CN106745481A - One kind fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups - Google Patents
One kind fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010453 quartz Substances 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000012530 fluid Substances 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 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 claims description 16
- 229940043267 rhodamine b Drugs 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000007857 degradation product Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- -1 Graphite alkene Chemical class 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 abstract description 12
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 29
- 230000015556 catabolic process Effects 0.000 description 18
- 239000000975 dye Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229940059939 kayexalate Drugs 0.000 description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
One kind fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups.The present invention relates to the continuous photocatalysis method that one kind fills Graphene/P25 laminated films based on secondary groups.The present invention is disposed waste liquid to solve the problems, such as that existing batch (-type) handling process cannot meet big commercial scale.Method：First, quartz plate upper strata connects layer (LbL) Technical form Graphene/P25 multilayer films (one-level assembling)；2nd, the quartz plate assembly array (secondary groups dress) of Graphene/P25 multilayer films is loaded；3rd, continuous photocatalytic degradation technique.The present invention prepares brand-new Graphene/P25 layers and connects a layer laminated film array using secondary groups dress technology, using pump circulation fluid, effectively realizes continuous photocatalytically degradating organic dye, is adapted to scale sewage disposal.Catalyst is carried on quartz plate, technological operation is greatly simplified, has both solved the problems, such as that catalyst reclaims difficult, photocatalysis efficiency is improve again, it is adaptable to high-volume sewage disposal.
Description
Technical field
The present invention relates to one kind based on secondary groups dress Graphene/P25 (commercial TiO2) laminated film continuous photocatalysis side
Method.
Background technology
In recent years, continuing to develop with industry, effectively utilizes and environmental protection to regenerative resource, the water resource of cleaning
What is become is increasingly important, the major issue as mankind institute urgent need to resolve.For example：Printing and dyeing are developed rapidly to water with textile industry
The pollution that body is caused is increasingly severe.Therefore, how to eliminate pollution, reducing energy consumption by effective means is that current science is ground
Study carefully the significant challenge for facing.In numerous wastewater processing technologies, using the Photocatalyst of solar energy be a kind of row it
Can solve effectively and simultaneously the means that the world today faces energy shortage and the hang-up of environmental pollution two.
Conventional conductor photocatalysis material includes TiO2、Fe2O3、ZnS、MoS2、WO3With CdS etc..TiO2Because its is excellent
Photocatalysis performance, good stability, it is nontoxic, cheap the advantages of, more broadly ground in numerous catalysis materials
Study carefully and apply.However, the semiconductor light-catalyst of most of reported in literature is the powder catalyst of nano-scale at present, use
Be batch (-type) handling process.During using this technique photocatalytic degradation, powder photocatalyst need to be directly dispersing in target dyestuff
In solution, degraded in a kettle. under conditions of continuously stirring, catalyst is passed through into centrifugation after degraded terminates
Out preparing for the next use.But actually this batch (-type) handling process cannot meet what big commercial scale disposed waste liquid at all
It is required that：One side liquid agitation amount is big, and required reactor volume is big, quantity is more and stirs huge energy consumption；Above all receive
It is difficult to be separated with the liquid that is degraded after the completion of the powder catalyst light degradation of metrical scale, causes the batch (-type) light based on powder catalyst
Degradation technique rests on laboratory stage always for a long time, it is difficult to put into production application.Therefore, exploitation is new without separating
Type photochemical catalyst, the continuous light degradation technology generations implemented in being flowed with liquid are photocatalysis technologies for interval batch processing degradation technique
Move towards the key of scale practical application.On the other hand, TiO2Used as catalysis material, haveing the shortcomings that can be wide with band gap, leads
The electronics that cause plays a decisive role to photocatalysis efficiency and hole low yield (electron-hole separates hardly possible, is easily combined after separation), seriously
Have impact on TiO2The disposal efficiency of catalysis material.
The content of the invention
The present invention is disposed waste liquid to solve the problems, such as that existing batch (-type) handling process cannot meet big commercial scale, and
The continuous photocatalysis method of Graphene/P25 laminated films is filled based on secondary groups there is provided one kind.
