CN104815638A - Preparation method of amorphous nano-porous titanium dioxide-supported graphene photocatalytic thin film - Google Patents
Preparation method of amorphous nano-porous titanium dioxide-supported graphene photocatalytic thin film Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 60
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010936 titanium Substances 0.000 title claims abstract description 6
- 239000010409 thin film Substances 0.000 title abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052719 titanium Inorganic materials 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000005275 alloying Methods 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000007146 photocatalysis Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 14
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 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 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 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 4
- 210000003041 ligament Anatomy 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
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- 239000002131 composite material Substances 0.000 abstract description 6
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 238000006722 reduction reaction Methods 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 238000006056 electrooxidation reaction Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 22
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000005518 electrochemistry Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
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- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
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- -1 Graphene compound Chemical class 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000002912 waste gas Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of an amorphous nano-porous titanium dioxide-supported graphene photocatalytic thin film and aims to provide a novel graphene-TiO2 composite electrode catalyst. According to the preparation method, firstly an electrochemical three-electrode system is employed in experiment with a nitric acid solution as an electrolyte solution, and an electrochemical workstation is used for respectively applying a constant-voltage to an amorphous alloy stripe to perform constant-voltage electrochemical corrosion, thereby forming a nano-porous thin film structure being uniform in pore distribution; and then graphite is fully oxidized through a strong oxidizing agent to prepare a graphene oxide solution; and then through a Czochralski method, an graphene oxide coating layer in a certain thickness is formed on the surface of the amorphous nano-porous titanium dioxide stripe; and finally the graphene thin film is prepared through an oxidation/reduction reaction. In the invention, preparation of the graphene thin film on the surface of the amorphous nano-porous titanium dioxide stripe is disclosed through dealloying, oxidation/reduction reaction with combination of the Czochralski method. The preparation method is low in cost, is strong in controllability, is low in reaction temperature and is a high-effective and economical synthetic method.
Description
Technical field
The present invention relates to a kind of preparation method of New-type nano porous film electrode, more particularly, particularly relate to a kind of preparation method being applied to the nano porous titanium dioxide load Graphene photocatalysis film electrode of the high catalytic activity in electro-catalysis field.
Background technology
Since finding that semiconductor titanium dioxide split water into hydrogen and oxygen under UV-irradiation from 1972, the research of optically catalytic TiO 2 and Optical Electro-Chemistry is always very active, is widely used in the exploitation of opto-electronic conversion solar cell, gas sensor, decomposing water with solar energy hydrogen, the photocatalytic degradation of sewage and waste gas, photo-catalyst, automatically cleaning and the many aspects such as antifog.Titanium dioxide cost is low, non-secondary pollution, stable performance, and utilize sunshine that light-catalyzed reaction just can be driven to carry out.But, TiO
2energy gap comparatively large (Eg=3.0 ~ 3.2Ev), can only be activated by the ultraviolet light of below 400nm, to the absorption difference of visible ray, significantly limit its range of application.The emphasis of research is concentrated on TiO by scientist
2visible ray modification and improve on catalytic efficiency.At present, the method for visible ray modification mainly contains doping and compound.This wherein, carbon nanomaterial, due to the physical and chemical performance of its uniqueness, makes itself and TiO
2the Photocatalytic Performance Study of composite becomes a popular direction.
Bidimensional (2D) the cycle honeycomb lattice structure that Graphene is made up of carbon hexatomic ring, it can be warped into the fullerene (fullerene) of zero dimension (0D), be rolled into CNT (the carbon nanotube of one dimension (1D), CNT) or be stacked to the graphite (graphite) of three-dimensional (3D), therefore Graphene is the elementary cell forming other graphite materials.Research shows, the theoretical specific surface area of Graphene is up to 2600 m
2g
-1, there are outstanding heat conductivility (3000 Wm
-1k
-1)) and mechanical property (1060 GPa), and electron mobility (15000cm at a high speed under room temperature
2v
-1s
-1)), the structure that Graphene is special, makes it have the series of properties such as perfect quantum tunneling effect, half integral quantum hall effect, the electrical conductivity that never disappears.These special character, all can make Graphene produce active influence to light-catalyzed reaction.Therefore, for other carbon nanomaterial, Graphene and TiO
2compound may be more preferably catalysis material.At present, TiO is prepared
2hydro-thermal method, sol-gel process two kinds is mainly contained with the method for graphene composite material.The feature of these methods is by TiO
2nano particle and Graphene carry out compound.But, because this composite photo-catalyst is the powder of micro-nano-scale, there is problems such as recycling and reclaim difficulty in actual applications, very large impact is brought on its photocatalysis efficiency and life-span, is difficult to functionalization and device.
