CN108772094A - A kind of nitridation carbon quantum dot/TiO 2 sol and preparation method thereof - Google Patents
A kind of nitridation carbon quantum dot/TiO 2 sol and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000000908 ammonium hydroxide Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002096 quantum dot Substances 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 241000370738 Chlorion Species 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 27
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 description 18
- 230000000694 effects Effects 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 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 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002023 wood 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
A kind of nitridation carbon quantum dot/TiO 2 sol, the TiO 2 sol contain titania, and 2 θ of angle of diffraction is 8.78o±0.2°、26.66o±0.2°、38.80o±0.2°、46.75o±0.2°、58.07oThere is diffraction maximum at ± 0.2 °.Composite titania material its catalytic effect obtained by a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol of the present invention significantly improves, at present 20mg commercial titanium dioxides P25 on the market（It is purchased from German Degussa）To 100mL methyl oranges（18mg/L）2 hours degradation rates are 34.4%, and the degradation rate of 20mg products of the present invention has reached 87.2% under the same conditions, improves 2.53 times, show that electron-hole is easily isolated by photoelectric current and impedance analysis test, quantum yield is high, and preparation process is not introduced into any mordant reagent, and preparation method is environmentally friendly, there is no second to pollute, product stability is good, in being placed at room temperature for 8 months, still has stronger catalytic effect, preparation process simple possible, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to carbonitride/composite titania materials, and in particular to a kind of nitridation carbon quantum dot/titanium dioxide is molten
Glue new material and preparation method thereof.
Background technology
With the continuous growth of population, economic and industry rapid development, the increasingly exacerbation of various environmental problems.For ring
The improvement of border problem is very urgent.In recent years, the research of environmental improvement is always one of the topic of scientific circles' hot topic.And wherein
Photocatalysis technology due to its can efficiently degradation of contaminant, applied in many fields, such as environmental pollution improvement, medical treatment
The fields such as health, therefore cause prodigious concern.
In many photochemical catalysts, TiO2It is most promising photochemical catalyst.It has nontoxic, chemical property stabilization,
And the features such as no selective to contaminant degradation.But due to TiO2The electron-hole of generation is easy to happen compound, quantum
Low yield results in and utilizes reduction, the catalytic activity of limitation to sunlight.
g-C3N4It is good with thermal stability, there is suitable conduction band valence band location（Band gap width is 2.7eV）The advantages that, it is close several
Nian Lai, g-C3N4Material shows prodigious application prospect, such as photolysis water hydrogen system and photochemical catalyst in terms of environment.
But g-C3N4Insufficient to the response of light, especially the high recombination rate of photo-generate electron-hole pair inhibits the catalytic activity of light.Cause
This, needs to develop mode appropriate and widens g-C3N4Visible light-responded range and promote separation of charge efficiency, and then improve its light
Catalytic activity.
Just at present apparently, there is a problem of in known composite titania material preparation process larger.First, preparing
Method is cumbersome, needs high temperature and high pressure environment, and energy consumption is larger, is not easy to form industrialized production, and traditional preparation methods can have soda acid
Pollution, secondary pollution is be easy to cause to environment.Second, the more particles of the composite titania material prepared are larger, catalytic activity
It is relatively low.Third, preparation process TiO 2 sol is easy reunion, bad dispersibility with carbonitride complex systems.Fourth, preparing
Product quantum low yield, manufacturing cost is high, just apparently yet there are no at present ripe about nitridation carbon quantum dot/titanium dioxide
The report of the preparation method of composite material.
Invention content
Present invention aims at provide a kind of nitridation that photocatalytic activity is high carbon quantum dot/TiO 2 sol composite wood
Material.
Another object of the present invention is to provide above-mentioned height monodisperse nitridation carbon quantum dot/TiO 2 sol composite material
Preparation method.
