CN105688937A - Preparation method for titanium dioxide-graphene-cadmium sulfide composite material - Google Patents
Preparation method for titanium dioxide-graphene-cadmium sulfide composite material Download PDFInfo
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- CN105688937A CN105688937A CN201610068733.8A CN201610068733A CN105688937A CN 105688937 A CN105688937 A CN 105688937A CN 201610068733 A CN201610068733 A CN 201610068733A CN 105688937 A CN105688937 A CN 105688937A
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 20
- 239000010936 titanium Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 229910052793 cadmium Inorganic materials 0.000 claims description 23
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011593 sulfur Substances 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 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 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical group [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 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 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical fields of nanometer composite materials and photocatalysis. A method comprises the following steps: ultrasonically dispersing graphite oxide in water to form a graphene oxide solution; dissolving modified mesoporous titanium dioxide with positive charges in the graphene oxide solution and uniformly stirring; centrifuging to obtain titanium dioxide-graphene oxide and dissolving in ethyl alcohol; adding a precursor of cadmium sulfide; reducing graphene oxide at one step according to a photocatalytic reduction method and depositing cadmium sulfide, thereby acquiring a titanium dioxide/graphene/cadmium sulfide photocatalyst. According to the method provided by the invention, the preparation process is simple and convenient, the cost is low, the raw materials are non-toxic and environmentally friendly, the prepared composite material has strong degradation ability for degrading dyes under visible light condition, and the photocatalytic efficiency is obviously higher than that of the traditional material.
Description
Technical field
The invention belongs to the technical field of the method for preparing catalyst of catalytic degradation dyestuff, particularly with regard to the preparation method of mesoporous TiO 2-graphene-sulfur cadmium trielement composite material。
Background technology
21 century, the energy gone from bad to worse and environmental problem, as pollution, the discharge of Fossil fuel and global warming, beaten alarm bell to human society。In these years, photocatalyst, because of its depollution of environment, the potentiality converting light energy into chemical energy, obtains the extensive concern of scientist, and wherein conductor photocatalysis becomes one of most active research field in the world。
TiO2Because excellent photocatalysis performance, and inexpensively, be easy to get, the advantage such as nontoxic, stable chemical nature, corrosion resistance are strong, be widely used in photocatalysis field。But pure titinium dioxide photocatalysis efficiency is very low, it is prone to reunite, in light-catalyzed reaction process, after photo-generate electron-hole separates, can not moving to catalyst surface in time with regard to compound, and can only absorb the ultraviolet portion in sunlight, the efficiency of light energy utilization is relatively low, composite is prepared, it is possible to be effectively improved TiO by doping2Photocatalytic activity。Graphene, has the light of excellence, heat, power, electricity (high conductivity) character, big specific surface area, adsorptivity；Graphene and TiO2Compound, TiO can be reduced2Reunion, due to the electric conductivity that Graphene is good, photo-generate electron-hole can transfer in time catalyst surface participate in reaction, improve reaction rate；Graphene and TiO simultaneously2Be compounded in and to a certain extent photoresponse scope widened, but effect is still not as obvious。
Summary of the invention
The technical problem to be solved in the present invention is in that, from background above technology, it is proposed to the preparation method of a kind of titanium dioxide-graphene-sulfur cadmium composite so that it is can quick catalysis degradation of dye under visible light conditions。
Technical scheme is as follows:
