CN106512975A - Preparation method and application of sulfur-doped titanium dioxide-graphene aerogel composite material - Google Patents
Preparation method and application of sulfur-doped titanium dioxide-graphene aerogel composite material Download PDFInfo
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- CN106512975A CN106512975A CN201610912427.8A CN201610912427A CN106512975A CN 106512975 A CN106512975 A CN 106512975A CN 201610912427 A CN201610912427 A CN 201610912427A CN 106512975 A CN106512975 A CN 106512975A
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- titanium dioxide
- graphene aerogel
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- 239000004964 aerogel Substances 0.000 title claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 34
- 239000010936 titanium Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- 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 claims abstract description 27
- 229940012189 methyl orange Drugs 0.000 claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 claims abstract description 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 55
- 229910052717 sulfur Inorganic materials 0.000 claims description 53
- 239000011593 sulfur Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 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 claims description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 17
- 239000012498 ultrapure water Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims 1
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004042 decolorization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to preparation and application of a sulfur-doped titanium dioxide-graphene aerogel composite material. The preparation includes the following steps that sulfur-doped titanium dioxide is prepared, graphene aerogel is prepared, the sulfur-doped titanium dioxide-graphene aerogel composite material is prepared, and the composite material is applied to degradation of general pollutant methyl orange of water. The preparation and application of the sulfur-doped titanium dioxide-graphene aerogel composite material have the beneficial effects that a preparation method of the sulfur-doped titanium dioxide-graphene aerogel composite material is simple, the degradation speed of the sulfur-doped titanium dioxide-graphene aerogel composite material on methyl orange and other organic molecules is high, and the composite material is easy to recycle and is free of pollution to the environment.
Description
Technical field
The present invention relates to a kind of preparation method and application of sulfur doping titanium dioxide-graphene aerogel composite, category
In wastewater treatment and materials synthesis field.
Technical background
With developing rapidly for China's industrial or agricultural, water pollution problem is increasingly serious.Wherein, persistence organic pollutant is made
For a kind of typical environmental contaminants, with high toxicity, extended residual, fat-solubility feature.Due to can be in food chain
Middle enrichment transmission, persistence organic pollutant have serious harm to health and ecological environment.Methyl orange is typical
Persistence organic pollutant, and widely use in industries such as printing and dyeing, textiles.The present invention chooses methyl orange as using right
As with certain representativeness.
Methyl orange is a kind of azo dyes, and the aqueous solution is in orange, if untreated in industrial production be just discharged in water body,
Not only make coloured water body hinder the absorption and reflection of light in water, and methyl orange itself is poisonous, this is moved to contaminated water body periphery
The existence of plant causes serious threat.
The features such as titanium dioxide has nontoxic, stable chemical nature, low price and does not produce secondary pollution, it is considered to be
Most there is the photochemical catalyst of application prospect.But the wider energy gap of titanium dioxide and low conversion quantum efficiency limit its reality
Using.Carry out to titanium dioxide that sulfur doping is modified can to improve the problems referred to above.
3D graphene aerogels have larger specific surface area, can serve as carrier and adsorbent, and the material has good
Good electric conductivity and mechanical strength.It is great that these excellent characteristics cause 3D graphene aerogels to have in terms of sewage disposal
Application potential.The present invention is supported on sulfur doping titanium dioxide on 3D graphene aerogels, not only can be by Graphene airsetting
The electric conductivity of glue separates light induced electron and hole, and graphene aerogel also causes dyestuff in catalysis to the adsorption capacity of dyestuff
It is enriched with material, improves catalytic efficiency.Further, since graphene aerogel has hydrophobicity, the composite is also beneficial to
The separation of catalyst and water body.
The content of the invention
It is to provide a kind of preparation side of sulfur doping titanium dioxide-graphene aerogel composite that the purpose of the present invention is
Method and application, and be conducive to industrial use.