Continuous photocatalysis method of the one kind based on secondary groups dress Graphene/P25 laminated films specifically enters according to the following steps
Capable：
First, a layer Technical form Graphene/P25 multilayer films are connect using layer on quartz plate：P25 is dispersed in the salt that pH is 2
In acid solution, ultrasonically treated 20min~60min obtains the P25 dispersion liquids with positive charge；To be prepared by Hummer ' s methods
Graphene oxide the solution of 2mg/mL is configured to via ultrasonic wave added method；Clean quartz substrate is immersed in polyethyleneimine
30min~60min in amine aqueous solution, obtains the quartz substrate with positive charge；The quartz substrate with positive charge is soaked successively again
Enter to graphene oxide solution and P25 dispersion liquids, dried up with deionized water rinsing after immersion is taken out every time and with nitrogen, born
It is loaded with the quartz plate of one layer of graphene oxide/P25 laminated films；Above step is repeated, obtains being loaded with the THIN COMPOSITE that the number of plies is n
The quartz plate of film；To be loaded with again under conditions of the quartz plate of the laminated film that the number of plies is n is 120 DEG C in temperature using hydrazine hydrate
Reductase 12 h, is loaded with [Graphene/P25]nQuartz plate；
2nd, the quartz plate assembly array of black alkene/P25 multilayer films is loaded：Several are loaded with [Graphene/P25]nStone
English piece is arranged in the reactor along fluid flow direction staggered parallel, and the left end of the reactor is provided with water inlet, and right-hand member sets
Delivery port is equipped with, the water inlet and delivery port are diagonally positioned；
3rd, continuous photocatalytic degradation technique：Opening water pump makes pending solution circulate in the reactor, first in dark
Under the conditions of circulate 20min~40min, then open uviol lamp, start light degradation process, every 30min to treating in reactor
Degradation product carries out Concentration Testing, when after degradation product degraded is complete, i.e. completion fills Graphene/P25 laminated films based on secondary groups
Continuous photocatalytic process；The pending solution is the rhodamine B solution that concentration is 10mg/L.
Operation principle：
The present invention connects layer electrostatic technique and is alternately assembled in its surface vertical direction with quartz plate as catalyst carrier, using layer
Graphene oxide/P25 composite membranes, then reduction obtains load multilayer [Graphene/P25] under 120 DEG C of hydrazine hydrate effectsn(n generations
Table alternately assembling the number of plies) quartz plate (one-level assembling), will load multilayer [Graphene/P25] quartz plate along flow direction row
Into array (secondary groups dress).Dye solution is set continuously to flow through catalyst surface by pump.When ultraviolet light catalyst
During surface, the electronics in P25 valence band is excited and transits to conduction band, is formed respectively with oxidation in valence band and conduction band and goes back proper energy
The photohole and electronics of power.Due to the two-dimentional pi-conjugated structure of Graphene, electronics can be transferred to graphite by the conduction band of P25
Alkene.The electronics that these are captured by Graphene can react to form active oxygen species with dissolving oxygen in aqueous, further with
Water reaction generation hydroxyl radical free radical (OH-), so that dye molecule is degraded.At the same time, the hole in valence band can be direct
Oxidation dye molecule is so that dye molecule is degraded.The present invention prepares brand-new Graphene/P25 layers and connects layer using secondary groups dress technology
Laminated film array, being combined again for electron-hole is effectively suppressed by introducing Graphene, so as to significantly improve the photocatalysis of P25
Degradation property.The structure novel catalysis material can conveniently realize efficiently separating for catalyst and degradation solution so that continuous light
Degradation treatment technique substitutes current batch (-type) handling process research and is possibly realized；It is realized as organic dye solution industry rule
Modelling continuous degradation basis prototype process.
Beneficial effects of the present invention：
1st, the novel photocatalysis membrane array of brand new is prepared using secondary groups dress technology, powder is used so as to avoid
Later stage separating step during catalyst, using pump circulation fluid continuous degradation technology generations for the indirect stirring batch for generally using at present
Secondary handling process, makes it possible the extensive continuous processing of waste water from dyestuff, is that the following real practical application of photocatalysis technology is established
Fixed basis.