In recent years, the life problems of catalysis material and device thereof apply the important research direction being.It is generally acknowledged and prepare TiO on matrix
2the method of film can overcome TiO
2the deficiency that nano particle brings.Current preparation TiO
2the method of film has pulsed laser deposition (PLD), magnetron sputtering method (sputtering), micro-arc oxidation (MAO) etc.But these masking techniques are for chemical preparation method, and technological requirement is more complicated, are particularly difficult to realize TiO
2with the compound of material with carbon element.
Summary of the invention
The present invention will solve current TiO
2and be difficult to the technical problem realizing compound between material with carbon element, a kind of preparation method of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film is provided.
The present invention for solving the problems of the technologies described above provided technical scheme is: a kind of preparation method of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film, comprise the following steps: (1) by after amorphous state Ti-Ag alloy strip cleaning-drying at its dual coating silica gel, reserve active length during coating silica gel, treat that silica gel hardens;
(2) preparing mass fraction is that the aqueous solution of nitric acid of 25%-55% is poured in reaction utensil, and reaction utensil is placed in the water-bath setting temperature, has the amorphous state Ti-Ag alloy strip of silica gel to be fixed in reaction utensil electrode system and above-mentioned dual coating;
(3) utilize electrochemical workstation to go alloy corrosion process to amorphous state Ti-Ag alloy strip, constant voltage goes the potential value of alloy to be 0.5V-1.5V, removes the time 3600s-10800s of alloy, reaction temperature 45 DEG C-85 DEG C;
(4) utilize strong oxidizer fully oxidized to graphite, then, band after removal alloying is fixed on pulling machine and lifts, strip face after removal alloying obtains graphene oxide clad, finally, the band after lift is immersed in graphene oxide solution, adds hydrazine hydrate and fully react, strip face after removal alloying can generate the graphene film of one deck even compact, thus obtain amorphous nano poriferous titanium dioxide load Graphene photocatalysis film.
The application passes through removal alloying, oxidation-reduction method combines lift coating method and prepares graphene film in amorphous nano poriferous titanium dioxide strip face, every step that described removal alloying adopts as the concentration of double spread, aqueous solution of nitric acid and electrochemical workstation the technological parameter that adopts make the surface of band extremely be conducive to the combination with graphene oxide film after treatment, be the key technology obtaining final products.
Further, in step (4), utilize strong oxidizer fully oxidized to graphite, described strong oxidizer adopts dense H
2sO
4, KMnO
4in ice bath, graphite is fully oxidized, namely on ice bath, 1.5h is stirred, temperature is risen to 30 DEG C, water bath with thermostatic control is warming up to 70 DEG C after stirring 1h, after stirring 15min, deionized water is added in reaction solution, adding required time is 1.5h, after constant temperature 70 DEG C reaction 30min, adds rapidly 500ml deionized water and 30ml H
2o
2, now solution is in golden yellow; Stir after leaving standstill, take off a layer solid solution, with rare HCl 5wt%, solid solution washing is centrifugal, dry at 80 DEG C, obtain graphite oxide (brownish black), ground by graphite oxide, it is ultrasonic to add deionized water, is made into the graphene oxide solution of 1mg/ml.Then, be fixed on by band on pulling machine and lift, obtaining certain thickness graphene oxide clad lift optimum configurations in strip face is: dip time 20s, time of staying 3s, the speed of service 2000 μm/s, lift number of times 20 times.Finally, namely in step 4, band after lift is immersed in graphene oxide solution, add hydrazine hydrate fully to react, specifically, the band after lift process is put into the graphene oxide solution of 100ml, add the 80wt% hydrazine hydrate of 0.2ml, utilize reflux, water bath with thermostatic control 24h at 80 DEG C in water-bath, the graphene film of one deck even compact can be generated in strip face.
Oxidation-reduction method of the present invention contribute to graphene oxide be coated on removal alloying after strip face; Water-bath step after lift then provides technology guarantee for finally realizing amorphous nano poriferous titanium dioxide load Graphene photocatalysis film.
