CN106334562A - Photocatalytic material with nano TiO2 loaded on graphene-foamed nickel and preparation method of photocatalytic material - Google Patents
Photocatalytic material with nano TiO2 loaded on graphene-foamed nickel and preparation method of photocatalytic material Download PDFInfo
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- CN106334562A CN106334562A CN201610839638.3A CN201610839638A CN106334562A CN 106334562 A CN106334562 A CN 106334562A CN 201610839638 A CN201610839638 A CN 201610839638A CN 106334562 A CN106334562 A CN 106334562A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 130
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 21
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000003980 solgel method Methods 0.000 claims abstract description 10
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006555 catalytic reaction Methods 0.000 claims description 31
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 18
- 238000007747 plating Methods 0.000 claims description 17
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001962 electrophoresis Methods 0.000 claims description 13
- 229960004756 ethanol Drugs 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 3
- 239000003054 catalyst Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
Abstract
The invention discloses a photocatalytic material with nano TiO2 loaded on graphene-foamed nickel and a preparation method of the photocatalytic material. The foamed nickel is taken as a base, a graphene film layer is deposited on the foamed nickel to form a graphene-foamed nickel composite carrier, a TiO2 sol film layer is formed on the graphene-foamed nickel composite carrier, the graphene is combined with the foamed nickel to serve as an organic carrier loaded with the nano TiO2, a three-layer structure is formed, the carrier is firmly loaded with the nano TiO2, and the photocatalytic activity of the TiO2 is greatly improved. An electrophoretic deposition method is used and a polyurethane foam serves as a base to prepare the foamed nickel with high specific surface area, the foamed nickel is then loaded with the graphene through the electrophoretic deposition method, the grapheme film layer is formed, a sol-gel method is used, no binder is used, the nano TiO2 with higher photocatalytic activity is loaded on the graphene-foamed nickel composite carrier, the whole process is simple in operation, the period is short, and the manufacturing cost is low.
Description
Technical field
The present invention relates to nano composite material technical field, particularly to a kind of Graphene-foamed nickel supported nanometer tio2
Catalysis material and preparation method thereof.
Background technology
Nanometer tio2Powder body has proven to be a kind of efficient, nontoxic, stable photocatalyst in the research in this year
Material, either all possessing in liquid phase reactor or gas phase reaction has good photocatalytic activity, but due to powder
Nanometer tio2Granule is trickle, and it is difficult to reclaim, catalyst active component loss is larger, is unfavorable for regeneration and the recycling of catalyst,
Bring much loaded down with trivial details operation to actual production, and a lot of extra-pays will be put into and go to safeguard giving birth to using satisfaction of catalyst
Produce and need.
With solid carrier by photocatalyst on carrier so that photocatalyst fixation, catalyst can be solved and divide
From the difficult problem reclaiming, suspended phase poor catalyst stability and the shortcoming of easy poisoning can also be overcome；Porous foam metal conduct
The carrier of photocatalyst, due to having lighter weight, high specific surface area, preferable vector stabilisation, and becomes research staff
The carrier of photocatalyst of the increasingly characteristic good of concern.
Wherein, nickel foam due to good mechanical property, porosity height, good stability and has good fluid behaviour, makees
For carrier of photocatalyst, apply the advantage in gas-phase photocatalysis field with uniqueness, but, in prior art, due to nickel foam
Load nanometer tio2The technology of preparing scheme of powder body, simply simply catalyst is supported in nickel foam, without to foam
During nickel carrier improves the activity to improve catalysis so that there is a problem of that catalyst activity can not fully act on and react；
And existing preparation method is often loaded using binding agent, and binding agent easily occurs hole to react with light, light itself
Catalyst action and oxidation deactivation are so that there is a problem of photocatalytic activity impacted and reducing.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of Graphene-foamed nickel supported nanometer tio2Photocatalysis material
Material, corresponding with this, another technical problem to be solved of the present invention is to provide a kind of Graphene-foamed nickel supported nanometer tio2
Catalysis material preparation method；To give full play to catalyst activity in the reaction, it is to avoid photocatalyst activity is impacted.
