CN108940250A - It is a kind of to prepare graphene-based TiO2The method of catalysis material - Google Patents
It is a kind of to prepare graphene-based TiO2The method of catalysis material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 36
- 239000013049 sediment Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 5
- 210000000232 gallbladder Anatomy 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 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
- 239000000126 substance Substances 0.000 abstract description 5
- 230000000505 pernicious effect Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Classifications
-
- 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
- B01J21/18—Carbon
-
- B01J35/39—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Abstract
The present invention, which discloses, a kind of prepares graphene-based TiO2The method of catalysis material, this method comprises the following steps: (1) preparing graphene oxide based on closed oxidizing process；(2) TiO is loaded based on hydro-thermal method redox graphene2Photochemical catalyst prepares graphene-based TiO2Catalysis material.This method is compared with traditional Hummers method, and the pernicious gas of generation is less, and yield is higher；The absorption property and photocatalysis performance of the catalyst photochemical catalyst of this method synthesis are all effectively enhanced, while its specific surface area is bigger, can more effectively adsorb Organic substance in water；During light-catalysed, the graphite base optic catalytic material that this method generates can preferably promote the generation of free radical, improve the degradation efficiency of reactant；The reaction time of this method is short, and raw material is simple, is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to field of novel, are related to a kind of preparation method of novel photocatalysis material, and in particular to a kind of
Graphene-based TiO is prepared based on closed oxidizing process2The method of catalysis material, this method relate generally to doped and compounded used and urge
Change material and carrier.
Background technique
Photocatalysis oxidation technique is an emerging technology in water treatment field, and numerous domestic and foreign scholars are by this method application
In the processing of organic wastewater, and it is studied on the factor of the mechanism of degradation of organic matter and influence degradation efficiency, make electrocatalytic oxidation
Method has obtained continuous development.Photochemical catalytic oxidation is that photochemical catalyst itself does not generate variation under the irradiation of light, but it is generated
Electron hole pair can react the OH for generating strong oxidizing property with the water of surrounding and oxygen, thus Organic substance in water of degrading.Common
Photochemical catalyst is mainly semiconductor material, when the light that energy is greater than semiconductor band gap is irradiated to semiconductor material surface, it
Electronics from valence to conduction band, and a positive hole is generated in valence band, a negative electronics, oxygen are generated on conduction band
The hole for the property changed directly is reacted with the organic matter in water, or is reacted with water and first generated OH, then indirect degradation of organic substances.
Compared to traditional biological effluent treatment method, photocatalysis oxidation technique has convenient operation and management, easily realizes automatic
Change control, operating cost is low, and device integration is high, takes up an area the advantages that few, has increasingly become the research in field of water pollution control
Hot spot.
Graphene is a kind of two-dimensional material with high light transmittance and high conductivity, negative using graphene as photochemical catalyst
Carrier material can significantly improve transmitting speed of the photogenerated charge inside composite photo-catalyst using its excellent electron transmission ability
Degree accelerates the separation of electron hole pair and compound, to enhance the reaction efficiency of photochemical catalyst.Redox graphene is as portion
Divide the graphene of reduction, although translucency and electric conductivity are inferior to flawless sunken graphene, redox graphene residual
Multiple and different functional groups and defect sites increase the activity of graphene surface so that redox graphene is to photocatalysis
The load of agent is more easier.TiO2It is that one kind is efficient, inexpensively, environmental-friendly photochemical catalyst has industrially obtained extensively
Application, TiO of the partial size in Nano grade2With stronger photocatalysis performance.By nano-TiO2It is supported on redox graphene
On, the reaction efficiency of catalyst can be improved and prevent nanocatalyst from comparing during the reaction because of mutually reuniting
Surface area reduces, performance decline.Traditional method for preparing graphene oxide is Hummers method, this method low yield, reaction
Time is long, can generate pernicious gas, and production process is complicated.Therefore it needs to provide and a kind of new prepares graphene-based TiO2Photocatalysis
The method of agent.
Summary of the invention
The purpose of the invention is to overcome the prior art, one kind is provided based on closed oxidizing process and prepares graphene
Base TiO2The method of catalysis material, the preparation method is new and effective, prepares photocatalysis material by carrier of redox graphene
Material, can the effectively organic matter in photochemical catalytic oxidation water in water.
Another object of the present invention is to provide the graphene-based TiO of above method preparation2Photochemical catalyst.