A kind of preparation method of titanium dioxide-graphene-sulfur cadmium composite, concrete steps have:
(1) mesoporous TiO 2 is dissolved in ethanol, and add silane coupler, wherein every 100mg titanium dioxide uses 20mL ethanol and 0.4mL silane coupler, refluxes 4 hours 80 DEG C of stirred in water bath, clean three times with deionized water, make titanium dioxide surface positively charged；
(2) graphite oxide is dissolved in deionized water, ultrasonic makes graphite oxide be dispersed into graphene oxide, obtain graphene oxide dispersion；
(3) titanium dioxide of the surface positively charged obtained in step (1) is dissolved in water, and join in the graphene oxide dispersion obtained in step (2), wherein, every 100mg titanium dioxide needs to use 5.26mg graphene oxide, stir 30 minutes, with deionized water wash three times, obtain titanium dioxide graphene oxide complex；
(4) the titanium dioxide graphene oxide complex that step (3) obtains is dissolved in ethanol, add four water cadmium nitrates and sulfur powder, wherein, in the titanium dioxide in complex, every 100mg titanium dioxide needs use 20～100mg tetra-water cadmium nitrate and 12mg sulfur powder, irradiate 2 hours with 300w xenon lamp (without filter plate), complete the reduction of graphene oxide and the deposition of cadmium sulfide；
(5) reacted suspension, is centrifuged with deionized water wash, dry, obtains titanium dioxide-graphene-sulfur cadmium composite。
In the present invention, in step (4), in the titanium dioxide in complex, it is preferable that every 100mg titanium dioxide uses 53.38mg tetra-water cadmium nitrate and 12mg sulfur powder。
In the present invention, described graphite oxide can utilize the hummbers method of improvement to prepare, and concrete operations are as follows:
Weighing 1g graphite powder, 1g sodium nitrate powder mixes, and is added dropwise over 33ml concentrated sulphuric acid, stirs 5～10 minutes under 5 DEG C of conditions of psychrolusia；Adding 6g potassium permanganate, speed is add once in 5 seconds, within 1 hour, adds, and is warming up to 35 DEG C, keeps 90 minutes；Add 40ml deionized water with the every 2 seconds speed of one, be warming up to 95 DEG C, keep 35 minutes；It is subsequently adding 100ml deionized water；It is added dropwise over hydrogen peroxide, is that glassy yellow stops dropping to solution；Gained suspension is stood 2 hours, after layering, outwells supernatant, lower floor's suspension is poured in centrifuge tube and clean, first remove manganese ion with the hydrochloric acid of 30%, then clean to neutral with water；Finally dry 48 hours in 60 DEG C of vacuum drying ovens, obtain graphite oxide。
In the present invention, described mesoporous TiO 2 can utilize solvent evaporation induced self-assembly method to prepare, and concrete operations are as follows:
Weigh 1.6gF127 (addition polymers of polypropylene glycol and oxirane) and be dissolved in 30ml alcoholic solution, at room temperature stirring is to transparent, it is separately added into 40mmol glacial acetic acid, 24mmol nitric acid, 10mmol butyl titanate again, stir 1 hour, then being poured into by the mixed sols obtained in the culture dish of 120mm, on electric hot plate, 40 DEG C are heated 12 hours；Move it into again in 65 DEG C of air dry ovens and dry 24 hours；Finally it is warming up to 350 DEG C with the speed of 2 DEG C/min in atmosphere, and calcines 5 hours at 350 DEG C, obtain mesoporous TiO 2。
The present invention has following clear advantage:
The compound of titanium dioxide first of the present invention and graphene oxide is connected by electrostatic interaction, and relative to some weak interactions such as hydrogen bonds, compound is easier to；
Secondly the present invention is completed by a step for the reduction of graphene oxide and the deposition of cadmium sulphide particle, under xenon lamp irradiates, utilizes light-catalyzed reaction, completes reduction and deposition process；
Titanium dioxide of the present invention-graphene-sulfur cadmium composite preparation process is simple and convenient again, and cost is low, raw material asepsis environment-protecting。
Finally, the titanium dioxide-graphene-sulfur cadmium composite prepared by the inventive method has the catalytic performance of excellence, when visible ray, dyestuff degraded is had stronger degradation capability, and photocatalysis efficiency is significantly improved than conventional material tool。