The present invention passes through removal alloying, oxidation-reduction method combines lift coating method and prepares graphene film in amorphous nano poriferous titanium dioxide strip face, and this layered composite film can be good at overcoming nano particle and is difficult to the difficult problem that separation and recovery and thin-film material be difficult to carry out with Graphene compound.It is advantageous that the material of different performance can be worked in coordination with together well, display one's respective advantages most possibly.And combine closely between rete and matrix, enhance TiO
2the photocatalysis performance of/graphene composite material and cycle life, have good prospect in the application aspect of functionalization and device.
The invention process expense is low, easy and simple to handle, and controllability is strong, and reproducible, reaction temperature is low, is a kind of synthetic method of high-efficiency and economic.
Accompanying drawing explanation
Shape appearance figure after Fig. 1 amorphous state Ti-Ag alloy removal alloying.
The shape appearance figure of 50,000 times is amplified after Fig. 2 amorphous state Ti-Ag alloy removal alloying.
The pattern photo of Fig. 3 amorphous nano poriferous titanium dioxide load Graphene.
Detailed description of the invention
A preparation method for amorphous nano poriferous titanium dioxide load Graphene photocatalysis film, is prepared according to following step:
(1) by after amorphous state Ti-Ag alloy strip (thickness is generally 20-60 μm, best 50 μm) cleaning-drying at its dual coating silica gel, reserve active length during coating silica gel, treat that silica gel hardens;
(2) prepare mass fraction be that 25%-55%(can select 25%, 30%, 35%, 40%, 45%, 50%, 55%) aqueous solution of nitric acid pour in reaction utensil, and reaction utensil is placed in the water-bath setting temperature, there is the amorphous state Ti-Ag alloy strip of silica gel to be fixed in reaction utensil electrode system and above-mentioned dual coating;
(3) electrochemical workstation is utilized to go alloy corrosion process to amorphous state Ti-Ag alloy strip, constant voltage goes the potential value of alloy to be that 0.5V-1.5V(can select 0.5V, 1.0V, 1.5V), the time 3600s-10800s(of alloy is gone to select 3600s, 5400s, 7200s, 10800s), reaction temperature 45 DEG C-85 DEG C (i.e. the temperature of water-bath can select 45 DEG C, 60 DEG C, 70 DEG C, 85 DEG C);
(4) utilize strong oxidizer fully oxidized to graphite, then, band after removal alloying is fixed on pulling machine and lifts, strip face after removal alloying obtains graphene oxide clad, finally, band after lift is immersed in graphene oxide solution, adds hydrazine hydrate and fully react, the strip face after removal alloying can generate the graphene film of one deck even compact.
The alloying component of described amorphous state Ti-Ag AMORPHOUS ALLOY RIBBONS presses atomic percentage, the content of Ti is that 30%-70%(can select 30%, 40%, 50%, 60%, 70%), the content of Ag is that 30%-70%(can select 70%, 60%, 50%, 40%, 30%).
The aperture finally obtaining the nanoporous in material is that 20-100nm(can select 20nm, 40nm, 60nm, 80nm, 100nm), hole wall is that 50-100nm(can select 50nm, 60nm, 70nm, 80 nm, 90nm, 100nm), ligament is of a size of 50 ± 25nm and nano aperture and ligament are uniformly distributed.
Below by way of several specific embodiment to illustrate the present invention.
Embodiment 1
Constant voltage is utilized to go alloyage to prepare nanoporous TiO on amorphous state Ti-Ag alloy strip surface
2the said constant voltage of membrane electrode goes alloyage to be utilize Gamry Reference600 electrochemical workstation, adopt traditional electrochemistry three-electrode system, wherein Pt plate electrode (2cm × 2cm × 5mm) conduct is to electrode, saturated calomel electrode (SCE) is as reference electrode, apply the Ti-Ag noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry go alloy reaction to obtain.Constant voltage goes the technological parameter adopted in alloy corrosion process to be: the composition (alloy element component is by atomic percentage) of Ti-Ag amorphous alloy: Ti:30%; Ag:70%; Concentration of electrolyte: mass fraction is the aqueous solution of nitric acid of 30%; Electrolyte; Temperature: 70 DEG C; Constant voltage current potential: 0.5V; Reaction time: 5400s.