2nd, connect layer electrostatic technique using layer and alternately assemble Graphene/P25 composite membranes in its surface vertical direction, formed
The heterogeneous energy-conservations of Graphene/P25 enough effectively suppress photo-generate electron-hole to being combined, so as to significantly improve the photocatalytic degradation of P25
Performance.Graphene is alternately assembled with P25 in addition, is effectively inhibited the reunion of P25 nano-particles, be conducive to light to urge
Change performance to improve.The catalysis material for being obtained has that porosity is high, specific surface area is big, mechanical strength is big, photocatalysis performance is steady
Calmly, the features such as long service life (repeatedly using performance unattenuated).High catalytic efficiency of the present invention, energy saving, low cost
Honest and clean, module design, simple structure, it is easy to operation and maintenance.
Brief description of the drawings
Fig. 1 is the continuous photocatalytic mechanism figure that Graphene/P25 laminated films are filled based on secondary groups；
Fig. 2 is plural layers [Graphene/P25] prepared in embodiment one5SEM figure；
Fig. 3 is [Graphene/P25] prepared in embodiment one5(magnetic force is stirred laminated film under traditional batch mode
Mix) contrasted with (pump circulation flowing) light degradation property under continuation mode of the present invention；
Fig. 4 is the performance comparison figure using embodiment one, embodiment three, example IV and the rhodamine B degradation of embodiment five；
Wherein 1 is embodiment three, and 2 is example IV, and 3 is embodiment five, and 4 is embodiment one；As can be seen from the figure when load is compound
When the number of plies of film is 5, laminated film has maximum photocatalysis efficiency.Therefore the laminated film that selection tool is of five storeys is used as rear
The photochemical catalyst of continuous research.
Fig. 5 is the performance comparison figure of embodiment one, embodiment six and the photocatalytic degradation rhodamine B of embodiment seven；Wherein a is
Rhodamine B degraded certainly under ultraviolet light during without catalyst, b is embodiment six, and c is embodiment seven, and d is embodiment one；
Fig. 6 is the comparison diagram that embodiment carries out dyestuff degraded for continuous 8 time.
Specific embodiment
Specific embodiment one：One kind of present embodiment is based on the continuous light that secondary groups fill Graphene/P25 laminated films
What catalysis process was specifically carried out according to the following steps：
First, a layer Technical form Graphene/P25 multilayer films are connect using layer on quartz plate：P25 is dispersed in the salt that pH is 2
In acid solution, ultrasonically treated 20min~60min obtains the P25 dispersion liquids with positive charge；To be prepared by Hummer ' s methods
Graphene oxide the solution of 2mg/mL is configured to via ultrasonic wave added method；Clean quartz substrate is immersed in polyethyleneimine
30min~60min in amine aqueous solution, obtains the quartz substrate with positive charge；The quartz substrate with positive charge is soaked successively again
Enter to graphene oxide solution and P25 dispersion liquids, dried up with deionized water rinsing after immersion is taken out every time and with nitrogen, born
It is loaded with the quartz plate of one layer of graphene oxide/P25 laminated films；Above step is repeated, obtains being loaded with the THIN COMPOSITE that the number of plies is n
The quartz plate of film；To be loaded with again under conditions of the quartz plate of the laminated film that the number of plies is n is 120 DEG C in temperature using hydrazine hydrate
Reductase 12 h, is loaded with [Graphene/P25]nQuartz plate；
2nd, the quartz plate assembly array of black alkene/P25 multilayer films is loaded：Several are loaded with [Graphene/P25]nStone
English piece is arranged in the reactor along fluid flow direction staggered parallel, and the left end of the reactor is provided with water inlet, and right-hand member sets
Delivery port is equipped with, the water inlet and delivery port are diagonally positioned；
3rd, continuous photocatalytic degradation technique：Opening water pump makes pending solution circulate in the reactor, first in dark
Under the conditions of circulate 20min~40min, then open uviol lamp, start light degradation process, every 30min to treating in reactor
Degradation product carries out Concentration Testing, when after degradation product degraded is complete, i.e. completion fills Graphene/P25 laminated films based on secondary groups
Continuous photocatalytic process；The pending solution is the rhodamine B solution that concentration is 10mg/L.