The object of the invention is achieved through the following technical solutions：
A kind of nitridation carbon quantum dot/TiO 2 sol, it is characterised in that：The TiO 2 sol contains titanium dioxide crystalline substance
Grain, the titania are 8.78 in 2 θ of angle of diffractiono±0.2°、26.66o±0.2°、38.80o±0.2°、46.75o
±0.2°、58.07oThere is diffraction maximum at ± 0.2 °.Inventor has found in R&D process, the titanium dioxide containing above-mentioned specific crystal formation
Colloidal sol and carbonitride complex systems do not reunite, good dispersion, and photocatalytic activity is high.
A kind of preparation method of nitridation carbon quantum dot/TiO 2 sol, which is characterized in that it is with melamine, ammonia
Water, titanium tetrachloride, absolute ethyl alcohol, deionized water, cutting agent are raw material, pass through g-C respectively3N4The preparation of powder, g-C3N4Quantum
Point the preparation of liquid, the preparation of mixed solution, pH adjust, washing, back flow reaction and etc. be made；The wherein described cutting agent was
The mixed liquor of sodium oxide molybdena or sodium peroxide and hydrogen peroxide.
Further, a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol, which is characterized in that the g-C3N4Powder
The preparation at end is that melamine is placed in Muffle furnace, and 500 ~ 700 DEG C of calcination temperature is arranged, and keeps the temperature 1 ~ 4h, and natural cooling takes
Go out, grinding is to get g-C in agate mortar3N4Powder.
Further, a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol, which is characterized in that the g-C3N4Amount
The preparation of son point liquid is by g-C3N4Powder is mixed with ammonium hydroxide and is positioned in ptfe autoclave, and temperature 170 ~ 190 is arranged
DEG C hydro-thermal reaction 10 ~ 12 hours is carried out, taking-up is placed in Rotary Evaporators, and rotary evaporation falls ammonium hydroxide, and ultrasound obtains g-C3N4Quantum
Point liquid；The wherein described ammonia concn is 25% ~ 28%, the g-C3N4The mass volume ratio of powder and ammonium hydroxide is 1：200 ~ 300,
Supersonic frequency is 20 ~ 30KHz, and ultrasonic time is 1 ~ 3h.
Further, a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol, which is characterized in that the mixing is molten
The preparation of liquid is by titanium tetrachloride, absolute ethyl alcohol, g-C3N4Quantum dot liquid and deionized water mixing stir and evenly mix to get mixing
Solution；The wherein described titanium tetrachloride：g-C3N4Quantum dot liquid：Absolute ethyl alcohol：The volume ratio of deionized water is 1~5：0.1~4：
3~5：3~30；The speed of agitator is 300 ~ 1000r/min, and mixing time is 10 ~ 30min.
Further, a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol, which is characterized in that the pH is adjusted
It is to adjust mixed solution pH as 6.5 ~ 7.5 to mixed solution and dripping ammonium hydroxide to get white precipitate；The ammoniacal liquor mass concentration
It is 25 ~ 28%.
Further, a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol, which is characterized in that the washing is
Extracting waste precipitates, and is washed 5 ~ 8 times with the deionized water of 10 ~ 15 times of quality of white precipitate, until cleaning solution chlorion inspection is nothing,
?.
Further, a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol, which is characterized in that the reflux is anti-
It should be the white precipitate after washing, cutting agent, deionized water, condensing reflux 3 ~ 4 at a temperature of being subsequently placed in 90 ~ 120 DEG C is added
Hour is to get nitridation charcoal quantum dot/TiO 2 sol；The mass concentration of the wherein described hydrogen peroxide is 30%, the cutting agent,
Deionized water and the volume ratio of titanium tetrachloride are 8~12：100~150：1~5；The cutting agent is preferably hydrogen peroxide and mistake
The mixed liquor of sodium oxide molybdena, its ratio be 8 ~ 9：2~1.