A kind of preparation and application of sulfur doping titanium dioxide-graphene aerogel composite of the present invention, including with
Lower step：
A, prepare sulfur doping titanium dioxide：Titanium tetrachloride is dissolved in into ultra-pure water, then in its solution plus thiocarbamide and poly- second
Glycol (600).Mixed liquor is transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reaction 3h.By the white solid of precipitation precipitate from
The heart is separated and is washed each 3 times with absolute ethyl alcohol and ultra-pure water alternating, is put into oven for drying, is obtained sulfur doping titanium dioxide.
B, prepare graphite oxide：Potassium permanganate and graphite powder is weighed, stirring, standby is placed in beaker.In there-necked flask
The concentrated sulfuric acid, phosphoric acid is sequentially added, the mixture of potassium permanganate and graphite powder is added slowly with stirring.48 DEG C of design temperature, water
Bath reaction 12h.After reaction terminates, prepare 1000mL beakers, add ice cube and hydrogen peroxide, pour reactant liquor into 1000mL beakers
In, stand 12h.Solution is layered, and removes a layer yellow, is centrifuged.Ultra-pure water is added repeatedly, stirring, centrifugation, until during solution is near
Property.Solution is poured in culture dish, 48h is stood, is obtained graphite oxide.
C, prepare sulfur doping titanium dioxide-graphene aerogel composite：Weigh sulfur doping titanium dioxide obtained in step a
Graphite oxide obtained in titanium and step b, is scattered in ultra-pure water, and ultrasound makes to be uniformly dispersed.Dispersion liquid is transferred to into 100mL hydro-thermals
In reactor, 180 DEG C of reaction 12h.After reaction terminates, product is taken out, the freeze-drying 24h at -45 DEG C obtains sulfur doping dioxy
Change titanium-graphene aerogel composite.
D, composite are applied to the methyl orange in degradation water：Certain density methyl orange solution is prepared, is obtained with step c
Sulfur doping titanium dioxide-graphene aerogel composite degradation water in methyl orange, while use UV, visible light light splitting light
The characteristic absorption peak intensity of degree meter detection methyl orange solution.When characteristic absorption peak disappears, that is, illustrate the methyl orange drop in solution
Solution is complete, records the time used by degraded.
Further, in step a, titanium tetrachloride consumption is 1～15mL.
Further, in step a, thiocarbamide consumption is 0.1～3g.
Further, in step a, ultrapure water consumption is 5～30mL.
Further, in step a, polyethylene glycol (600) consumption is 1～2 drop.
Further, in step b, potassium permanganate consumption is 1～10g.
Further, in step b, graphite powder consumption is 0.1～2g.
Further, in step b, concentrated sulfuric acid consumption is 80～180mL.
Further, in step b, phosphoric acid consumption is 1～20mL.
Further, in step b, hydrogen peroxide use is 5～15mL.
Further, in step c, sulfur doping titanium dioxide consumption is 0.01～1g.
Further, in step c, graphite oxide consumption is 0.001～0.5g.
Further, in step c, ultrapure water consumption is 40～80mL.
Further, in step d, the concentration of methyl orange solution is 1～100mg/L.
Further, in step d, the consumption of sulfur doping titanium dioxide-graphene aerogel composite is 0.01～1g/
L。
Further, in step d the characteristic absorption peak of methyl orange at 465nm.
The invention has the beneficial effects as follows：The preparation method of sulfur doping titanium dioxide-graphene aerogel composite is simple
And it is very fast to the degradation rate of the organic molecules such as methyl orange, the composite is easily recycled and environmentally safe.
Description of the drawings
Below in conjunction with the accompanying drawings this experiment is further illustrated.
Fig. 1 is the X-ray diffractogram of sulfur doping titanium dioxide in embodiment one；a：Pure titinium dioxide, b：Sulfur doping dioxy
Change titanium.
Fig. 2 is the uv drses figure of sulfur doping titanium dioxide in embodiment one；a：Pure titinium dioxide, b：Sulfur doping dioxy
Change titanium.
Fig. 3 is the field emission scanning electron microscope figure of sulfur doping titanium dioxide-graphene aerogel composite in embodiment two.
Fig. 4 is applied to methyl orange degradation for sulfur doping titanium dioxide-graphene aerogel composite in embodiment three
Design sketch.