Specific embodiment two：Present embodiment from unlike specific embodiment one：P25 dioxies described in step one
The quality and pH of changing titanium are that the volume ratio of 2 hydrochloric acid solution is 1mg:2mL.Other steps and parameter and the phase of specific embodiment one
Together.
Specific embodiment three：Present embodiment from unlike specific embodiment one or two：Described in step
Above step is repeated, obtains being loaded with the quartz plate of the laminated film that the number of plies is 5.Other steps and parameter and specific embodiment
One or three is identical.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Institute in step 3
The power for stating uviol lamp is 300W.Other steps and parameter are identical with one of specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Controlled in step 3
The flow velocity of water pump processed is 8mL/s.Other steps and parameter are identical with one of specific embodiment one to four.
Specific embodiment six：A kind of continuous light based on secondary groups dress Graphene/P25 laminated films of present embodiment is urged
The application of change is [rGO/P25] with Photocatalytic Degradation Property that will be prepared using LbL electrostatic assemblies technologynLaminated film is used
In photocatalytic degradation rhodamine B under ultraviolet light, concrete operation method is as follows：[rGO/P25] that will be preparednThe parallel friendship of laminated film
In quartz reactor for 10mg/L rhodamine B solution of the insertion equipped with 370mL, water pump is opened, rhodamine B is made under dark condition
Solution circulation flow moves 30min；Open 300W uviol lamps and start Photocatalytic Degradation Process, UV-vis spectroscopy is used every 30min
Photometer is detected to the concentration of the rhodamine B in reactor.
Beneficial effects of the present invention are verified by following examples：
Embodiment one：One kind of the present embodiment is based on the continuous photocatalysis method that secondary groups fill Graphene/P25 laminated films
Specifically carry out according to the following steps：
First, one-level assembling：Quartz plate upper strata connects layer (LbL) Technical form Graphene/P25 multilayer films：By 3mg P25 dispersions
In the hydrochloric acid solution that 6mL pH are 2, ultrasonically treated 20min~60min obtains the P25 dispersion liquids with positive charge；To pass through
Graphene oxide prepared by Hummer ' s methods is configured to the solution of 2mg/mL via ultrasonic wave added method；By clean quartz substrate
30min~60min in polyethylenimine solution is immersed in, the quartz substrate with positive charge is obtained.Again by the quartz substrate point
10min and 15min in graphene oxide solution and P25 dispersion liquids is not immersed in, and with deionized water rinsing and nitrogen is used after taking-up
Drying can obtain being loaded with the quartz plate of one layer of graphene oxide/P25 laminated films；Above step is repeated, is loaded with
The number of plies is the quartz plate of 5 laminated film；The quartz plate that the laminated film that the number of plies is 5 will be loaded with again is 120 DEG C in temperature
Under the conditions of use hydrazine hydrate reduction 2h, be loaded with [Graphene/P25]5Quartz plate；2nd, secondary groups dress：It is loaded with [stone
Black alkene/P25]5Quartz plate assembly array：[Graphene/P25] is loaded by 55Quartz glass plate along fluid flow direction hand over
Mistake is arranged in parallel in the reactor, and the left end of the reactor is provided with water inlet, and right-hand member is provided with delivery port, the water inlet
It is diagonally positioned with delivery port；3rd, continuous photocatalytic degradation technique：Make pending solution recycle stream in the reactor using water pump
Dynamic, flow velocity is 8mL/s, and 20min~40min is first circulated under dark condition, makes to treat degradation material in load [Graphene/P25]5
Quartz glass plate reach adsorption/desorption balance, then open 300W uviol lamps, start light degradation process, every 30min to anti-
Degradation product carries out Concentration Testing to answer treating in device, when after degradation product degraded completely after, that is, complete based on secondary groups dress Graphene/
The continuous photocatalytic process of P25 laminated films；The pending solution is the rhodamine B solution that concentration is 10mg/L.