In order to realize the XRD tests of TiO 2 sol, also need to be placed in TiO 2 sol obtained above to freeze to do
In dry machine, -45 DEG C of temperature is set, drying time 20h obtains titanium dioxide solids crystal grain, you can carry out XRD tests.
The present invention has following advantageous effect：
Contained titania catalytic activity is strong in TiO 2 sol of the present invention, to each dyestuff, organic pollution, excrement etc.
Larger Photocatalytic activity, especially especially strong to the degrading activity of methyl orange is all had, 20mg titanias can make
The degradation rate that the methyl orange solution 100ml of a concentration of 18mg/L degrades 3 hours is up to 80.6%, and degradation time is short, efficient.This
Its catalytic effect of invention nitridation carbon quantum dot/TiO 2 sol composite material significantly improves, 20mg commercializations two on the market at present
Titanium oxide P25（It is purchased from German Degussa）To 100mL methyl oranges（18mg/L）2 hours degradation rates are 34.4%, in the same terms
The degradation rate of lower 20mg products of the present invention has reached 87.2%, improves 2.53 times, is shown by photoelectric current and impedance analysis test
Electron-hole is easily isolated, and quantum yield is high.The present invention is prepared using one kettle way, be made the monodispersed zero dimension material of height and
The composite material of one-dimensional titanium dioxide；It is not introduced into any mordant reagent in preparation process, preparation method is environmentally friendly,
There is no second to pollute, and product stability is good, in being placed at room temperature for 8 months, still has stronger catalytic effect, preparation process letter
It is single feasible, it is easy to accomplish industrialized production.
Description of the drawings
Fig. 1 is the TEM figures for nitrogenizing carbon quantum dot/composite titania material.
Fig. 2 is the UV-Vis figures for nitrogenizing carbon quantum dot/composite titania material.
Fig. 3 is the impedance diagram for nitrogenizing carbon quantum dot/composite titania material.
Fig. 4 is the degradation rate figure to methyl orange for nitrogenizing carbon quantum dot/composite titania material.
Fig. 5 is the X-ray powder diffraction figure of titanium dioxide crystal form contained by TiO 2 sol.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, person skilled in art can
To make some nonessential modifications and adaptations to the present invention according to aforementioned present invention content.
Embodiment 1：A kind of preparation method of nitridation carbon quantum dot/titanium dioxide
1. nitrogenizing carbon quantum dot（g-CNQDS）Preparation
It is presoma by the melamine of 5g, is fired to 600 DEG C by Muffle furnace, keeps the temperature 3 hours, natural cooling is taken out, grinding
It crosses and grinds to obtain powdered g-C3N4.By powdered g-C3N4The ammonium hydroxide for being 26% with volume fraction is uniformly mixed, the g-C3N4Powder
The mass volume ratio of end and ammonium hydroxide is 1：250, after be placed in ptfe autoclave hydro-thermal reaction under conditions of 180 DEG C
11h, rotary evaporation falls ammonium hydroxide after taking-up, and ultrasound obtains albescent g-C3N4 quantum dots liquid, and supersonic frequency 25KHz surpasses
Sound time 2 h.
2. nitrogenizing the preparation of carbon quantum dot/TiO 2 sol
Under 0 DEG C of cryogenic conditions, 3ml absolute ethyl alcohols, 1ml carbonitrides quantum dot solution and 3ml is added in 1ml titanium tetrachlorides and is gone
The in the mixed solvent of ionized water composition, mixed solution is stirred to get in rotating speed 600r/min, mixing time 20min；It is molten mixing
The pH value for the ammonium hydroxide adjusting mixed solution that volumetric concentration is 27% is added dropwise in liquid to 7.0, obtains white precipitate；By white precipitate from
The heart is simultaneously washed 6 times with the deionized water of 13 times of white precipitate amounts, until not containing chlorion；In white precipitate after washing
Mixed solution, the deionized water of hydrogen peroxide and sodium peroxide composition that mass concentration is 30% is added, it is 110 to be subsequently placed at temperature
Condensing reflux 3h is carried out under the conditions of DEG C, obtains nitridation carbon quantum dot/TiO 2 sol.Described 30% hydrogen peroxide and peroxidating
The volume ratio of mixed solution, deionized water and titanium tetrachloride that sodium forms is 9：120：2；The hydrogen peroxide and sodium peroxide quality
Than being 8 for mass ratio:1.
