step (1) and add the ethanol of 60mL, surpass
Sound about 1h forms dispersion liquid, afterwards by above-mentioned TiO2Presoma is added in reactor simultaneously with the dispersion liquid of gained, in 120 DEG C
Reaction 12h, is finally centrifuged, washing is dried, 5h is calcined at 350 DEG C obtains final product the TiO2The nitrogen co-doped grapheme material of/boron.
Embodiment 3
A kind of preparation method of graphene composite nano material, specifically includes following steps：
(1) preparation of the nitrogen co-doped Graphene of boron：20g graphene oxides are weighed, the deionized water of 40mL, ultrasound point is added
Dissipate and obtain graphene oxide dispersion, then under constantly stirring, 1.5g sodium borohydrides and 1 are added toward above-mentioned dispersion liquid
~3g urea, and the mixed liquor that will be obtained is transferred in hydrothermal reaction kettle and reacts 12h in 200 DEG C, obtains sediment, washing, dries
Obtain final product the nitrogen co-doped Graphene of boron；
(2)TiO2The preparation of the nitrogen co-doped grapheme material of/boron：Take 3-5g cetylamines and be added to 2mL concentration and be
In 0.05mol/L potassium chloride solutions and 240mL absolute ethyl alcohols, ultrasound is then slowly added into the reaction 20 of 0mL isopropyl titanates small
When, filtering, washing, dry acquisition TiO2Presoma；Then take in step (1) the nitrogen co-doped Graphene 20g of boron and add 100mL
Ethanol, ultrasound about 1h formed dispersion liquid, afterwards by above-mentioned TiO2Presoma is added to reactor simultaneously with the dispersion liquid of gained
In, 6h are reacted in 200 DEG C, finally it is centrifuged, washing is dried, 3h is calcined at 450 DEG C obtains final product the TiO2The nitrogen co-doped Graphene of/boron
Material.
Embodiment 4
A kind of preparation method of graphene composite nano material, specifically includes following steps：
(1) preparation of the nitrogen co-doped Graphene of boron：12g graphene oxides are weighed, the deionized water of 25mL, ultrasound point is added
Dissipate obtain graphene oxide dispersion, then constantly stirring under, toward above-mentioned dispersion liquid addition 0.8g sodium borohydrides and
1.5g urea, and the mixed liquor that will be obtained is transferred in hydrothermal reaction kettle and reacts 16h in 160 DEG C, obtains sediment, washing, dries
Obtain final product the nitrogen co-doped Graphene of boron；
(2)TiO2The preparation of the nitrogen co-doped grapheme material of/boron：Take 3.5g cetylamines and be added to 1.2mL concentration and be
In 0.08mol/L potassium chloride solutions and 170mL absolute ethyl alcohols, ultrasound is then slowly added into the reaction 16 of 7mL isopropyl titanates small
When, filtering, washing, dry acquisition TiO2Presoma；Then take in step (1) the nitrogen co-doped Graphene 13g of boron and add 70mL
Ethanol, ultrasound about 1h formed dispersion liquid, afterwards by above-mentioned TiO2Presoma is added to reactor simultaneously with the dispersion liquid of gained
In, 9h are reacted in 150 DEG C, finally it is centrifuged, washing is dried, 4h is calcined at 380 DEG C obtains final product the TiO2The nitrogen co-doped Graphene of/boron
Material.
Embodiment 5
The embodiment of the present invention 1-4 and preparation method of graphene oxide is specially described in following comparative example 1-2：By 3g stones
Ink powder is added in the ice-water bath containing 3g sodium nitrate and the concentrated sulfuric acid that 60mL mass concentrations are 98%, and then magnetic stirring is about
30min, under stirring, adds 8g potassium permanganate, and in stir about 1h under room temperature environment, added in above-mentioned solution afterwards
200mL deionized waters, flow back 20min in 95 DEG C, is cooled to after room temperature and is diluted with deionized water, and adds the 30mL mass concentrations to be
30% H2O2, now solution be changed into yellowish-brown, the solution suction filtration that will be obtained, and being washed with deionized to neutrality will finally be produced
Product drying graphene oxide in 60 DEG C of vacuum drying ovens.
Comparative example 1
A kind of preparation method of graphene composite nano material, specifically includes following steps：
(1) preparation of boron doped graphene：15g graphene oxides are weighed, the deionized water of 30mL is added, ultrasonic disperse is obtained
To graphene oxide dispersion, then under constantly stirring, 1.0g sodium borohydrides are added toward above-mentioned dispersion liquid, and will obtain
Mixed liquor be transferred in hydrothermal reaction kettle and react 16h in 180 DEG C, obtain sediment, wash, be drying to obtain boron doped graphene；
(2)TiO2The preparation of/boron doped graphene material：Take 4g cetylamines and be added to 1.5mL concentration for 0.1mol/L chlorine
Change in aqueous solutions of potassium and 160mL absolute ethyl alcohols, ultrasound is then slowly added into 8mL isopropyl titanates and reacts 18 hours, filters, washes
Wash, dry acquisition TiO2Presoma；Then take boron doped graphene 16g in step (1) and add the ethanol of 80mL, ultrasound about 1h
Dispersion liquid is formed, afterwards by above-mentioned TiO2Presoma is added in reactor simultaneously with the dispersion liquid of gained, in 170 DEG C of reactions
8h, is finally centrifuged, washing is dried, 4h is calcined at 400 DEG C obtains final product the TiO2/ boron doped graphene material.