Embodiment two：The present embodiment is with the difference of embodiment one：When carrying out photocatalytic degradation reaction, using magnetic
Power agitator is treated degradation material and is stirred, and rotating speed is 250rpm.Other are identical with embodiment one.
Embodiment three：The present embodiment is with the difference of embodiment one：The catalyst number of plies is 1 layer in step one, its
He is identical with embodiment one.
Example IV：The present embodiment is with the difference of embodiment one：Repeated in step one 2 times, born
It is loaded with the quartz glass plate of the laminated film that the number of plies is 3.Other are identical with embodiment one.
Embodiment five：The present embodiment is with the difference of embodiment one：Repeated in step one 6 times, born
It is loaded with the quartz glass plate of the laminated film that the number of plies is 7.Other are identical with embodiment one.
Embodiment six：The present embodiment is with the difference of embodiment one：[oxygen is prepared using LbL electrostatic assembly technologies
Graphite alkene/P25]5After laminated film, hydrazine hydrate reduction is not used, will directly load [graphene oxide/P25]5Quartz plate
Photocatalytic degradation experiment is carried out in insertion quartz reactor.Other are identical with embodiment one.
Embodiment seven：The present embodiment is with the difference of embodiment one：Substituted using kayexalate solution
Graphene oxide solution, is prepared [kayexalate/P25] using LbL electrostatic assembly technologies5Laminated film, uses preparation
[kayexalate/P25]5Laminated film carries out photocatalytic degradation.Other are identical with embodiment one.
Fig. 1 is the continuous photocatalytic mechanism figure that Graphene/P25 laminated films are filled based on secondary groups；It will be seen from figure 1 that
[GO/P25]nLaminated film is to connect a layer electrostatic technique by layer to be assembled on quartz supports substrate, followed by hydrazine hydrate also
Former graphene oxide (GO) is finally loaded [rGO/P25] for reduced graphene (rGO)nThe thin quartz plate of MULTILAYER COMPOSITE.And
And by the alternate intercalation reaction device of the quartz plate of obtained supported catalyst after, dye solution can be realized by pump circulation fluid
Continuous light degradation process.
Fig. 2 is in embodiment one prepared [Graphene/P25]5The SEM figures of laminated film, can be from figure simultaneously
To in the composite membrane presence of Graphene and P25, it was demonstrated that the successful preparation of multilayer film.And the porous knot of the surface porosity of film
Structure, this is highly beneficial for photocatalytic degradation.
Fig. 3 is [Graphene/P25] prepared in embodiment one5(magnetic force is stirred laminated film under traditional batch mode
Mix) contrasted with (pump circulation flowing) light degradation property under continuation mode of the present invention.It can be seen that being answered for prepared
Close multilayer film catalyst [Graphene/P25]5For, continuous light degradation technique will be substantially due to traditional batch light degradation technique.
Fig. 4 is the performance comparison figure using embodiment one, embodiment three, example IV and the rhodamine B degradation of embodiment five；
Wherein 1 is embodiment three, and 2 is example IV, and 3 is embodiment five, and 4 is embodiment one；As can be seen from the figure when load is compound
When the number of plies of film is 5, laminated film has maximum photocatalysis efficiency.Therefore the laminated film that selection tool is of five storeys is used as rear
The photochemical catalyst of continuous research.