In order to solve above-mentioned technical problem, the technical scheme is that
A kind of Graphene-foamed nickel supported nanometer tio2Catalysis material, using nickel foam as substrate, heavy in nickel foam
Long-pending have Graphene film layer to define Graphene-nickel foam complex carrier, and Graphene-nickel foam complex carrier forms one layer of tio2
Sol pellicle layer.
As further technical scheme, nickel foam adopts polyurethane foam as matrix, by electrodeposition process preparation
Obtain；Graphene-nickel foam complex carrier is prepared using electrophoretic deposition；tio2Sol pellicle layer be using dipping-
Heating in-situ preparation loads and is formed.
As further technical scheme, nickel foam is three-dimensional net structure, and pore is intercommunicating pore, porosity is 96～
98%, aperture is 150～300 μm, and nickel mass percent is 99.9%.
Prepare above-mentioned Graphene-foamed nickel supported nanometer tio2Catalysis material method, comprise the steps:
(1) preparation of nickel foam: by polyurethane foam matrix h2cr2o7/h2so4/h3po4Mixture carry out pre-treatment
Afterwards, molten it is immersed in pdcl2In solution, carry out activation processing；Then polyurethane foam matrix is put in the plating solution containing nickel ion
Carry out electroless plating reaction, finally carry out electroplating, dry and obtain nickel foam；
(2) Graphene-nickel foam complex carrier preparation: Graphene and electrolyte are added in organic solvent, ultrasonic 1～
2h, obtains electrophoresis liquid, and with nickel foam as negative electrode, platinum electrode is anode, is placed in electrophoresis liquid, after plating 20～40min, nickel foam
Upper deposition has Graphene film layer, takes out cathode material, is dried to obtain Graphene-nickel foam complex carrier；
(3) pretreatment of Graphene-nickel foam complex carrier: by Graphene-nickel foam complex carrier through dehydrated alcohol
Supersound washing, distilled water wash, after drying at room temperature, high temperature oxidation process 10min；
(4)tio2The formation of sol pellicle layer: prepare tio with sol-gel process2Colloidal sol, by pretreated Graphene-
Nickel foam complex carrier impregnated in tio2In colloidal sol, then, it is slowly withdrawn, filters off unnecessary colloidal sol, form one layer of tio2Sol pellicle
Layer, after drying at room temperature, high temperature drying, obtain Graphene-foamed nickel supported nanometer tio2Catalysis material.
As further technical scheme, in step (4), prepare tio with sol-gel process2Colloidal sol step is: by metatitanic acid
Four butyl esters and diethanolamine is continuously stirred successively is dissolved in dehydrated alcohol, the mixed liquor of water and dehydrated alcohol is stirred vigorously
It is added dropwise in butyl titanate and the ethanol solution of diethanolamine, sealing and standing after completion of dropping is continuously stirred, obtain
tio2Colloidal sol.
As further technical scheme, nickel foam is three-dimensional net structure, and pore is intercommunicating pore, porosity is 96～
98%, aperture is 150～300 μm, and nickel mass percent is 99.9%.
As further technical scheme, in step (3), the temperature that high temperature oxidation process controls is 500～800 DEG C；Step
Suddenly, in (4), pretreated Graphene-nickel foam complex carrier be impregnated in tio2The time of colloidal sol is 5～10min, high temperature
The temperature of drying control is 500～700 DEG C.
As further technical scheme, in step (2), in electrophoresis liquid, the concentration of Graphene is 0.3～0.5mg/ml, electricity
The quality of solution matter is 2 times of Graphene.
As further technical scheme, in step (2), organic solvent is one kind of dehydrated alcohol, methanol or isopropanol
Or it is several.
As further technical scheme, nickel foam thickness is 0.8～1.0mm, the thickness of Graphene film layer is 0.2～
0.4 μm, tio2The thickness of sol pellicle layer is 0.1～0.3 μm.
Graphene-foamed nickel supported nanometer tio that the present invention provides2Catalysis material, using nickel foam as substrate, steep
On foam nickel, deposition has Graphene film layer to define Graphene-nickel foam complex carrier, and Graphene-nickel foam complex carrier is formed
One layer of tio2Sol pellicle layer, is combined as loading nanometer tio using Graphene and nickel foam2Organic carrier, define three layers
Structure is so that nanometer tio2Can firmly be carried on carrier, substantially increase tio2Photocatalytic activity, the light of the present invention is urged
Change the structural material with photo-catalysis function that material is a kind of excellent performance.