The purpose of the present invention can be achieved by the following measures:
It is a kind of to prepare graphene-based TiO2The method of catalysis material, this method comprises the following steps:
(1) graphene oxide is prepared based on closed oxidizing process；
(2) TiO is loaded based on hydro-thermal method redox graphene2Photochemical catalyst prepares graphene-based TiO2Catalysis material.
The process of graphene oxide is prepared in step (1) based on closed oxidizing process are as follows:
(1.1) crystalline flake graphite and potassium permanganate are put into tetrafluoroethene reaction kettle by the mass ratio of 1:5~8, and measured
The concentrated sulfuric acid is mixed with, and the concentrated sulfuric acid should be able to not have crystalline flake graphite and potassium permanganate；
(1.2) reaction kettle is stood into 2~4h under cryogenic；
(1.3) reaction kettle is stood into 2~4h under the high temperature conditions, carries out closed oxidation reaction；
(1.4) after reaction kettle is fully cooled, reaction kettle kettle cover is opened, the mixture in polytetrafluoroethylkettle kettle gallbladder is poured into
In container, be added ultrapure water agitation and dilution, then be added dropwise hydrogen peroxide (30% hydrogen peroxide, but not limited to this), until mixed liquor is
Yellowish-brown or golden yellow, are staticly settled；
(1.5) after sufficiently precipitating, supernatant is removed, with collected by suction sediment, after adding ultrapure water agitation and dilution
Collected by suction sediment repeats this process until sediment supernatant pH value is greater than 5；
(1.6) it will filter after the obtained vacuum dried ware of sediment is dried and obtain graphene oxide solid powder through grinding
End.
TiO is loaded based on hydro-thermal method redox graphene in step (2)2The process of photochemical catalyst are as follows:
(2.1) the graphene oxide solid powder for taking step (1) to prepare is added ultrapure water and forms graphene oxide mixture
Solution；Ethyl alcohol is added in mixture solution, is ultrasonically formed evenly dispersed graphene oxide layer solution；
(2.2) TiO is added into graphene oxide layer solution2, stir 2~4h；
(2.3) by solution obtained in step (2.2) hydrothermal synthesis reaction kettle high temperature react 12~for 24 hours；
(2.4) solution in reaction kettle is poured into Suction filtration device to be filtered and dried, obtains graphene-based TiO2Light is urged
Agent.
Preferably, in step (1.1), the concentrated sulfuric acid concentration is 0.1~0.5mmol/L (preferably 0.1~0.3mmol/
L), the volume of the concentrated sulfuric acid should be able to not there be crystalline flake graphite and potassium permanganate.
Cryogenic conditions described in step (1.2) are 0~5 DEG C；Hot conditions described in step (1.3) are 70~80
℃。
In step (2.1), the graphene oxide mixture solution that ultrapure water forms 2~8mg/L is added, the ethyl alcohol exists
Final volume percentage concentration in graphene oxide layer solution is not less than 30%.
In step (2.3), the temperature of the hydrothermal synthesis reaction maintains 120~140 DEG C.
In step (2.2), the TiO2The nano-TiO for being 25nm for average grain diameter2, the TiO2With graphene oxide
The mass ratio of solid powder is 1:15~30.
In step (2.1), ultrasonic 30min forms evenly dispersed graphene oxide layer solution.
The graphene-based TiO of above method preparation2Photochemical catalyst.
Compared with prior art, the beneficial effects of the present invention are:
(1) preparation that graphene oxide is carried out using closed oxidizing process, compared with traditional Hummers method, generation
Pernicious gas is less, and yield is higher；
(2) graphene-supported TiO is carried out using hydro-thermal method2The synthesis of photochemical catalyst enhances the adsorptivity of photochemical catalyst
Energy and photocatalysis performance, while its specific surface area is bigger, can more effectively adsorb Organic substance in water；In light-catalysed process
In, graphite-based catalysis material can preferably promote the generation of free radical, improve the degradation efficiency of reactant；
(3) reaction time is short, and raw material is simple, is suitable for large-scale industrial production.
Detailed description of the invention
Fig. 1 is to prepare graphene-based TiO the present invention is based on closed oxidizing process2The flow diagram of catalysis material.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description.