In order to realize the XRD tests of nitridation carbon quantum dot/TiO 2 sol, also need nitridation carbon quantum obtained above
Point/TiO 2 sol is placed in freeze drier, and -45 DEG C of temperature is arranged, and drying time 20h obtains titanium dioxide solids
Crystal grain, you can carry out XRD tests.
Nitridation carbon quantum dot/titanium dioxide solids obtained by embodiment 1 are done into XRD tests：
Radiation source is Cu cakes, and wavelength is 1.54060 m, and scanning angle is 20 ° ~ 80 °, voltage 40kV, electric current 40mA, scanning
Speed is 2.4 °/min, the results showed that：2 θ is 8.78 for its X angle of diffractiono±0.2°、26.66o±0.2°、38.80o±0.2°、
46.75o±0.2°、58.07o± 0.2 ° etc. has rank to penetrate peak.Because the amount of nitridation carbon quantum dot is very little, and under cryogenic conditions
Reason, too weak etc. reasons of peak shape, so can't see the peak of nitridation carbon quantum dot, detection of diffracted peak is several with titania
It is identical.
Experiment 1：Product obtained by Example 1 carries out photocatalysis effect experiment.
Product made from Example 1（20mg）100ml methyl orange solutions (18mg/L) are added to, dark place preserves 2 hours,
It opens the light（The use of light source is high-pressure sodium lamp）, degradation efficiency is measured every half an hour.Experimental data is as shown in figure 4, as seen from the figure, and 2
After hour, this product is 87.2% to the degradation rate of methyl blue.Separately take 20mg commercial titanium dioxide P25 on the market（It is solid to be purchased from German moral
Match）By the experimental method of embodiment 1, photocatalysis effect experiment is carried out to methyl orange solution, the experimental results showed that, commercially available commercial two
Titanium oxide P25 is to 100mL methyl oranges（18mg/L）Degradation rate be 34.4%, the more commercially available quotient of product made from the embodiment of the present invention 1
2.35 times are improved to methyl orange degradation rate with product, shows the present invention to methyl orange degradation excellent effect.
Experiment 2：Product obtained by Example 1 carries out stability test.
After taking this product to place 8 months in room conditions, product remain on stablize and it is transparent, after measured, catalysis effect
Fruit is still good, therefore this product has good stability.
A kind of preparation method of nitridation carbon quantum dot/titanium dioxide of embodiment 2
1. nitrogenizing carbon quantum dot（g-CNQDS）Preparation
It is presoma by the melamine of 5g, is fired to 500 DEG C by Muffle furnace, keeps the temperature 1 hour, natural cooling is taken out, grinding
It crosses and grinds to obtain powdered g-C3N4.By powdered g-C3N4The ammonium hydroxide for being 25% with volume fraction is uniformly mixed, the g-C3N4Powder
The mass volume ratio of end and ammonium hydroxide is 1：200, after be placed in ptfe autoclave hydro-thermal reaction under conditions of 170 DEG C
10h, rotary evaporation falls ammonium hydroxide after taking-up, and ultrasound obtains albescent g-C3N4 quantum dots liquid, and supersonic frequency 20KHz surpasses
1 hour sound time.