Fig. 5 is impact of the sulfur doping amount to catalyst photocatalysis effect in example IV.
Fig. 6 is sulfur doping titanium dioxide institute in sulfur doping titanium dioxide in embodiment five-graphene aerogel composite
Impact of the accounting example to catalytic effect.
Fig. 7 is pure titinium dioxide, sulfur doping titanium dioxide, graphene aerogel, sulfur doping in comparative example one, two, three, four
Titanium dioxide-graphene aerogel is applied to the design sketch of methyl orange degradation.
Specific embodiment
Presently in connection with specific embodiment, the present invention will be further described, and following examples are intended to illustrate rather than
Limitation of the invention further.
The percent of decolourization of the methyl orange solution shown in narration in detail of the invention and examples of implementation is to calculate as follows
's：Certain density methyl orange solution is configured, and the absorbance at 465nm is measured using ultraviolet-visible spectrophotometer, is designated as
a0.Sample during UV degradation, the absorbance at 465nm is measured using ultraviolet-visible spectrophotometer, be designated as an(n
For sampling number of times).Percent of decolourization bnCalculated by below equation：
bn=1-an/a0(n=0,1,2 ...)
Embodiment one：
12mL ultra-pure waters are slowly added dropwise in 14.4mL titanium tetrachloride solutions (2.5M), then in its solution plus 2.055g
Thiocarbamide and 2 drops polyethylene glycol (600).Mixed liquor is transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reaction 3h.It is white by what is separated out
The centrifugation of color solids of sedimentation is simultaneously washed each 3 times with absolute ethyl alcohol and ultra-pure water alternating, is put into oven for drying, sulfur doping two is obtained
Titanium oxide.X ray diffracting spectrum as shown in Figure 1, shows that sulfur doping mode will not change titanium dioxide crystal form used by the present invention,
In product of the present invention, titanium dioxide crystal form is photocatalytic activity highest Detitanium-ore-type.Solid uv drses collection of illustrative plates such as accompanying drawing 2
It is shown, show that the doping of sulphur makes the obvious red shift of Titanium dioxide absorption spectrum.
Embodiment two：
6g potassium permanganate and 1g graphite powders is weighed, stirring, standby is placed in beaker.Sequentially add in there-necked flask
The 120mL concentrated sulfuric acids, 13.3mL phosphoric acid, are added slowly with stirring the mixture of potassium permanganate and graphite powder.48 DEG C of design temperature,
Water-bath 12h.After reaction terminates, prepare 1000mL beakers, add ice cube and 10mL hydrogen peroxide, reactant liquor is poured into
In 1000mL beakers, 12h is stood.Solution is layered, and removes a layer yellow, is centrifuged.Ultra-pure water is added repeatedly, stirring, centrifugation, until molten
Liquid is in weakly acidic pH.Solution is poured in culture dish, 48h is stood, is obtained graphite oxide.Weigh the sulfur doping two of the preparation of embodiment one
Graphite oxide 0.01g prepared by titanium oxide 0.75g and said method, is scattered in 70mL ultra-pure waters, and ultrasound makes to be uniformly dispersed.Will
Dispersion liquid is transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reaction 12h.After reaction terminates, product is taken out, freezed at -45 DEG C
24h is dried, sulfur doping titanium dioxide-graphene aerogel composite is obtained.Its scanning electron microscope image such as 3 institute of accompanying drawing
Show, illustrate that the composite has the three-dimensional porous stereochemical structure of graphene aerogel.
Embodiment three：
Compound concentration is 6mg/L methyl orange solution 500mL, weighs the sulfur doping titanium dioxide-graphite of the preparation of embodiment two
Alkene aerogel composite 0.05g, the methyl orange in degradation water under 11W ultra violet lamps were sampled once per half an hour, were used
Ultraviolet-uisible spectrophotometer detects the characteristic absorption peak intensity of methyl orange solution, calculates solution percent of decolourization.As a result such as 4 institute of accompanying drawing
Show, decolouring needs time-consuming 1.5h completely.