Fig. 5 is the performance comparison figure of embodiment one, embodiment six and the photocatalytic degradation rhodamine B of embodiment seven；Wherein a is
Rhodamine B degraded certainly under ultraviolet light during without catalyst, b is embodiment six, and c is embodiment seven, and d is embodiment one；Selection
Rhodamine B is used as photodegradative target substance.For embodiment one, under 300W ultra violet lamps, with the increasing of light application time
Plus, the concentration of dyestuff is constantly reduced, and rhodamine B can be made degradable after 180min, the color of dyestuff also from start piece
Red becomes colorless.In order to further prove the degradation property of prepared embodiment one, and made under identical experiment condition
For [graphene oxide/P25]5[kayexalate/P25]5Film as a comparison, wherein kayexalate pair
Photocatalysis effect is without influence.When without catalyst, the degraded certainly of dyestuff can almost be ignored；And photocatalysis efficiency is according to [oxygen
Graphite alkene/P25]5<[kayexalate/P25]5<[Graphene/P25]5Order gradually increase.Result above is proved
Embodiment one has most excellent photocatalysis performance.
Fig. 6 is the comparison diagram that embodiment carries out dyestuff degraded for continuous 8 time；As can be seen from Figure 6 embodiment one is used
After continuous 8 times carry out dyestuff degradation process, catalytic efficiency does not have obvious reduction, it was demonstrated that prepared catalyst has excellent
Different stability, can be with Reusability.
Continuous photocatalytically degradating organic dye can effectively be realized by above example, catalyst has both certainly been solved and reclaimed difficult
Problem, photocatalysis efficiency is improve again, can be used for high-volume sewage disposal.
Claims (5)
1. it is a kind of to be based on the continuous photocatalysis method that secondary groups fill Graphene/P25 laminated films, it is characterised in that based on secondary groups
Fill what the continuous photocatalysis method of Graphene/P25 laminated films was specifically carried out according to the following steps：
First, a layer Technical form Graphene/P25 multilayer films are connect using layer on quartz plate：P25 is dispersed in the hydrochloric acid that pH is 2 molten
In liquid, ultrasonically treated 20min~60min obtains the P25 dispersion liquids with positive charge；The oxygen that will be prepared by Hummer ' s methods
Graphite alkene is configured to the solution of 2mg/mL via ultrasonic wave added method；Clean quartz substrate is immersed in polyethyleneimine molten
30min~60min in liquid, obtains the quartz substrate with positive charge；The quartz substrate with positive charge is immersed in successively again
Graphene oxide solution and P25 dispersion liquids, dry up with deionized water rinsing after immersion is taken out every time and with nitrogen, are loaded with
One layer of quartz plate of graphene oxide/P25 laminated films；Above step is repeated, it is the laminated film of n to obtain being loaded with the number of plies
Quartz plate；To be loaded with again under conditions of the quartz plate of the laminated film that the number of plies is n is 120 DEG C in temperature using hydrazine hydrate reduction
2h, is loaded with [Graphene/P25]nQuartz plate；
2nd, the quartz plate assembly array of black alkene/P25 multilayer films is loaded：Several are loaded with [Graphene/P25]nQuartz plate
Along the arrangement of fluid flow direction staggered parallel in the reactor, the left end of the reactor is provided with water inlet, and right-hand member is provided with
Delivery port, the water inlet and delivery port are diagonally positioned；
3rd, continuous photocatalytic degradation technique：Opening water pump makes pending solution circulate in the reactor, first in dark condition
Lower circulation 20min~40min, then opens uviol lamp, starts light degradation process, and treating in reactor is degraded every 30min
Thing carries out Concentration Testing, when after degradation product degraded is complete, that is, completes the company based on secondary groups dress Graphene/P25 laminated films
Continuous photocatalytic process；The pending solution is the rhodamine B solution that concentration is 10mg/L.
2. one kind according to claim 1 fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups,
It is characterized in that the quality of P25 titanium dioxide described in step one is 1mg with the volume ratio of the hydrochloric acid solution that pH is 2:2mL.
3. one kind according to claim 1 fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups,
It is characterized in that the repetition above step described in step one, obtains being loaded with the quartz plate of the laminated film that the number of plies is 5.
4. according to claim 3 a kind of based on the two multistage continuous photocatalysis sides for assembling Graphene/P25 laminated films
Method, it is characterised in that the power of uviol lamp described in step 3 is 300W.
5. one kind according to claim 3 fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups,
It is characterized in that the flow velocity that water pump is controlled in step 3 is 8mL/s.
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