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of titanium dioxide-graphene-sulfur cadmium composite prepared by embodiment 3 present invention。
Fig. 2 is the scanning electron microscope diagram of titanium dioxide-graphene-sulfur cadmium composite prepared by embodiment 3 present invention。
Fig. 3 is the transmission electron microscope figure of titanium dioxide-graphene-sulfur cadmium composite prepared by embodiment 3 present invention。
Fig. 4 is the infrared spectrogram of the titanium dioxide-graphene-sulfur cadmium composite of the embodiment of the present invention 2～4 preparation。
Fig. 5 is the uv-visible absorption spectra figure of titanium dioxide-graphene-sulfur cadmium composite prepared by the present invention。
In figure, a represents titanium dioxide-graphene-sulfur cadmium composite that pure titinium dioxide, b represent prepared by embodiment 3, and as can be seen from the figure titanium dioxide-graphene-sulfur cadmium composite is compared with pure titinium dioxide, and light abstraction width has widened visible region。
Fig. 6 is the pure mesoporous TiO 2 titanium dioxide-graphene-sulfur cadmium composite photocatalytic degradation figure to methyl orange with different cadmium sulfide content of the embodiment of the present invention 1～4 preparation。
In Fig. 4 and Fig. 6, A, B, C, D represents sample prepared by embodiment 1,2,3,4 prepared by the present invention respectively, and as seen from the figure, dyestuff be there is no degradation capability by titanium dioxide under visible light；The doping of Graphene and cadmium sulfide makes the catalytic capability of titanium dioxide extend to visibility region, and when wherein cadmium sulfide doping is 20%, catalytic capability is the strongest, in 120 minutes, the degradation rate of methyl orange is reached 94%。
Detailed description of the invention
Embodiment 1
Weigh 1.6gF127 (addition polymers of polypropylene glycol and oxirane) and be dissolved in 30ml alcoholic solution, at room temperature stirring is to transparent, it is separately added into 40mmol glacial acetic acid, 24mmol nitric acid, 10mmol butyl titanate again, stir 1 hour, then being poured into by the mixed sols obtained in the culture dish of 120mm, on electric hot plate, 40 DEG C are heated 12 hours；Move it into again in 65 DEG C of air dry ovens and dry 24 hours；Finally it is warming up to 350 DEG C with the speed of 2 DEG C/min in atmosphere, and calcines 5 hours at 350 DEG C, obtain mesoporous TiO 2。Take sample segment as blank group。
Embodiment 2
The mesoporous TiO 2 taking 100mg embodiment 1 preparation is dissolved in 20mL ethanol, and adds 0.4mLATPES, refluxes 4 hours 80 DEG C of stirred in water bath, cleans three times with deionized water, makes titanium dioxide surface positively charged；5.26mg graphite oxide is dissolved in deionized water, ultrasonic power ultrasonic 3 hours at 560w, make graphite oxide be dispersed into graphene oxide；The titanium dioxide of surface positively charged is dissolved in water, puts in graphene oxide dispersion, stir 30 minutes, with deionized water wash three times；The titanium dioxide graphene oxide complex obtained is dissolved in ethanol, add 23.72mg tetra-water cadmium nitrate and 12mg sulfur powder, 2 hours are irradiated with 300w xenon lamp (without filter plate), complete the reduction of graphene oxide and the deposition of cadmium sulfide, by reacted suspension, it is centrifuged with deionized water wash, dry, obtaining titanium dioxide-graphene-sulfur cadmium composite, wherein cadmium sulfide accounts for the 10% of total complex mass fraction。
Embodiment 3:
The mesoporous TiO 2 taking 100mg embodiment 1 preparation is dissolved in 20mL ethanol, and adds 0.4mLATPES, refluxes 4 hours 80 DEG C of stirred in water bath, cleans three times with deionized water, makes titanium dioxide surface positively charged；5.26mg graphite oxide is dissolved in deionized water, ultrasonic power ultrasonic 3 hours at 560w, make graphite oxide be dispersed into graphene oxide；The titanium dioxide of surface positively charged is dissolved in water, puts in graphene oxide dispersion, stir 30 minutes, with deionized water wash three times；The titanium dioxide graphene oxide complex obtained is dissolved in ethanol, add 53.38mg tetra-water cadmium nitrate and 12mg sulfur powder, 2 hours are irradiated with 300w xenon lamp (without filter plate), complete the reduction of graphene oxide and the deposition of cadmium sulfide, by reacted suspension, it is centrifuged with deionized water wash, dry, obtaining titanium dioxide-graphene-sulfur cadmium composite, wherein cadmium sulfide accounts for the 20% of total complex mass fraction。