Comparative example 2
A kind of preparation method of graphene composite nano material, specifically includes following steps：
(1) preparation of nitrogen-doped graphene：15g graphene oxides are weighed, the deionized water of 30mL is added, ultrasonic disperse is obtained
To graphene oxide dispersion, then under constantly stirring, 2g urea, and the mixing that will be obtained are added toward above-mentioned dispersion liquid
Liquid reacts 16h in being transferred to hydrothermal reaction kettle in 180 DEG C, obtains sediment, washs, is drying to obtain nitrogen-doped graphene；
(2)TiO2The preparation of/nitrogen-doped graphene material：Take 4g cetylamines and be added to 1.5mL concentration for 0.1mol/L chlorine
Change in aqueous solutions of potassium and 160mL absolute ethyl alcohols, ultrasound is then slowly added into 8mL isopropyl titanates and reacts 18 hours, filters, washes
Wash, dry acquisition TiO2Presoma；Then take nitrogen-doped graphene 16g in step (1) and add the ethanol of 80mL, ultrasound about 1h
Dispersion liquid is formed, afterwards by above-mentioned TiO2Presoma is added in reactor simultaneously with the dispersion liquid of gained, in 170 DEG C of reactions
8h, is finally centrifuged, washing is dried, 4h is calcined at 400 DEG C obtains final product the TiO2/ nitrogen-doped graphene material.
Photocatalysis performance evaluation experimental of the present invention：
Composite nano materials prepared by the embodiment of the present invention 1 and comparative example 1-2 are applied to photocatalyst for degrading
The 1 × 10 of 100mL-5M MO (methyl orange) solution：Above-mentioned solution is taken first in quartz glass reactor, and adds 10mg light to urge
Change nano composite material, be subsequently placed in dark place and stir 30 minutes to reach adsorption/desorption balance.Then at once by the atmosphere lamp of 300W
It is positioned over and is irradiated away from reactor lOcm, in dark reaction and photoreaction stage, is all sampled according to certain period of time and be centrifuged, test
The absorbance of methyl orange in its solution, so as to draw out the degradation rate for changing over time.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
Modified with to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in of the invention
Within protection domain.
Claims (8)
1. a kind of preparation method of graphene composite nano material, it is characterised in that the composite nano materials are TiO2/ boron nitrogen
Codope grapheme material, the preparation method of the material specifically includes following steps：
(1) preparation of the nitrogen co-doped Graphene of boron：10~20g graphene oxides are weighed, the deionized water of 20~40mL is added, surpassed
Sound dispersion obtains graphene oxide dispersion, then under constantly stirring, 0.5~1.5g boron hydrogen is added toward above-mentioned dispersion liquid
Change sodium and 1~3g urea, and the mixed liquor that will be obtained is transferred in hydrothermal reaction kettle and reacts 12-18h in 150~200 DEG C, obtains
Sediment, washs, is drying to obtain the nitrogen co-doped Graphene of boron；
(2)TiO2The preparation of the nitrogen co-doped grapheme material of/boron：Take 3-5g cetylamines be added to 1~2mL potassium chloride solutions and
In 120-240mL absolute ethyl alcohols, ultrasound is then slowly added into 5-10mL isopropyl titanates and reacts 15-20 hours, filter, wash,
Dry and obtain TiO2Presoma；Then take the nitrogen co-doped 10~20g of Graphene of boron in step (1) and add the second of 60-100mL
Alcohol, ultrasound about 1h forms dispersion liquid, afterwards by above-mentioned TiO2Presoma is added in reactor simultaneously with the dispersion liquid of gained, in
120-200 DEG C of reaction 6-12h, finally centrifugation, washing are dried, roasting obtains final product the TiO2The nitrogen co-doped grapheme material of/boron.
2. the preparation method of composite nano materials according to claim 1, it is characterised in that the preparation of the graphene oxide
Method is：2~4g graphite powders are added in the ice-water bath containing 2~4g sodium nitrate and 40~80mL concentrated sulfuric acids, then magnetic
Stir about 30min, under stirring, adds 6~12g potassium permanganate, and in stir about 1h under room temperature environment, afterwards to above-mentioned
180~240mL deionized waters are added in solution, flow back 15~30min in 90~95 DEG C, use deionized water dilute after being cooled to room temperature
Release, and add 30mLH2O2, now solution be changed into yellowish-brown, the solution suction filtration that will be obtained, and being washed with deionized to neutrality,
Finally by product in 60 DEG C of vacuum drying ovens drying graphene oxide.
3. the preparation method of composite nano materials according to claim 2, it is characterised in that the mass concentration of the concentrated sulfuric acid
It is 98%, the H2O2Mass concentration be 30%.
4. according to claim any one of 3-4 composite nano materials preparation method, it is characterised in that the hydro-thermal reaction
It is to be carried out in homogeneous reactor.
5. according to claim any one of 4-5 composite nano materials preparation method, it is characterised in that the potassium chloride
Concentration is 0.05-0.15mol/L.
6. the preparation method of composite nano materials according to claim 5, it is characterised in that the roasting is in 350-450
3-5h is calcined at DEG C.
7. according to claim any one of 1-6 composite nano materials the preparation-obtained TiO of preparation method2/ boron nitrogen is co-doped with
Miscellaneous graphene composite nano material.
8. TiO described in a kind of claim 72The application of the nitrogen co-doped graphene composite nano material of/boron, it is characterised in that described
Materials application is in fields such as photocatalytic pollutant degradation, photolysis water hydrogens.
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| CN111841614A (en) * | 2020-08-18 | 2020-10-30 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
| CN111841614B (en) * | 2020-08-18 | 2021-10-29 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
| CN115403853A (en) * | 2022-09-30 | 2022-11-29 | 万华化学（宁波）有限公司 | Composite material for shielding direct/alternating current high-voltage cable and preparation method thereof |
| CN115403853B (en) * | 2022-09-30 | 2024-04-09 | 万华化学（宁波）有限公司 | Composite material for shielding direct-current/alternating-current high-voltage cable and preparation method thereof |
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