2. nitrogenizing the preparation of carbon quantum dot/TiO 2 sol
Under 0 DEG C of cryogenic conditions, 5ml absolute ethyl alcohols, 0.1ml carbonitrides quantum dot solution and 3ml is added in 1ml titanium tetrachlorides
The in the mixed solvent of deionized water composition, mixed solution is stirred to get in rotating speed 300r/min, mixing time 10min；It is mixing
The pH value for the ammonium hydroxide adjusting mixed solution that volumetric concentration is 25% is added dropwise in solution to 6.5, obtains white precipitate；By white precipitate
It centrifuges and is washed 5 times with the deionized water of 10 times of white precipitate amounts, until not containing chlorion；White precipitate after washing
Middle mixed solution, the deionized water that hydrogen peroxide and sodium peroxide composition that mass concentration is 30% is added, it is 90 to be subsequently placed at temperature
Condensing reflux 4h is carried out under the conditions of DEG C, obtains nitridation carbon quantum dot/two dimension TiO 2 sol.Described 30% hydrogen peroxide and mistake
The volume ratio of mixed solution, deionized water and titanium tetrachloride that sodium oxide molybdena forms is 8：100：1；The hydrogen peroxide and sodium peroxide
Mass ratio is that mass ratio is 8:2.
By the experimental method of embodiment 1, product made from embodiment 2 is subjected to product respectively and carries out photocatalysis effect experiment
And stability test, the experimental results showed that, this product photocatalysis effect is excellent, to methyl orange degradation excellent effect, product stability
Good, after this product places 8 months in room conditions, product, which remains on, to be stablized and transparent, and after measured, catalytic effect is still good
It is good, therefore this product has good stability.
Embodiment 3：A kind of preparation method of nitridation carbon quantum dot/titanium dioxide
1. nitrogenizing carbon quantum dot（g-CNQDS）Preparation
It is presoma by the melamine of 5g, is fired to 700 DEG C by Muffle furnace, keeps the temperature 1 hour, natural cooling is taken out, grinding
It crosses and grinds to obtain powdered g-C3N4.By powdered g-C3N4The ammonium hydroxide for being 28% with volume fraction is uniformly mixed, the g-C3N4Powder
The mass volume ratio of end and ammonium hydroxide is 1：300, after be placed in ptfe autoclave hydro-thermal reaction under conditions of 190 DEG C
12h, rotary evaporation falls ammonium hydroxide after taking-up, and ultrasound obtains albescent g-C3N4 quantum dots liquid, and supersonic frequency 30KHz surpasses
3 hours sound time.
2. nitrogenizing the preparation of carbon quantum dot/TiO 2 sol
Under 0 DEG C of cryogenic conditions, 5ml absolute ethyl alcohols, 4ml carbonitrides quantum dot solution and 30ml is added in 5ml titanium tetrachlorides
The in the mixed solvent of deionized water composition, mixed solution is stirred to get in rotating speed 1000r/min, mixing time 30min；It is mixing
The pH value for the ammonium hydroxide adjusting mixed solution that volumetric concentration is 28% is added dropwise in solution to 7.5, obtains white precipitate；By white precipitate
It centrifuges and is washed 8 times with the deionized water of 15 times of white precipitate amounts, until not containing chlorion；White precipitate after washing
Middle mixed solution, the deionized water that hydrogen peroxide and sodium peroxide composition that mass concentration is 30% is added, being subsequently placed at temperature is
Condensing reflux 3h is carried out under the conditions of 120 DEG C, obtains nitridation carbon quantum dot/two dimension TiO 2 sol.Described 30% hydrogen peroxide and
The volume ratio of mixed solution, deionized water and titanium tetrachloride that sodium peroxide forms is 12：150：5；The hydrogen peroxide and peroxide
It is 9 that change sodium mass ratio, which is mass ratio,:2.
By the experimental method of embodiment 1, product made from embodiment 3 is subjected to product respectively and carries out photocatalysis effect experiment
And stability test, the experimental results showed that, this product photocatalysis effect is excellent, to methyl orange degradation excellent effect, product stability
Good, after this product places 8 months in room conditions, product, which remains on, to be stablized and transparent, and after measured, catalytic effect is still good
It is good, therefore this product has good stability.