Embodiment 4:
The mesoporous TiO 2 taking 100mg embodiment 1 preparation is dissolved in 20mL ethanol, and adds 0.4mLATPES, refluxes 4 hours 80 DEG C of stirred in water bath, cleans three times with deionized water, makes titanium dioxide surface positively charged；5.26mg graphite oxide is dissolved in deionized water, ultrasonic power ultrasonic 3 hours at 560w, make graphite oxide be dispersed into graphene oxide；The titanium dioxide of surface positively charged is dissolved in water, puts in graphene oxide dispersion, stir 30 minutes, with deionized water wash three times；The titanium dioxide graphene oxide complex obtained is dissolved in ethanol, add 91.49mg tetra-water cadmium nitrate and 12mg sulfur powder, 2 hours are irradiated with 300w xenon lamp (without filter plate), complete the reduction of graphene oxide and the deposition of cadmium sulfide, by reacted suspension, it is centrifuged with deionized water wash, dry, obtaining titanium dioxide-graphene-sulfur cadmium composite, wherein cadmium sulfide accounts for the 30% of total complex mass fraction。
Embodiment 5:
The each 20mg of sample of Example 1～4 preparation, it is placed in different beakers, add the methyl orange solution 50ml that concentration is 10mg/L respectively, beaker is placed in magnetic stirrer, camera bellows absorption stirring 30 minutes, use 300w xenon lamp that sample is irradiated, radiate 2 hours under more than 400nm wavelength, period all took out 4ml solution from each beaker and is placed in different 4ml centrifuge tubes every 30 minutes, centrifugation precipitates out sample, removal supernatant is to 5ml centrifuge tube, to be measured, uses the concentration of methyl orange in UV-vis spectrophotometer measurement centrifuge tube。Measure the absorbance under the different photocatalysis time, thus obtaining each sample photocatalytic degradation effect to methyl orange under each time period, as shown in Figure 6。
As can be seen from the above embodiments, the composite material and preparation method thereof that the present invention relates to has with low cost, environmental friendliness, repeatable high, tests through photo-catalytic degradation of methyl-orange, after camera bellows adsorbs 30 minutes, the radiation of visible light sample degradation ability that after 120 minutes, embodiment 3 prepares is the strongest, 94% can be reached, it is possible to be widely used in the field of Environment Protections such as process waste water from dyestuff, it is possible to reduce energy resource consumption。
Claims (4)
1. a preparation method for titanium dioxide-graphene-sulfur cadmium composite, concrete steps have:
(1) mesoporous TiO 2 is dissolved in ethanol, and add silane coupler, wherein every 100mg titanium dioxide uses 20mL ethanol and 0.4mL silane coupler, refluxes 4 hours 80 DEG C of stirred in water bath, clean three times with deionized water, make titanium dioxide surface positively charged；
(2) graphite oxide is dissolved in deionized water, ultrasonic makes graphite oxide be dispersed into graphene oxide, obtain graphene oxide dispersion；
(3) titanium dioxide of the surface positively charged obtained in step (1) is dissolved in water, and join in the graphene oxide dispersion obtained in step (2), wherein, every 100mg titanium dioxide needs to use 5.26mg graphene oxide, stir 30 minutes, with deionized water wash three times, obtain titanium dioxide graphene oxide complex；
(4) the titanium dioxide graphene oxide complex that step (3) obtains is dissolved in ethanol, add four water cadmium nitrates and sulfur powder, wherein, in the titanium dioxide in complex, every 100mg titanium dioxide needs use 20～100mg tetra-water cadmium nitrate and 12mg sulfur powder, irradiate 2 hours with 300w xenon lamp, complete the reduction of graphene oxide and the deposition of cadmium sulfide；
(5) reacted suspension, is centrifuged with deionized water wash, dry, obtains titanium dioxide-graphene-sulfur cadmium composite。