Embodiment 1
One kind preparing graphene-based TiO based on closed oxidizing process2The process of catalysis material includes the following steps:
(1) graphene oxide is prepared based on closed oxidizing process:
(1.1) crystalline flake graphite and potassium permanganate that mass ratio is 1:6 are put into tetrafluoroethene reaction kettle, and measured
The 0.1mmol/L concentrated sulfuric acid is mixed with, and the concentrated sulfuric acid should be able to not have crystalline flake graphite and potassium permanganate；
(1.2) by reaction kettle in (0~5 DEG C) standing 3h of low temperature；
(1.3) reaction kettle is subjected to closed oxidation reaction in (75~80 DEG C) standing 3h of high temperature；
(1.4) after reaction kettle is fully cooled, reaction kettle kettle cover is opened, the mixture in polytetrafluoroethylkettle kettle gallbladder is poured into
In beaker, mixture can extremely not had by pouring into appropriate ultrapure water, and 30% hydrogen peroxide is then added dropwise, until mixed liquor is in agitation and dilution
Yellowish-brown or golden yellow, are staticly settled；
(1.5) after sufficiently precipitating, supernatant is removed, with collected by suction sediment, after adding ultrapure water agitation and dilution
Collected by suction sediment repeats this process until sediment supernatant pH value is greater than 5；
(1.6) it will filter after the obtained vacuum dried ware of sediment is dried and obtain graphite oxide through agate mortar grinding
Alkene solid powder.
(2) TiO is loaded based on hydro-thermal method redox graphene2Photochemical catalyst prepares graphene-based TiO2Photochemical catalyst:
(2.1) graphene oxide solid powder is taken, ultrapure water is added and forms 5mg/L graphene oxide mixture solution；?
Ethyl alcohol is added in mixture solution, and (final volume percentage concentration of the ethyl alcohol in graphene oxide layer solution be
30%) it, is subsequently transferred in beaker, ultrasonic 30min, that is, forms evenly dispersed graphene oxide layer solution；
(2.2) TiO is added into graphene oxide layer solution2(average grain diameter is the nano-TiO of 25nm2)TiO2With oxygen
The mass ratio of graphite alkene solid powder is 1:20, stirs 3h；
(2.3) it transfers the solution into hydrothermal synthesis reaction kettle, 18~22h is reacted in 120 DEG C of high temperature；
(2.4) solution in reaction kettle is poured into Suction filtration device to filter, is then dried graphene-based to get arriving
TiO2Photochemical catalyst.
Embodiment 2
One kind preparing graphene-based TiO based on closed oxidizing process2The process of catalysis material includes the following steps:
(1) graphene oxide is prepared based on closed oxidizing process:
(1.1) crystalline flake graphite and potassium permanganate that mass ratio is 1:5 are put into tetrafluoroethene reaction kettle, and measured
The 0.2mmol/L concentrated sulfuric acid is mixed with, and the concentrated sulfuric acid should be able to not have crystalline flake graphite and potassium permanganate；
(1.2) by reaction kettle in (0~5 DEG C) standing 4h of low temperature；
(1.3) reaction kettle is subjected to closed oxidation reaction in (75~80 DEG C) standing 4h of high temperature；
(1.4) after reaction kettle is fully cooled, reaction kettle kettle cover is opened, the mixture in polytetrafluoroethylkettle kettle gallbladder is poured into
In beaker, pours into after appropriate ultrapure water can extremely not have mixture, using glass bar agitation and dilution, 30% hydrogen peroxide is then added dropwise,
Until mixed liquor be yellowish-brown or golden yellow, staticly settled；
(1.5) after sufficiently precipitating, supernatant is removed, with collected by suction sediment, after adding ultrapure water agitation and dilution
Collected by suction sediment repeats this process until sediment supernatant pH value is greater than 5；
(1.6) it will filter after the obtained vacuum dried ware of sediment is dried and obtain graphite oxide through agate mortar grinding
Alkene solid powder.
(2) TiO is loaded based on hydro-thermal method redox graphene2Photochemical catalyst prepares graphene-based TiO2Photochemical catalyst:
(2.1) graphene oxide solid powder is taken, it is molten that a small amount of ultrapure water formation 5mg/L graphene oxide mixture is added
Liquid；Ethyl alcohol (final volume percentage concentration of the ethyl alcohol in graphene oxide layer solution is added in mixture solution
30%), to be subsequently transferred in beaker, ultrasonic 30min forms evenly dispersed graphene oxide layer solution；
(2.2) graphene oxide layer solution is separately added into TiO2(average grain diameter is the nano-TiO of 25nm2), TiO2With
The mass ratio of graphene oxide solid powder is 1:25, stirs 4h；
(2.3) it transfers the solution into hydrothermal synthesis reaction kettle, 18~20h is reacted in 130 DEG C of high temperature；
(2.4) solution in reaction kettle is poured into Suction filtration device to filter, is then dried graphene-based to get arriving
TiO2Photochemical catalyst.
