CN106076378A - A kind of preparation method and application of titanium dioxide graphene oxide carbon composite (TiO2 GO AC) - Google Patents
A kind of preparation method and application of titanium dioxide graphene oxide carbon composite (TiO2 GO AC) Download PDFInfo
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- CN106076378A CN106076378A CN201610456286.3A CN201610456286A CN106076378A CN 106076378 A CN106076378 A CN 106076378A CN 201610456286 A CN201610456286 A CN 201610456286A CN 106076378 A CN106076378 A CN 106076378A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 238000007667 floating Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000005446 dissolved organic matter Substances 0.000 abstract description 3
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 11
- 229940043267 rhodamine b Drugs 0.000 description 9
- 239000008187 granular material Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003608 titanium Chemical class 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- 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
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- 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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- 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
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- 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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Abstract
The invention provides a kind of titanium dioxide graphene oxide carbon composite (TiO2GO AC) preparation method and application, belong to technical field of composite materials.Titanium dioxide (the TiO that this composite is modified with graphene oxide2GO) it is presoma, then uses mineral carbon load TiO2GO and obtain.There is the advantages such as photocatalytic activity is high, specific surface area is big.TiO2GO uses Ti O C chemical bonds, its photocatalysis effect and TiO2Compare and improve a lot.Activated carbon, as the porous adsorbent of micropore prosperity, has the strongest absorbability to dissolved organic matter in water, some polluter being difficult to biochemistry or oxidative degradation is also had good adsorption effect.Activated carbon is joined TiO2In GO composite so that the catalysis activity of this material improves further.Therefore, this titanium dioxide graphene oxide carbon composite is a kind of good light-catalyzed reaction catalyst.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of titanium dioxide-graphene oxide-carbon composite
(TiO2-GO-AC) preparation method；The invention still further relates to the application of this titanium dioxide-graphene oxide-carbon composite.
Background technology
Titanium dioxide (TiO2) have that chemical stability is strong, nontoxic and low cost and other advantages, and by extensively
Pay close attention to.But TiO2Energy gap big (about 3.2 eV), it is impossible to make full use of solar energy, its light induced electron and hole
Compound probability is big, so the most sub-efficiency is low, is nanoscale additionally, due to granular size, so being difficult to reclaim after making to be finished.Oxidation
Graphene has that specific surface area is big, conducts electricity very well, the easy advantage such as preparation, is well suited as catalyst carrier, Graphene
It is incorporated in semi-conducting material, plays their synergism, the photocatalysis performance of material will be effectively improved.TiO2-GO
Use Ti-O-C chemical bonds, highly stable, its photocatalysis effect and TiO2Compare and improve a lot.Activated carbon is as micropore
Flourishing porous adsorbent, has the strongest absorbability to dissolved organic matter in water, some is difficult to biochemistry or oxidation
The polluter of degraded also has good adsorption effect.The manufacturing cost of activated carbon also tends to reduce, and active carbon adsorption technology exists
Wastewater treatment industry is extensively applied both at home and abroad.Activated carbon is joined TiO2In-GO composite, can be given full play to them
Synergism so that the catalysis activity of this material improves further.
Summary of the invention
The invention aims to overcome problems of the prior art, utilize the stability of Ti-O-C chemical bond,
The preparation method and application of a kind of titanium dioxide-graphene oxide-carbon composite with highlight catalytic active are provided.
A kind of titanium dioxide-graphene oxide-carbon composite (TiO2-GO-AC) preparation method, be by titanium dioxide
Titanium, graphene oxide and the mass ratio that activated carbon ratio is 5:20:4 are added to the water, and stir, are then added to hydro-thermal anti-
Answer in still, at 180 DEG C, react 12h, after having reacted, sucking filtration, be dried to obtain titanium dioxide-graphene oxide-carbon composite wood
Material.
Further, a kind of titanium dioxide-graphene oxide-carbon composite (TiO2-GO-AC) preparation method, institute
The activated carbon stated first passes through pretreatment, through grinding, crosses 60-80 mesh sieve, takes proper amount of active carbon powder, add while stirring
1mol/L dust technology, after standing a few hours, filters off solution and the floating thing on upper strata, by remaining activated carbon through sucking filtration, washing
After, put into baking oven, under conditions of 100 DEG C, be dried 2h, after taking-up, filter out the active carbon powder of 60-100 mesh with sieve,
It is placed in exsiccator as standby.
A kind of titanium dioxide-graphene oxide-carbon composite can be as the photocatalyst of organic dyestuff.