The preparation method that the present invention provides, using electrophoretic deposition, is matrix with polyurethane foam, prepares high-specific surface area
Nickel foam, then by electrophoretic deposition by graphene-supported in nickel foam, formed Graphene film layer, using sol-gel
Method, without any binding agent, has loaded the nanometer with high light catalysis activity on Graphene-nickel foam complex carrier
tio2, whole technological operation is simple, cycle is short, the raw material adopting and adjuvant price are low, not using high-end devices, therefore, whole
Individual technique greatly reduces Graphene-foamed nickel supported nanometer tio2Catalysis material manufacturing cost, the light prepared urges
Change material property superior, there is the performances such as specific surface area is big, high mechanical strength, corrosion resistance, high temperature resistant, low resistance, load
Nanometer tio2Fastness is good, and light-catalyzed reaction activity is high.
The present invention, in preparation process, when carrying out electrophoretic deposition, can be controlled by adjusting electric current density and sedimentation time
The Graphene thicknesses of layers of the deposition of nickel and Graphene formation of deposits, tio2The thickness of sol pellicle layer can pass through tio2Colloidal sol
Tio2Concentration and dip time controlling, therefore so that the catalysis material thickness prepared can be reasonable according to actual needs
Regulation and control.
Specific embodiment
Below the specific embodiment of the present invention is described further.Here is it should be noted that implement for these
The explanation of mode is used to help understand the present invention, but does not constitute limitation of the invention.Additionally, invention described below
As long as involved technical characteristic does not constitute conflict each other and just can be mutually combined in each embodiment.
A kind of Graphene-foamed nickel supported nanometer tio that the present invention provides2Catalysis material, using nickel foam as base
Bottom, in nickel foam, deposition has Graphene film layer to define Graphene-nickel foam complex carrier, Graphene-nickel foam complex carrier
One layer of tio of upper formation2Sol pellicle layer.
Nickel foam adopts polyurethane foam as matrix, is prepared by electrodeposition process；Graphene-nickel foam is combined
Carrier is prepared using electrophoretic deposition；tio2Sol pellicle layer is to be formed using dipping-heating in-situ preparation load.
Nickel foam is three-dimensional net structure, and pore is intercommunicating pore, and porosity is 96～98%, and aperture is 150～300 μm,
Nickel mass percent is 99.9%.
Embodiment 1
Graphene-foamed nickel supported nanometer tio2Catalysis material preparation
The polyurethane foam matrix that aperture is 200 μm, weight is about 80mg, uses h2cr2o7/h2so4/h3po4Mass ratio
After mixture for 5:3:1 carries out pre-treatment, the molten pdcl being immersed in 20g/l2In solution, room temperature carries out activation processing；Then will
Polyurethane foam matrix is put into containing 20g/lniso4、30g/lna3cyt、45g/lna3po4Plating solution in carry out chemical plating anti-
Should, finally, polyurethane foam is negative electrode, and platinum electrode carries out electroplating after 20min for anode, dries and obtains nickel foam；Scanned electricity
The photo of mirror and transmission electron microscope observes that nickel foam is in three-dimensional net structure, and pore is intercommunicating pore, and porosity is 96%, and aperture is
300 μm, nickel mass percent is 99.9%, and thickness is 0.8mm.
Take 25mg Graphene and 50mgmg (no3)·6h2O electrolyte adds in dehydrated alcohol, and compound concentration is 0.3mg/ml
Electrophoresis liquid, ultrasonic 1h, with nickel foam as negative electrode, platinum electrode be anode, be placed in electrophoresis liquid, plating 20min after, obtain black alkene
The thickness of film layer is 0.2 μm, takes out cathode material, is dried to obtain Graphene-nickel foam complex carrier.
By the dehydrated alcohol supersound washing 2 times of Graphene-nickel foam complex carrier, distilled water wash 2 times, drying at room temperature
After 12h, it is placed in Muffle furnace, 500 DEG C of high temperature oxidation process 10min, be cooled to room temperature stand-by.