Embodiment 3
One kind preparing graphene-based TiO based on closed oxidizing process2The process of catalysis material includes the following steps:
(1) graphene oxide is prepared based on closed oxidizing process:
(1.1) crystalline flake graphite and potassium permanganate that mass ratio is 1:8 are put into tetrafluoroethene reaction kettle, and measured
The 0.1mmol/L concentrated sulfuric acid is mixed with, and the concentrated sulfuric acid should be able to not have crystalline flake graphite and potassium permanganate；
(1.2) by reaction kettle in (0~5 DEG C) standing 2h of low temperature；
(1.3) reaction kettle is subjected to closed oxidation reaction in (75~80 DEG C) standing 2h of high temperature；
(1.4) after reaction kettle is fully cooled, reaction kettle kettle cover is opened, the mixture in polytetrafluoroethylkettle kettle gallbladder is poured into
In beaker, mixture can extremely not had by pouring into appropriate ultrapure water, and 30% hydrogen peroxide is then added dropwise, until mixed liquor is in agitation and dilution
Yellowish-brown or golden yellow, are staticly settled；
(1.5) after sufficiently precipitating, supernatant is removed, with collected by suction sediment, after adding ultrapure water agitation and dilution
Collected by suction sediment repeats this process until sediment supernatant pH value is greater than 5；
(1.6) it will filter after the obtained vacuum dried ware of sediment is dried and obtain graphite oxide through agate mortar grinding
Alkene solid powder.
(2) TiO is loaded based on hydro-thermal method redox graphene2Photochemical catalyst prepares graphene-based TiO2Photochemical catalyst:
(2.1) graphene oxide solid powder is taken, ultrapure water is added and forms 5mg/L graphene oxide mixture solution；?
Ethyl alcohol is added in mixture solution, and (final volume percentage concentration of the ethyl alcohol in graphene oxide layer solution be
30%) it, is subsequently transferred in beaker, ultrasonic 30min, that is, forms evenly dispersed graphene oxide layer solution；
(2.2) TiO is added into graphene oxide layer solution2(average grain diameter is the nano-TiO of 25nm2), TiO2 and oxygen
The mass ratio of graphite alkene solid powder is 1:20, stirs 4h；
(2.3) it transfers the solution into hydrothermal synthesis reaction kettle, 16~18h is reacted in 140 DEG C of high temperature；
(2.4) solution in reaction kettle is poured into Suction filtration device to filter, is then dried graphene-based to get arriving
TiO2Photochemical catalyst.
The graphene-based TiO that embodiment 4 is prepared using Examples 1 to 32Treatment effect when photocatalyst treatment sewage
The pharmacy waste water that 300mL is taken from certain pharmaceutical factory, the concentration through paracetamol in detection waste water are higher than 50mg/L, and
The graphene-based TiO prepared in 25mg embodiment is added thereto2Photochemical catalyst is 4.4 × 10 in outdoor solar illuminance4lux
When, after reacted 4h, then surveying its concentration is 7.82mg/L, and degradation rate is up to 84% or more.
In conclusion advantage of the invention has: (1) preparation of graphene oxide is carried out using closed oxidizing process, with tradition
Hummers method compare, the pernicious gas of generation is less, and yield is higher；(2) graphene-supported TiO is carried out using hydro-thermal method2
The synthesis of photochemical catalyst enhances the absorption property and photocatalysis performance of photochemical catalyst, while its specific surface area is bigger, Neng Gougeng
Effective absorption Organic substance in water；During light-catalysed, graphite-based catalysis material can preferably promote the life of free radical
At improving the degradation efficiency of reactant；(3) reaction time is short, and raw material is simple, is suitable for large-scale industrial production.
Claims (10)
1. a kind of prepare graphene-based TiO2The method of catalysis material, which is characterized in that this method comprises the following steps:
(1) graphene oxide is prepared based on closed oxidizing process；
(2) TiO is loaded based on hydro-thermal method redox graphene2Photochemical catalyst prepares graphene-based TiO2Catalysis material.