Take 3g graphite powder, after putting into beaker, add the dense H that 90ml concentration is 98wt%
2sO
4, and be placed on magnetic stirring apparatus and constantly stir, slowly add KMnO
4powder 12g, after ice bath stirs 1.5h, rises to 30 DEG C by temperature, water bath with thermostatic control is warming up to 70 DEG C after stirring 1h.After 15min, in reaction solution, slowly add 250ml deionized water, the time is 1.5h, after reaction 30min, adds rapidly 500ml deionized water and 30mlH
2o
2, now solution is in golden yellow.Stir after leaving standstill, take off a layer solid solution, wash and centrifugal with rare HCl 5wt%, dry, obtain graphite oxide (brownish black) at 80 DEG C, by its grinding, it is ultrasonic to add deionized water, is made into the graphene oxide solution of 1mg/ml.Be fixed on by band after removal alloying on pulling machine and carry out lift plated film, lift optimum configurations is: dip time: 20s; The time of staying: 3s; The speed of service: 2000 μm/s; Lift number of times: 20 times.Treated band adheres to graphene oxide film, band after lift process is put into the graphene oxide solution of 100ml, add 80% hydrazine hydrate of 0.2ml, utilize reflux, water bath with thermostatic control 24h at 80 DEG C in water-bath, can generate the graphene film of one deck even compact in strip face.
Embodiment 2
Constant voltage is utilized to go alloyage to prepare nanoporous TiO on amorphous state Ti-Ag alloy strip surface
2the said constant voltage of membrane electrode goes alloyage to be utilize Gamry Reference600 electrochemical workstation, adopt traditional electrochemistry three-electrode system, wherein Pt net electrode (2cm × 2cm) conduct is to electrode, saturated calomel electrode (SCE) is as reference electrode, apply the Ti-Ag noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry go alloy reaction to obtain.Constant voltage goes the technological parameter adopted in alloy corrosion process to be: the composition (alloy element component is by atomic percentage) of Ti-Ag amorphous alloy: Ti:40%; Ag:60%; Concentration of electrolyte: mass fraction is the aqueous solution of nitric acid of 30%; Electrolyte; Temperature: 50 DEG C; Constant voltage current potential: 1.5V; Reaction time: 3600s.
Take 3g natural graphite powder, after putting into beaker, add the dense H that 120ml concentration is 98wt%
2sO
4, and be placed on magnetic stirring apparatus and constantly stir, slowly add KMnO
4powder 15g, after ice bath stirs 1.5h, rises to 40 DEG C by temperature, water bath with thermostatic control is warming up to 60 DEG C after stirring 1h.After 15min, in reaction solution, slowly add 250ml deionized water, the time is 1.5h, after reaction 30min, adds rapidly 500ml deionized water and 30ml H
2o
2, now solution is in golden yellow.Stir after leaving standstill, take off a layer solid solution, wash and centrifugal with rare HCl 5wt%, dry, obtain graphite oxide (brownish black) at 80 DEG C, by its grinding, it is ultrasonic to add deionized water, is made into the graphene oxide solution of 1mg/ml.Be fixed on by band after removal alloying on pulling machine and carry out lift plated film, lift optimum configurations is: dip time: 20s; The time of staying: 3s; The speed of service: 2000 μm/s; Lift number of times: 20 times.Band after lift process is put into the graphene oxide solution of 100ml, add 80% hydrazine hydrate of 0.1ml, utilize reflux, water bath with thermostatic control 24h at 80 DEG C in water-bath, the strip face after removal alloying can generate the graphene film of one deck even compact.
Claims (7)
1. a preparation method for amorphous nano poriferous titanium dioxide load Graphene photocatalysis film, is characterized in that, is prepared according to following step:
(1) by after amorphous state Ti-Ag alloy strip cleaning-drying at its dual coating silica gel, coating silica gel time reserve active length, treat that silica gel hardens;
(2) preparing mass fraction is that the aqueous solution of nitric acid of 25%-55% is poured in reaction utensil, and reaction utensil is placed in the water-bath setting temperature, has the amorphous state Ti-Ag alloy strip of silica gel to be fixed in reaction utensil electrode system and above-mentioned dual coating;
(3) utilize electrochemical workstation to go alloy corrosion process to amorphous state Ti-Ag alloy strip, constant voltage goes the potential value of alloy to be 0.5V-1.5V, removes the time 3600s-10800s of alloy, reaction temperature 45 DEG C-85 DEG C;
(4) utilize strong oxidizer fully oxidized to graphite, then, band after removal alloying is fixed on pulling machine and lifts, strip face after removal alloying obtains graphene oxide clad, finally, be immersed in graphene oxide solution by the band after lift, add hydrazine hydrate and fully react, the strip face namely after removal alloying generates the graphene film of one deck even compact.