Titanium dioxide-graphene oxide-carbon composite prepared by the present invention has that photocatalytic activity is high, specific surface area is big
Etc. advantage.TiO2-GO uses Ti-O-C chemical bonds, highly stable, its photocatalysis effect and TiO2Compare and improve a lot.
Activated carbon, as the porous adsorbent of micropore prosperity, has the strongest absorbability to dissolved organic matter in water, to some
The polluter being difficult to biochemistry or oxidative degradation also has good adsorption effect.The manufacturing cost of activated carbon also tends to reduce, and lives
Property charcoal adsorption technology wastewater treatment industry at home and abroad is extensively applied.Activated carbon is joined TiO2In-GO composite,
Their synergism can be given full play to so that the catalysis activity of this material improves further.
Accompanying drawing explanation
Fig. 1 is TiO2The SEM figure of-GO-ACl.
Fig. 2 is TiO2The SEM figure of-GO-AC2.
Fig. 3 is TiO2The absorbance figure of-GO-ACl photocatalysis rhodamine B.
Fig. 4 is TiO2The absorbance figure of-GO-AC2 photocatalysis rhodamine B.
Fig. 5 is TiO2-GO-AC1、TiO2-GO-AC2、TiO2-GO、TiO2After catalysis, rhodamine B dulling luminosity ratio is relatively.
Fig. 6 is TiO2-GO-AC1、TiO2-GO-AC2、TiO2-GO、TiO2Rhodamine B absorbance block diagram after catalysis.
Detailed description of the invention
Below by specific embodiment, the preparation of the composite of the present invention and corresponding catalyst thereof is described further.
Embodiment 1
By ultrasonic for 31.25mlGO 1h, add 0.125g titania powder, add coal mass active carbon (being abbreviated as AC1), stirring
0.5h, is then transferred to 50ml hydrothermal reaction kettle by mixed liquor, puts into drying baker and reacts 12h at 180 DEG C.Sucking filtration after cooling,
It is washed with water to there is no Cl-(checking with silver nitrate solution), then i.e. can get activated carbon supported dioxy after 60 DEG C of vacuum drying
Change the composite photo-catalyst TiO that titanium-GO is formed2-GO-AC l)。
By 50 ml rhodamine Bs (2 × 10 during experiment-4Mol/L), during solution is placed in reactor, TiO is added2-GO-ACl granule
72.46mg.In black box, under the conditions of blowing air, stir 30 min, make rhodamine B balance in titanium dioxide granule surface adsorption, with
After, in reactor, taking 0.5 ml serosity be centrifuged separating, in its supernatant, the concentration markers of rhodamine B is C0.Then open
Opening light source and carry out light-catalyzed reaction, every 30 min sample 0.5 ml, sample liquid by centrifugation after, take supernatant detection rhodamine B dense
Degree, is labeled as C, and total reaction time is 2 h, and after 40 min, degradation rate reaches 99.42%.
Embodiment 2
By ultrasonic for 31.25mlGO 1h, add 0.125g titania powder, add cocoanut active charcoal (being abbreviated as AC2) 0.025g,
Stirring 0.5h, is then transferred to mixed liquor 50ml hydrothermal reaction kettle, puts into drying baker and react 12h at 180 DEG C.Take out after cooling
Filter, is washed with water to do not have Cl-(checking with silver nitrate solution), then i.e. can get activated carbon supported two after 60 DEG C of vacuum drying
The composite photo-catalyst TiO that titanium oxide is formed2-GO-AC2)。
By 50 ml rhodamine Bs (2 × 10 during experiment-4Mol/L), during solution is placed in reactor, TiO is added2-GO-AC2 granule
72.46mg.In black box, under the conditions of blowing air, stir 30 min, make rhodamine B balance in titanium dioxide granule surface adsorption, with
After, in reactor, taking 0.5 ml serosity be centrifuged separating, in its supernatant, the concentration markers of rhodamine B is C0.Then open
Opening light source and carry out light-catalyzed reaction, every 30 min sample 0.5 ml, sample liquid by centrifugation after, take supernatant detection rhodamine B dense
Degree, is labeled as C, and total reaction time is 2 h, and after 40 min, degradation rate reaches 87.87%.
Claims (3)
1. a preparation method for titanium dioxide-graphene oxide-carbon composite, be by titanium dioxide, graphene oxide and
Activated carbon ratio is that the mass ratio of 5:20:4 is added to the water, and stirs, is then added in hydrothermal reaction kettle, at 180 DEG C
Lower reaction 12h, after having reacted, sucking filtration, is dried to obtain titanium dioxide-graphene oxide-carbon composite.