2. the method according to claim 1, wherein preparing graphite oxide based on closed oxidizing process in step (1)
The process of alkene are as follows:
(1.1) crystalline flake graphite and potassium permanganate are put into tetrafluoroethene reaction kettle by the mass ratio of 1:5~8, and measure dense sulphur
Acid is mixed with；
(1.2) reaction kettle is stood into 2~4h under cryogenic；
(1.3) reaction kettle is stood into 2~4h under the high temperature conditions, carries out closed oxidation reaction；
(1.4) after reaction kettle is fully cooled, reaction kettle kettle cover is opened, the mixture in polytetrafluoroethylkettle kettle gallbladder is poured into container
In, ultrapure water agitation and dilution is added, hydrogen peroxide is then added dropwise, until mixed liquor is yellowish-brown or golden yellow, it is heavy stand
It forms sediment；
(1.5) after sufficiently precipitating, supernatant is removed, with collected by suction sediment, is filtered after adding ultrapure water agitation and dilution
Sediment is collected, repeats this process until sediment supernatant pH value is greater than 5；
(1.6) it will filter after the obtained vacuum dried ware of sediment is dried and obtain graphene oxide solid powder through grinding.
3. the method according to claim 1, wherein negative based on hydro-thermal method redox graphene in step (2)
Carry TiO2The process of photochemical catalyst are as follows:
(2.1) it is molten that ultrapure water formation graphene oxide mixture is added in the graphene oxide solid powder for taking step (1) to prepare
Liquid；Ethyl alcohol is added in mixture solution, is ultrasonically formed evenly dispersed graphene oxide layer solution；
(2.2) TiO is added into graphene oxide layer solution2, stir 2~4h；
(2.3) by solution obtained in step (2.2) in hydrothermal synthesis reaction kettle pyroreaction 12~for 24 hours；
(2.4) solution in reaction kettle is poured into Suction filtration device to be filtered and dried, obtains graphene-based TiO2Photochemical catalyst.
4. according to the method described in claim 2, it is characterized in that, in step (1.1), the concentrated sulfuric acid concentration is 0.1~
The volume of 0.5mmol/L, the concentrated sulfuric acid should be able to not there be crystalline flake graphite and potassium permanganate.
5. according to the method described in claim 2, it is characterized in that, cryogenic conditions described in step (1.2) are 0~5 DEG C；Step
Suddenly hot conditions described in (1.3) are 70~80 DEG C.
6. according to the method described in claim 3, it is characterized in that, the final volume percentage of the ethyl alcohol is dense in step (2.1)
Degree is not less than 30%.
7. according to the method described in claim 3, it is characterized in that, the temperature of the hydrothermal synthesis reaction is tieed up in step (2.3)
It holds at 120~140 DEG C.
8. according to the method described in claim 3, it is characterized in that, in step (2.2), the TiO2It is for average grain diameter
The nano-TiO of 25nm2。
9. preparation method according to claim 3, which is characterized in that in step (2.1), ultrasonic 30min, which is formed, uniformly to be divided
Scattered graphene oxide layer solution.
10. the graphene-based TiO of any the method preparation in claim 1~92Photochemical catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332678A (en) * | 2013-05-24 | 2013-10-02 | 东莞上海大学纳米技术研究院 | Preparation methods of graphene and graphene-oxide compound |
| CN104941621A (en) * | 2015-05-26 | 2015-09-30 | 华南理工大学 | Composite photocatalyst for efficiently degrading antibiotics as well as preparation method and application thereof |
| CN106207121A (en) * | 2016-08-11 | 2016-12-07 | 山西大学 | A kind of porous graphene load carbon coated iron oxide nano particle composite material and preparation method |
| CN106492885A (en) * | 2016-11-15 | 2017-03-15 | 河海大学 | A kind of GNs/CoPcS/TiO2The preparation method of photocatalyst |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332678A (en) * | 2013-05-24 | 2013-10-02 | 东莞上海大学纳米技术研究院 | Preparation methods of graphene and graphene-oxide compound |
| CN104941621A (en) * | 2015-05-26 | 2015-09-30 | 华南理工大学 | Composite photocatalyst for efficiently degrading antibiotics as well as preparation method and application thereof |
| CN106207121A (en) * | 2016-08-11 | 2016-12-07 | 山西大学 | A kind of porous graphene load carbon coated iron oxide nano particle composite material and preparation method |
| CN106492885A (en) * | 2016-11-15 | 2017-03-15 | 河海大学 | A kind of GNs/CoPcS/TiO2The preparation method of photocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| CHENLU BAO等: "Preparation of graphene by pressurized oxidation and multiplex reduction and its polymer nanocomposites by masterbatch-based melt blending", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| 金春吉: "二氧化钛/石墨烯复合材料的制备及其光催化性能的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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