2. according to the preparation method of a kind of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film described in claim 1, it is characterized in that, described constant voltage goes the potential value of alloy to be 1.0V-1.5V, removes the time 5400s-7200s of alloy, reaction temperature 60 DEG C-70 DEG C.
3. according to the preparation method of a kind of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film described in claim 1, it is characterized in that, the alloying component of described amorphous state Ti-Ag AMORPHOUS ALLOY RIBBONS presses atomic percentage, the content of Ti be 30%-70%, Ag content be 30%-70%.
4. according to the preparation method of a kind of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film described in claim 1, it is characterized in that, the aperture finally obtaining the nanoporous in material is 20-100nm, hole wall is 50-100nm, and ligament is of a size of 50 ± 25nm and nano aperture and ligament are uniformly distributed.
5. the preparation method of a kind of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film according to any one of claim 1 ~ 4, it is characterized in that, utilize strong oxidizer fully oxidized to graphite, described strong oxidizer adopts dense H
2sO
4and KMnO
4; Dense H
2sO
4, KMnO
4in ice bath, graphite is fully oxidized, namely on ice bath, 1.5h is stirred, temperature is risen to 30 DEG C, water bath with thermostatic control is warming up to 70 DEG C after stirring 1h, after stirring 15min, deionized water is added in reaction solution, adding required time is 1.5h, after constant temperature 70 DEG C reaction 30min, adds rapidly 500ml deionized water and 30ml H
2o
2, now solution is in golden yellow; Stir after leaving standstill, take off a layer solid solution, with rare HCl 5wt%, solid solution washing is centrifugal, dry at 80 DEG C, obtain graphite oxide, ground by graphite oxide, it is ultrasonic to add deionized water, is made into the graphene oxide solution of 1mg/ml.
6. the preparation method of a kind of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film according to any one of claim 1 ~ 4, it is characterized in that, in described step 4, band after removal alloying is fixed on pulling machine and lifts, obtain graphene oxide clad in strip face, lift optimum configurations is: dip time 20s, time of staying 3s, the speed of service 2000 μm/s, lift number of times 20 times.
7. the preparation method of a kind of amorphous nano poriferous titanium dioxide load Graphene photocatalysis film according to any one of claim 1 ~ 4, it is characterized in that, in described step 4, band after lift process is put in the graphene oxide solution of 100ml, add the 80wt% hydrazine hydrate of 0.2ml, utilize reflux, water bath with thermostatic control 24h at 80 DEG C in water-bath, the graphene film of one deck even compact can be generated in porous strip face.
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| CN110560010A (en) * | 2019-07-31 | 2019-12-13 | 北京建筑大学 | Preparation method and application of multilayer cyclodextrin-graphene oxide framework film adsorbent |
| CN112844040A (en) * | 2021-01-26 | 2021-05-28 | 中国人民解放军火箭军工程大学 | Method for purifying gas-phase unsymmetrical dimethylhydrazine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107570190A (en) * | 2017-07-26 | 2018-01-12 | 湖南大学 | The preparation method of carbon doping carbon nitride films electrode |
| CN107570190B (en) * | 2017-07-26 | 2020-08-28 | 湖南大学 | Preparation method of carbon-doped carbon nitride film electrode |
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| CN110560010B (en) * | 2019-07-31 | 2022-06-28 | 北京建筑大学 | Preparation method and application of multilayer cyclodextrin-graphene oxide framework film adsorbent |
| CN112844040A (en) * | 2021-01-26 | 2021-05-28 | 中国人民解放军火箭军工程大学 | Method for purifying gas-phase unsymmetrical dimethylhydrazine |
| CN112844040B (en) * | 2021-01-26 | 2022-07-15 | 中国人民解放军火箭军工程大学 | Method for purifying gas-phase unsymmetrical dimethylhydrazine |
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