Example IV：
Investigate impact of the sulfur doping amount to sulfur doping titanium dioxide photocatalysis effect.In 14.4mL titanium tetrachloride solutions
(2.5M) 12mL ultra-pure waters and 2 drops polyethylene glycol (600) are added dropwise in, then add in its solution respectively 1.370g, 2.055g,
2.740g, 5.480g thiocarbamides.Mixed liquor is transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reaction 3h.Will be the white for separating out solid
Body precipitation and centrifugal separation is simultaneously washed each 3 times with absolute ethyl alcohol and ultra-pure water alternating, is put into oven for drying, is obtained different sulfur doping amounts
Titanium dioxide.Compound concentration is 6mg/L methyl orange solution 500mL, weighs the titanium dioxide of 0.05g difference sulfur doping amounts respectively
Titanium, the methyl orange in degradation water under 11W ultra violet lamps are sampled once per half an hour, using ultraviolet-uisible spectrophotometer
The characteristic absorption peak intensity of detection methyl orange solution, calculates solution percent of decolourization.As a result as shown in Figure 5, thiocarbamide and titanium tetrachloride
Mol ratio is 3:When 4, photocatalysis effect is optimal.
Embodiment five：
Investigate impact of the titanium dioxide proportion to catalytic effect in graphene aerogel composite.Weigh respectively
0.01g, 0.1g, 0.5g, 0.75g, 1g sulfur doping titanium dioxide and 0.01g graphite oxides, are scattered in ultra-pure water, and ultrasound makes point
Dissipate uniform.Dispersion liquid is transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reaction 12h.After reaction terminates, product is taken out, -45
Freeze-drying 24h at DEG C, obtains the sulfur doping titanium dioxide-graphene aerogel composite of different ratio.Compound concentration is
6mg/L methyl orange solution 500mL, weigh the sulfur doping titanium dioxide-graphene aerogel composite wood of 0.05g different ratios respectively
Material, the methyl orange in degradation water under 11W ultra violet lamps are sampled once per half an hour, using ultraviolet-uisible spectrophotometer
The characteristic absorption peak intensity of detection methyl orange solution, calculates solution percent of decolourization.As a result as shown in Figure 6, titanium dioxide institute accounting
When weight is 98.7%, photocatalysis effect is optimal.
Comparative example one：
Investigate degradation capability of the pure titinium dioxide to methyl orange.It is slowly added dropwise in 14.4mL titanium tetrachloride solutions (2.5M)
12mL ultra-pure waters, are transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reaction 3h.By the white solid precipitation and centrifugal separation for separating out simultaneously
Washed each 3 times with absolute ethyl alcohol and ultra-pure water alternating, be put into oven for drying, obtain pure titinium dioxide.Compound concentration is 6mg/L first
Base orange solution 500mL, weighs the titanium dioxide 0.05g of said method preparation, the methyl in degradation water under 11W ultra violet lamps
Orange, solution decolourize to take 4h altogether completely.
Comparative example two：
Investigate degradation capability of the sulfur doping titanium dioxide to methyl orange.Compound concentration is 6mg/L methyl orange solution 500mL,
Weigh the sulfur doping titanium dioxide 0.05g of the preparation of embodiment one, the methyl orange in degradation water under 11W ultra violet lamps, solution
Decolourize completely to take 2.5h altogether.
Comparative example three：
Investigate degradation capability of the graphene aerogel to methyl orange.The graphite oxide 0.085g of the preparation of embodiment two is weighed,
It is scattered in 70mL ultra-pure waters, ultrasound makes to be uniformly dispersed.Dispersion liquid is transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reactions
12h.After reaction terminates, product, the freeze-drying 24h at -45 DEG C is taken out.Obtain graphene aerogel.Compound concentration is 6mg/L
Methyl orange solution 500mL, weighs the graphene aerogel 0.05g of said method preparation, in degradation water under 11W ultra violet lamps
Methyl orange, reach adsorption equilibrium altogether take 0.5h, now solution percent of decolourization be 23.8%.