Prepare tio with sol-gel process2Colloidal sol step is: 20ml butyl titanate and 6ml diethanolamine are continued successively
Stir to being dissolved completely in 60ml dehydrated alcohol, the mixed liquor of 1ml water and 2ml dehydrated alcohol is stirred vigorously and is added dropwise over
To in the ethanol solution of above-mentioned butyl titanate and diethanolamine, treat the continuously stirred 2h of completion of dropping, seal overnight stand, obtain
tio2Colloidal sol, in colloidal sol, each Component molar content is than for butyl titanate: diethanolamine: water: ethanol=1:1:1:8.
Pretreated Graphene-nickel foam complex carrier be impregnated in tio25min in colloidal sol, then, is slowly withdrawn,
Filter off unnecessary colloidal sol, form the tio that a layer thickness is 0.1 μm2Sol pellicle layer, 12h after drying at room temperature, it is placed in Muffle furnace,
500 DEG C of high temperature dryings 50min, obtain Graphene-foamed nickel supported nanometer tio2Catalysis material.
Embodiment 2
Graphene-foamed nickel supported nanometer tio2Catalysis material preparation
The polyurethane foam matrix that aperture is 400 μm, weight is about 80mg, uses h2cr2o7/h2so4/h3po4Mass ratio
After mixture for 5:3:1 carries out pre-treatment, the molten pdcl being immersed in 20g/l2In solution, room temperature carries out activation processing；Then will
Polyurethane foam matrix is put into containing 20g/lniso4、30g/lna3cyt、45g/lna3po4Plating solution in carry out chemical plating anti-
Should, finally, polyurethane foam is negative electrode, and platinum electrode carries out electroplating after 30min for anode, dries and obtains nickel foam；Scanned electricity
The photo of mirror and transmission electron microscope observes that nickel foam is in three-dimensional net structure, and pore is intercommunicating pore, and porosity is 97.5%, aperture
For 200 μm, nickel mass percent is 99.9%, and thickness is 0.82mm.
Take 25mg Graphene and 50mgmg (no3)·6h2O electrolyte adds in methanol, and compound concentration is the electricity of 0.4mg/ml
Swimming liquid, ultrasonic 2h, with nickel foam as negative electrode, platinum electrode is anode, is placed in electrophoresis liquid, after plating 30min, obtains black alkene film layer
Thickness be 0.29 μm, take out cathode material, be dried to obtain Graphene-nickel foam complex carrier.
By the dehydrated alcohol supersound washing 2 times of Graphene-nickel foam complex carrier, distilled water wash 2 times, drying at room temperature
After 12h, it is placed in Muffle furnace, 700 DEG C of high temperature oxidation process 10min, be cooled to room temperature stand-by.
Prepare tio with sol-gel process2Colloidal sol step is: 20ml butyl titanate and 6ml diethanolamine are continued successively
Stir to being dissolved completely in 60ml dehydrated alcohol, the mixed liquor of 1ml water and 2ml dehydrated alcohol is stirred vigorously and is added dropwise over
To in the ethanol solution of above-mentioned butyl titanate and diethanolamine, treat the continuously stirred 2h of completion of dropping, seal overnight stand, obtain
tio2Colloidal sol, in colloidal sol, each Component molar content is than for butyl titanate: diethanolamine: water: ethanol=1:1:1:8.
Pretreated Graphene-nickel foam complex carrier be impregnated in tio28min in colloidal sol, then, is slowly withdrawn,
Filter off unnecessary colloidal sol, form the tio that a layer thickness is 0.18 μm2Sol pellicle layer, 12h after drying at room temperature, it is placed in Muffle furnace,
600 DEG C of high temperature dryings 50min, obtain Graphene-foamed nickel supported nanometer tio2Catalysis material.
Embodiment 3
Graphene-foamed nickel supported nanometer tio2Catalysis material preparation
The polyurethane foam matrix that aperture is 400 μm, weight is about 80mg, uses h2cr2o7/h2so4/h3po4Mass ratio
After mixture for 5:3:1 carries out pre-treatment, the molten pdcl being immersed in 20g/l2In solution, room temperature carries out activation processing；Then will
Polyurethane foam matrix is put into containing 20g/lniso4、30g/lna3cyt、45g/lna3po4Plating solution in carry out chemical plating anti-
Should, finally, polyurethane foam is negative electrode, and platinum electrode carries out electroplating after 40min for anode, dries and obtains nickel foam；Scanned electricity
The photo of mirror and transmission electron microscope observes that nickel foam is in three-dimensional net structure, and pore is intercommunicating pore, and porosity is 98.1%, aperture
For 200 μm, nickel mass percent is 99.9%, and thickness is 0.88mm.