2., in the preparation method of a kind of titanium dioxide according to claim 1-graphene-sulfur cadmium composite, in the titanium dioxide in complex in step (4), every 100mg titanium dioxide uses 53.38mg tetra-water cadmium nitrate and 12mg sulfur powder。
3., in the preparation method of a kind of titanium dioxide according to claim 1 and 2-graphene-sulfur cadmium composite, described graphite oxide is to utilize the hummbers method improved to prepare, and concrete operations are as follows:
Weighing 1g graphite powder, 1g sodium nitrate powder mixes, and is added dropwise over 33ml concentrated sulphuric acid, stirs 5～10 minutes under 5 DEG C of conditions of psychrolusia；Adding 6g potassium permanganate, speed is add once in 5 seconds, within 1 hour, adds, and is warming up to 35 DEG C, keeps 90 minutes；Add 40ml deionized water with the every 2 seconds speed of one, be warming up to 95 DEG C, keep 35 minutes；It is subsequently adding 100ml deionized water；It is added dropwise over hydrogen peroxide, is that glassy yellow stops dropping to solution；Gained suspension is stood 2 hours, after layering, outwells supernatant, lower floor's suspension is poured in centrifuge tube and clean, first remove manganese ion with the hydrochloric acid of 30%, then clean to neutral with water；Finally dry 48 hours in 60 DEG C of vacuum drying ovens, obtain graphite oxide。
4., in the preparation method of a kind of titanium dioxide according to claim 1 and 2-graphene-sulfur cadmium composite, described mesoporous TiO 2 utilizes solvent evaporation induced self-assembly method to prepare, and concrete operations are as follows:
Weigh 1.6gF127 (addition polymers of polypropylene glycol and oxirane) and be dissolved in 30ml alcoholic solution, at room temperature stirring is to transparent, it is separately added into 40mmol glacial acetic acid, 24mmol nitric acid, 10mmol butyl titanate again, stir 1 hour, then being poured into by the mixed sols obtained in the culture dish of 120mm, on electric hot plate, 40 DEG C are heated 12 hours；Move it into again in 65 DEG C of air dry ovens and dry 24 hours；Finally it is warming up to 350 DEG C with the speed of 2 DEG C/min in atmosphere, and calcines 5 hours at 350 DEG C, obtain mesoporous TiO 2。
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| CN106513020A (en) * | 2016-11-01 | 2017-03-22 | 吉林大学 | Preparation method of bismuth tungstate-molybdenum disulfide/graphene composite |
| CN108097267A (en) * | 2017-12-19 | 2018-06-01 | 长沙理工大学 | Preparation method of sulfide quantum dot modified graphene/titanium oxide nano microsphere photocatalytic material |
| CN109651860A (en) * | 2018-12-24 | 2019-04-19 | 湖北航天化学技术研究所 | A kind of graphene/nanometer titanium dioxide composite material and preparation method and application |
| CN110615429A (en) * | 2019-10-30 | 2019-12-27 | 武汉低维材料研究院有限公司 | Method for preparing graphene through visible light reduction |
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| CN105214689A (en) * | 2015-09-07 | 2016-01-06 | 上海应用技术学院 | A kind of TiO 2/ CdS/ Graphene composite photocatalyst material and preparation method thereof |
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| CN102658176A (en) * | 2012-04-23 | 2012-09-12 | 上海师范大学 | Method for embedding cadmium selenide quantum dots in mesoporous titanium dioxide framework |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106513020A (en) * | 2016-11-01 | 2017-03-22 | 吉林大学 | Preparation method of bismuth tungstate-molybdenum disulfide/graphene composite |
| CN108097267A (en) * | 2017-12-19 | 2018-06-01 | 长沙理工大学 | Preparation method of sulfide quantum dot modified graphene/titanium oxide nano microsphere photocatalytic material |
| CN108097267B (en) * | 2017-12-19 | 2020-04-24 | 长沙理工大学 | Preparation method of sulfide quantum dot modified graphene/titanium oxide nano microsphere photocatalytic material |
| CN109651860A (en) * | 2018-12-24 | 2019-04-19 | 湖北航天化学技术研究所 | A kind of graphene/nanometer titanium dioxide composite material and preparation method and application |
| CN109651860B (en) * | 2018-12-24 | 2021-06-11 | 湖北航天化学技术研究所 | Graphene/nano titanium dioxide composite material and preparation method and application thereof |
| CN110615429A (en) * | 2019-10-30 | 2019-12-27 | 武汉低维材料研究院有限公司 | Method for preparing graphene through visible light reduction |
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