2. according to a kind of titanium dioxide-graphene oxide-carbon composite (TiO described in claims 12-GO-AC)
Preparation method, described activated carbon first passes through pretreatment, through grinding, crosses 60-80 mesh sieve, takes active carbon powder, while stirring
Add the dust technology of concentration 1mol/L, after standing a few hours, filter off solution and the floating thing on upper strata, by remaining activated carbon warp
Sucking filtration, after washing, puts into baking oven, is dried 2h, after taking-up, filters out the work of 60-100 mesh with sieve under conditions of 100 DEG C
Property carbon powder.
3. titanium dioxide-graphene oxide-carbon composite can be as the photocatalyst of organic dyestuff.
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| CN201610456286.3A CN106076378A (en) | 2016-06-22 | 2016-06-22 | A kind of preparation method and application of titanium dioxide graphene oxide carbon composite (TiO2 GO AC) |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824157A (en) * | 2017-02-22 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of modified composite titania material and preparation method thereof, application |
| CN107174919A (en) * | 2017-06-28 | 2017-09-19 | 中国航发北京航空材料研究院 | The composite mesopore carbosphere air purifying preparation that graphene is modified |
| CN107185489A (en) * | 2016-12-30 | 2017-09-22 | 常州碳星科技有限公司 | The preparation method of the sorbing material of Atmospheric Organic Pollutants |
| CN107321340A (en) * | 2017-06-29 | 2017-11-07 | 南通大学 | A kind of graphene composite photocatalyst aeroge of hierarchical porous structure and preparation method thereof |
| CN107362788A (en) * | 2017-06-20 | 2017-11-21 | 四川大学 | A kind of graphene oxide/titanium dioxide activated carbon three-dimensional composite material and preparation method thereof |
| CN108249655A (en) * | 2018-02-02 | 2018-07-06 | 上海师范大学 | Rotary-type photocatalysis-absorption-UF membrane concerted reaction device |
| CN108786729A (en) * | 2018-06-06 | 2018-11-13 | 张小伏 | The preparation method of mask graphene/active carbon in-situ plural gel adsorbent |
| CN108927225A (en) * | 2018-06-27 | 2018-12-04 | 浙江工业大学膜分离与水处理协同创新中心湖州研究院 | A kind of photocatalysis membrana preparation method for dyestuff degradation |
| CN109289777A (en) * | 2018-12-10 | 2019-02-01 | 安徽万山红环保科技有限公司 | A kind of waste-gas adsorbant |
| CN109772301A (en) * | 2019-02-27 | 2019-05-21 | 知合环境（北京）有限责任公司 | Modified ozone oxidation catalyst of a kind of graphene oxide and preparation method thereof |
| CN110142042A (en) * | 2019-04-25 | 2019-08-20 | 东北大学秦皇岛分校 | A kind of RGO/TiO2The preparation method and application of/Ag aerogel type photochemical catalyst |
| CN112138645A (en) * | 2020-11-02 | 2020-12-29 | 上海第二工业大学 | Glass fiber ball beam supported GO/TiO2Photocatalyst and preparation method thereof |
| CN112169784A (en) * | 2020-09-23 | 2021-01-05 | 宁波石墨烯创新中心有限公司 | Titanium dioxide/graphene/carbon composite material and preparation method and application thereof |
| CN112495361A (en) * | 2020-12-22 | 2021-03-16 | 深圳笨鸟冰虫环保科技有限公司 | Environment-friendly efficient composite photocatalyst |
| CN113307326A (en) * | 2021-05-20 | 2021-08-27 | 江西善拓环境科技有限公司 | Preparation of tungsten-based oxide/carbon-based nano composite hydrosol and application of tungsten-based oxide/carbon-based nano composite hydrosol in wastewater treatment |
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| CN107185489A (en) * | 2016-12-30 | 2017-09-22 | 常州碳星科技有限公司 | The preparation method of the sorbing material of Atmospheric Organic Pollutants |
| CN106824157A (en) * | 2017-02-22 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of modified composite titania material and preparation method thereof, application |
| CN107362788A (en) * | 2017-06-20 | 2017-11-21 | 四川大学 | A kind of graphene oxide/titanium dioxide activated carbon three-dimensional composite material and preparation method thereof |
| CN107362788B (en) * | 2017-06-20 | 2020-06-16 | 四川大学 | Graphene oxide/titanium dioxide-activated carbon three-dimensional composite material and preparation method thereof |
| CN107174919A (en) * | 2017-06-28 | 2017-09-19 | 中国航发北京航空材料研究院 | The composite mesopore carbosphere air purifying preparation that graphene is modified |
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| CN107321340A (en) * | 2017-06-29 | 2017-11-07 | 南通大学 | A kind of graphene composite photocatalyst aeroge of hierarchical porous structure and preparation method thereof |
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