Take 25mg Graphene and 50mgmg (no3)·6h2It is the dehydrated alcohol of 1:1 that o electrolyte adds volume ratio, methanol mixes
Close in liquid, compound concentration is the electrophoresis liquid of 0.4mg/ml, ultrasonic 2h, with nickel foam as negative electrode, platinum electrode is anode, is placed in electrophoresis
In liquid, after plating 40min, the thickness obtaining black alkene film layer is 0.32 μm, takes out cathode material, is dried to obtain Graphene-foam
Nickel complex carrier.
By the dehydrated alcohol supersound washing 2 times of Graphene-nickel foam complex carrier, distilled water wash 2 times, drying at room temperature
After 12h, it is placed in Muffle furnace, 700 DEG C of high temperature oxidation process 10min, be cooled to room temperature stand-by.
Prepare tio with sol-gel process2Colloidal sol step is: 20ml butyl titanate and 6ml diethanolamine are continued successively
Stir to being dissolved completely in 60ml dehydrated alcohol, the mixed liquor of 1ml water and 2ml dehydrated alcohol is stirred vigorously and is added dropwise over
To in the ethanol solution of above-mentioned butyl titanate and diethanolamine, treat the continuously stirred 2h of completion of dropping, seal overnight stand, obtain
tio2Colloidal sol, in colloidal sol, each Component molar content is than for butyl titanate: diethanolamine: water: ethanol=1:1:1:8.
Pretreated Graphene-nickel foam complex carrier be impregnated in tio28min in colloidal sol, then, is slowly withdrawn,
Filter off unnecessary colloidal sol, form the tio that a layer thickness is 0.18 μm2Sol pellicle layer, 12h after drying at room temperature, it is placed in Muffle furnace,
600 DEG C of high temperature dryings 50min, obtain Graphene-foamed nickel supported nanometer tio2Catalysis material.
Embodiment 4
Graphene-foamed nickel supported nanometer tio2Catalysis material preparation
The polyurethane foam matrix that aperture is 500 μm, weight is about 80mg, uses h2cr2o7/h2so4/h3po4Mass ratio
After mixture for 5:3:1 carries out pre-treatment, the molten pdcl being immersed in 20g/l2In solution, room temperature carries out activation processing；Then will
Polyurethane foam matrix is put into containing 20g/lniso4、30g/lna3cyt、45g/lna3po4Plating solution in carry out chemical plating anti-
Should, finally, polyurethane foam is negative electrode, and platinum electrode carries out electroplating after 40min for anode, dries and obtains nickel foam；Scanned electricity
The photo of mirror and transmission electron microscope observes that nickel foam is in three-dimensional net structure, and pore is intercommunicating pore, and porosity is 98.2%, aperture
For 290 μm, nickel mass percent is 99.9%, and thickness is 1.0mm.
Take 25mg Graphene and 50mgmg (no3)·6h2It is the methanol of 1:1 that o electrolyte adds volume ratio, isopropanol mixing
In liquid, compound concentration is the electrophoresis liquid of 0.5mg/ml, ultrasonic 2h, and with nickel foam as negative electrode, platinum electrode is anode, is placed in electrophoresis liquid
In, after plating 40min, the thickness obtaining black alkene film layer is 0.4 μm, takes out cathode material, is dried to obtain Graphene-nickel foam multiple
Close carrier.
By the dehydrated alcohol supersound washing 2 times of Graphene-nickel foam complex carrier, distilled water wash 2 times, drying at room temperature
After 12h, it is placed in Muffle furnace, 800 DEG C of high temperature oxidation process 10min, be cooled to room temperature stand-by.