Comparative example four：
Investigate sulfur doping titanium dioxide-degradation capability of the graphene aerogel composite to methyl orange.Compound concentration is
6mg/L methyl orange solution 500mL, weigh the sulfur doping titanium dioxide-graphene aerogel composite of the preparation of embodiment two
0.05g, the methyl orange in degradation water under 11W ultra violet lamps, solution decolourize to take 1.5h altogether completely.
Claims (5)
1. the preparation and application of a kind of sulfur doping titanium dioxide-graphene aerogel composite, step are as follows：
A, prepare sulfur doping titanium dioxide：A certain amount of ultra-pure water is added in titanium tetrachloride solution, then in its solution plus sulphur
Urea and polyethylene glycol (600).Mixed liquor is transferred in 100mL hydrothermal reaction kettles, 180 DEG C of reaction 3h.Will be the white for separating out solid
Body precipitation and centrifugal separation is simultaneously washed each 3 times with absolute ethyl alcohol and ultra-pure water alternating, is put into oven for drying, is obtained sulfur doping titanium dioxide
Titanium.
B, prepare graphite oxide：Potassium permanganate and graphite powder is weighed, is placed in beaker and is stirred, it is standby.In there-necked flask
The concentrated sulfuric acid, phosphoric acid is sequentially added, the mixture of potassium permanganate and graphite powder is added slowly with stirring.48 DEG C of design temperature, water
Bath reaction 12h.After reaction terminates, prepare 1000mL beakers, add ice cube and hydrogen peroxide, pour reactant liquor into 1000mL beakers
In, stand 12h.Solution is layered, and removes a layer yellow, is centrifuged.Ultra-pure water is added repeatedly, stirring, centrifugation, until during solution is near
Property.Solution is poured in culture dish, 48h is stood, is obtained graphite oxide.
C, prepare sulfur doping titanium dioxide-graphene aerogel composite：Weigh sulfur doping titanium dioxide obtained in step a and
Graphite oxide obtained in step b, is scattered in ultra-pure water, and ultrasound makes to be uniformly dispersed.Dispersion liquid is transferred to into 100mL hydro-thermal reactions
In kettle, 180 DEG C of reaction 12h.After reaction terminates, product is taken out, the freeze-drying 24h at -45 DEG C obtains sulfur doping titanium dioxide
Titanium-graphene aerogel composite.
D, composite are applied to the methyl orange in degradation water：Certain density methyl orange solution is prepared, with sulphur obtained in step c
Methyl orange in titania-doped-graphene aerogel composite degradation water, while use ultraviolet-uisible spectrophotometer
The characteristic absorption peak intensity of detection methyl orange solution.When characteristic absorption peak disappears, that is, illustrate that the methyl orange degradation in solution is complete
Entirely, record the time used by degraded.
2. the preparation and application of a kind of sulfur doping titanium dioxide-graphene aerogel composite according to claim 1, its
It is characterized in that：In the step a titanium tetrachloride consumption be 1～15mL, thiocarbamide consumption be 0.1～3g, ultrapure water consumption be 5～
30mL, polyethylene glycol (600) consumption are 1～2 drop.
3. the preparation and application of a kind of sulfur doping titanium dioxide-graphene aerogel composite according to claim 1, its
It is characterized in that：In the step b potassium permanganate consumption be 1～10g, graphite powder consumption be 0.1～2g, concentrated sulfuric acid consumption be 80～
180mL, phosphoric acid consumption are 1～20mL, and hydrogen peroxide use is 5～15mL.
4. the preparation and application of a kind of sulfur doping titanium dioxide-graphene aerogel composite according to claim 1, its
It is characterized in that：In step c, sulfur doping titanium dioxide consumption is 0.01～1g, and graphite oxide consumption is 0.001～0.5g, ultrapure
Water consumption is 40～80mL.
5. the preparation and application of a kind of sulfur doping titanium dioxide-graphene aerogel composite according to claim 1, its
It is characterized in that：In step d, the concentration of methyl orange solution is 1～100mg/L, and sulfur doping titanium dioxide-graphene aerogel is multiple
The consumption of condensation material is 0.01～1g/L.The characteristic absorption peak of methyl orange is at 465nm.
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