Claims (8)
1. a kind of nitridation carbon quantum dot/TiO 2 sol, it is characterised in that：The TiO 2 sol contains titanium dioxide crystalline substance
Grain, the titania are 8.78 in 2 θ of angle of diffractiono±0.2°、26.66o±0.2°、38.80o±0.2°、46.75o
±0.2°、58.07oThere is diffraction maximum at ± 0.2 °.
2. the preparation method of nitridation carbon quantum dot/TiO 2 sol as described in claim 1, which is characterized in that it is with three
Poly cyanamid, ammonium hydroxide, titanium tetrachloride, absolute ethyl alcohol, deionized water, cutting agent are raw material, pass through g-C respectively3N4The preparation of powder,
g-C3N4The preparation of quantum dot liquid, the preparation of mixed solution, pH adjust, washing, back flow reaction and etc. be made；It is wherein described
Cutting agent is the mixed liquor of sodium peroxide or sodium peroxide and hydrogen peroxide.
3. a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol as claimed in claim 2, which is characterized in that institute
State g-C3N4The preparation of powder is that melamine is placed in Muffle furnace, and 500 ~ 700 DEG C of calcination temperature is arranged, and keeps the temperature 1 ~ 4h, natural
It is cooling, it takes out, grinding is to get g-C in agate mortar3N4Powder.
4. a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol as claimed in claim 3, which is characterized in that institute
State g-C3N4The preparation of quantum dot liquid is by g-C3N4Powder is mixed with ammonium hydroxide and is positioned in ptfe autoclave, setting
170 ~ 190 DEG C of temperature carries out hydro-thermal reaction 10 ~ 12 hours, and taking-up is placed in Rotary Evaporators, and rotary evaporation falls ammonium hydroxide, ultrasonic to obtain
To g-C3N4Quantum dot liquid；The wherein described ammonia concn is 25% ~ 28%, the g-C3N4The mass volume ratio of powder and ammonium hydroxide
It is 1：200 ~ 300, supersonic frequency is 20 ~ 30KHz, and ultrasonic time is 1 ~ 3h.
5. a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol as claimed in claim 4, which is characterized in that institute
The preparation for stating mixed solution is by titanium tetrachloride, absolute ethyl alcohol, g-C3N4Quantum dot liquid and deionized water mixing stir and evenly mix,
Up to mixed solution；The wherein described titanium tetrachloride：g-C3N4Quantum dot liquid：Absolute ethyl alcohol：The volume ratio of deionized water be 1~
5：0.1~4：3~5：3~30；The speed of agitator is 300 ~ 1000r/min, and mixing time is 10 ~ 30min.
6. a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol as claimed in claim 5, which is characterized in that institute
It is to adjust mixed solution pH as 6.5 ~ 7.5 to mixed solution and dripping ammonium hydroxide to get white precipitate to state pH adjustings；The ammonium hydroxide
Mass concentration is 25 ~ 28%.
7. a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol as claimed in claim 6, which is characterized in that institute
It is extracting waste precipitation to state washing, is washed 5 ~ 8 times with the deionized water of 10 ~ 15 times of quality of white precipitate, until cleaning solution chlorion
Check to be nothing, you can.
8. a kind of preparation method of nitridation carbon quantum dot/TiO 2 sol as claimed in claim 7, which is characterized in that institute
It is that cutting agent, deionized water is added in the white precipitate after washing to state back flow reaction, is condensed at a temperature of being subsequently placed in 90 ~ 120 DEG C
3 ~ 4 hours are flowed back to get nitridation charcoal quantum dot/TiO 2 sol；The mass concentration of the wherein described hydrogen peroxide is 30%, described
The volume ratio of cutting agent, deionized water and titanium tetrachloride is 8~12：100~150：1~5；The cutting agent is preferably double
The mixed liquor of oxygen water and sodium peroxide, its ratio be 8 ~ 9：2~1.
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