Prepare tio with sol-gel process2Colloidal sol step is: 20ml butyl titanate and 6ml diethanolamine are continued successively
Stir to being dissolved completely in 60ml dehydrated alcohol, the mixed liquor of 1ml water and 2ml dehydrated alcohol is stirred vigorously and is added dropwise over
To in the ethanol solution of above-mentioned butyl titanate and diethanolamine, treat the continuously stirred 2h of completion of dropping, seal overnight stand, obtain
tio2Colloidal sol, in colloidal sol, each Component molar content is than for butyl titanate: diethanolamine: water: ethanol=1:1:1:8.
Pretreated Graphene-nickel foam complex carrier be impregnated in tio210min in colloidal sol, then, is slowly withdrawn,
Filter off unnecessary colloidal sol, form the tio that a layer thickness is 0.3 μm2Sol pellicle layer, 12h after drying at room temperature, it is placed in Muffle furnace,
700 DEG C of high temperature dryings 50min, obtain Graphene-foamed nickel supported nanometer tio2Catalysis material.
Above embodiments of the present invention are explained in detail, but the invention is not restricted to described embodiment.Right
For those skilled in the art, in the case of without departing from the principle of the invention and spirit, these embodiments are carried out many
Plant change, modification, replace and modification, still fall within protection scope of the present invention.
Claims (10)
1. a kind of Graphene-foamed nickel supported nanometer tio2Catalysis material it is characterised in that using nickel foam as substrate, steeping
On foam nickel, deposition has Graphene film layer to define Graphene-nickel foam complex carrier, on described Graphene-nickel foam complex carrier
Form one layer of tio2Sol pellicle layer.
2. Graphene according to claim 1-foamed nickel supported nanometer tio2Catalysis material it is characterised in that described
Nickel foam adopts polyurethane foam as matrix, is prepared by electrodeposition process；Described Graphene-nickel foam complex carrier
It is prepared using electrophoretic deposition；tio2Sol pellicle layer is to be formed using dipping-heating in-situ preparation load.
3. Graphene according to claim 1-foamed nickel supported nanometer tio2Catalysis material it is characterised in that described
Nickel foam is three-dimensional net structure, and pore is intercommunicating pore, and porosity is 96～98%, and aperture is 150～300 μm, nickel quality hundred
Divide ratio for 99.9%.
4. the Graphene according to claims 1 to 3-foamed nickel supported nanometer tio2Catalysis material preparation method, its
It is characterised by, comprise the steps:
(1) preparation of nickel foam: by polyurethane foam matrix h2cr2o7/h2so4/h3po4Mixture carry out pre-treatment after, molten
It is immersed in pdcl2In solution, carry out activation processing；Then polyurethane foam matrix is put in the plating solution containing nickel ion and changed
Learn plating reaction, finally carry out electroplating, dry and obtain nickel foam；
(2) Graphene-nickel foam complex carrier preparation: Graphene and electrolyte are added in organic solvent, ultrasonic 1～2h, obtain
To electrophoresis liquid, with nickel foam as negative electrode, platinum electrode is anode, is placed in electrophoresis liquid, after plating 20～40min, heavy in nickel foam
Long-pending have Graphene film layer, takes out cathode material, is dried to obtain Graphene-nickel foam complex carrier；
(3) pretreatment of Graphene-nickel foam complex carrier: will be ultrasonic through dehydrated alcohol for Graphene-nickel foam complex carrier
Washing, distilled water wash, after drying at room temperature, high temperature oxidation process 10min；
(4)tio2The formation of sol pellicle layer: prepare tio with sol-gel process2Colloidal sol, by pretreated Graphene-foam
Nickel complex carrier impregnated in tio2In colloidal sol, then, it is slowly withdrawn, filters off unnecessary colloidal sol, form one layer of tio2Sol pellicle layer,
After drying at room temperature, high temperature drying, obtain Graphene-foamed nickel supported nanometer tio2Catalysis material.
5. Graphene according to claim 4-foamed nickel supported nanometer tio2Catalysis material preparation method, it is special
Levy and be, in step (4), prepare tio with sol-gel process2Colloidal sol step is: butyl titanate and diethanolamine are held successively
Continuous stirring and dissolving in dehydrated alcohol, by the mixed liquor of water and dehydrated alcohol, be stirred vigorously be added dropwise to butyl titanate and
In the ethanol solution of diethanolamine, sealing and standing after completion of dropping is continuously stirred, obtain tio2Colloidal sol.
6. Graphene according to claim 4-foamed nickel supported nanometer tio2Catalysis material preparation method, it is special
Levy and be, described nickel foam is three-dimensional net structure, pore is intercommunicating pore, porosity is 96～98%, aperture is 150～300 μ
M, nickel mass percent is 99.9%.
7. Graphene according to claim 4-foamed nickel supported nanometer tio2Catalysis material preparation method, it is special
Levy and be, in step (3), the temperature that high temperature oxidation process controls is 500～800 DEG C；In step (4), by pretreated stone
Black alkene-nickel foam complex carrier impregnated in tio2The time of colloidal sol be 5～10min, high temperature drying control temperature be 500～
700℃.
8. Graphene according to claim 4-foamed nickel supported nanometer tio2Catalysis material preparation method, it is special
Levy and be, in step (2), in described electrophoresis liquid, the concentration of Graphene is 0.3～0.5mg/ml, the quality of electrolyte is Graphene
2 times.
9. Graphene according to claim 4-foamed nickel supported nanometer tio2Catalysis material preparation method, it is special
Levy and be, in step (2), described organic solvent is one or more of dehydrated alcohol, methanol or isopropanol.
10. Graphene according to claim 4-foamed nickel supported nanometer tio2Catalysis material preparation method, it is special
Levy and be, described nickel foam thickness is 0.8～1.0mm, the thickness of described Graphene film layer is 0.2～0.4 μm, described tio2Molten
The thickness of glue thin layer is 0.1～0.3 μm.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021645A (en) * | 2017-03-17 | 2017-08-08 | 东南大学 | A kind of titanium dioxide self-cleaning film and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436939A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-graphene composite material and preparation method thereof |
| CN103551198A (en) * | 2013-11-19 | 2014-02-05 | 南京工业大学 | Magnetic-control dynamic ciliary bionic photocatalytic array and preparation method thereof |
| CN104163421A (en) * | 2014-07-27 | 2014-11-26 | 北京工业大学 | Preparation method of three-dimensional flocculent graphene substrate material and application |
| CN104307525A (en) * | 2014-10-08 | 2015-01-28 | 西安华陆环保设备有限公司 | Preparation method of foamed nickel-supported TiO2 photocatalyst |
| KR20160039539A (en) * | 2014-10-01 | 2016-04-11 | 한양대학교 산학협력단 | hybrid structure having three-dimensional structure and method for manufacturing the same |
| CN105682442A (en) * | 2016-04-06 | 2016-06-15 | 常州市奥普泰科光电有限公司 | Preparation method for light-weight graphite fiber foam nickel electromagnetic shielding material |
-
2016
- 2016-09-21 CN CN201610839638.3A patent/CN106334562A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436939A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-graphene composite material and preparation method thereof |
| CN103551198A (en) * | 2013-11-19 | 2014-02-05 | 南京工业大学 | Magnetic-control dynamic ciliary bionic photocatalytic array and preparation method thereof |
| CN104163421A (en) * | 2014-07-27 | 2014-11-26 | 北京工业大学 | Preparation method of three-dimensional flocculent graphene substrate material and application |
| KR20160039539A (en) * | 2014-10-01 | 2016-04-11 | 한양대학교 산학협력단 | hybrid structure having three-dimensional structure and method for manufacturing the same |
| CN104307525A (en) * | 2014-10-08 | 2015-01-28 | 西安华陆环保设备有限公司 | Preparation method of foamed nickel-supported TiO2 photocatalyst |
| CN105682442A (en) * | 2016-04-06 | 2016-06-15 | 常州市奥普泰科光电有限公司 | Preparation method for light-weight graphite fiber foam nickel electromagnetic shielding material |
Non-Patent Citations (3)
| Title |
|---|
| 伍学高: "《塑料电镀技术》", 30 April 1983 * |
| 刘培生: "《多孔材料引论》", 30 September 2004 * |
| 北京矿冶研究总院: "《冶金和材料学术会议论文集》", 31 December 1994 * |
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