CN102534742A - Titanium dioxide nano thin film composite material and constant-current preparation method thereof - Google Patents

Titanium dioxide nano thin film composite material and constant-current preparation method thereof Download PDF

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CN102534742A
CN102534742A CN201210011172XA CN201210011172A CN102534742A CN 102534742 A CN102534742 A CN 102534742A CN 201210011172X A CN201210011172X A CN 201210011172XA CN 201210011172 A CN201210011172 A CN 201210011172A CN 102534742 A CN102534742 A CN 102534742A
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alloy
electrode
titanium dioxide
electrolytic solution
dioxide nano
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刘涛
朱胜利
崔振铎
杨贤金
何茂山
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Tianjin University
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Abstract

The invention discloses a titanium dioxide nano thin film composite material and a constant-current preparation method of the composite material. The constant-current preparation method comprises the steps of: placing an amorphous Ti-Cu alloy in an electrolysis solution, and carrying out dealloying process by utilizing a three-electrode system and adopting a constant-current method, wherein a netted platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the amorphous alloy Ti-Cu is used as a working electrode, the current density is 0.8-2mA/cm<2>, the dealloying time is 3600-10800s, the electrolysis solution is 20-50wt% nitric acid aqueous solution, and the electrolysis solution temperature is 50-80 DEG C. According to the technical scheme disclosed by the invention, Ti-Cu amorphous alloy strips are placed in the electrolysis solution, and dealloying is carried out by three-electrode system reaction, thus a nano porous thin film structure with uniform pore distribution is prepared, the implementation cost is low, the operation is simple and convenient, the reaction temperature is low and the method is an efficient and economical synthesis method.

Description

A kind of titanium dioxide nano-film matrix material and continuous current preparation method thereof
Technical field
The present invention relates to a kind of nano-porous film and preparation method thereof, relate in particular to that a kind of aperture that is applied to the electrocatalysis field is little, the nanoporous TiO of high porosity 2Film and preparation method thereof.
Background technology
The nano porous metal material be meant have remarkable surface effects, the aperture between 0.1-100nm, porosity greater than 40%, have a cellular solid of high-specific surface area.It is except having the basic Special metallic features of metallic substance (high thermal conductivity, high conductivity, solidity to corrosion, fatigue resistence etc.); Also has the unexistent performance of some compact metal block materials; Such as: the structure that is full of nanoaperture diminishes its proportion relatively, has also increased its specific surface area accordingly; The metal junctions framework of nanoscale has kept the good mechanical performance, and this is also with regard to the corresponding starting material of having practiced thrift.Nanoporous TiO 2Material has big specific surface area because of it, and high specific conductivity, thermal conductivity, and stable machinery, chemistry, chemical property have become electrocatalysis material carrier commonly used.These carriers help nano noble metal particles high dispersing therein, promote the transfer transport in the catalytic oxidation process, impel the quick transportation of the reactant and the product of fuel cell electrode, to improve the performance of integer catalyzer.It is at new forms of energy, and especially there is very big application prospect the alcohol fuel battery aspect.
The nano porous metal preparation methods mainly contains two kinds: template and removal alloying method.Template is to be template with the porous material, and metal target is passed through certain deposition techniques on this template, removes foraminous die plate through methods such as thermal treatment or chemistry after deposition is accomplished, thereby obtains the nano-porous materials of or same structure similar with original template.The hole of the porous material that this method the makes high-sequential of arranging, the shape of the hole that obtains and size all depend on formwork structure, but the preparation technology of template is numerous and diverse, and expense is high, is not suitable for mass production.Take off alloyage, be meant under electropotential between the alloy constituent element differs bigger condition, the more active element of chemical property selective dissolution under electrolytical effect gets into electrolytic solution and stays the corrosion process of chemical property than stable element in the alloy constituent element.The technology of taking off alloyage is simple, and process is controlled easily, also can mass production; Therefore take off alloyage and become the present nano porous metal material method commonly used for preparing; Taking off alloyage now generally has and freely corrodes with the constant potential electrochemical erosion method etc., but the dissolution rate of these two kinds of method copper can not be by directly control, and in potentiostatic method; When current potential reached critical potential, the dissolution rate of copper reached peak.After surpassing critical potential, the dissolution rate of copper can descend rapidly.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide that a kind of cost is low, the preparation process is simply at Ti-Cu non-crystaline amorphous metal surface preparation nanoporous TiO 2The method of membrane structure utilizes that continuous current takes off that alloyage prepares that the aperture is little, high porosity and the multiwalled nano-porous structure matrix material that is evenly distributed.
The object of the invention is achieved through following technical proposals:
Select for use non-crystalline state Ti-Cu alloy to place electrolytic solution; Utilize three-electrode system to adopt galvanostatic method to take off alloy process, gauze platinum electrode is as counter electrode, and SCE is as reference electrode; Amorphous alloy Ti-Cu is as working electrode, and current density is 0.8mA/cm 2-2mA/cm 2, the time of taking off alloy is 3600s-10800s, and electrolytic solution is the aqueous nitric acid of 20%-50wt%, and the temperature of electrolytic solution is 50 ℃-80 ℃.
Said current density is preferably 1.2mA/cm 2-1.8mA/cm 2
Saidly take off the alloy time and be preferably 5000s-10000s
Said electrolytic solution is preferably the aqueous nitric acid of 25%-35wt%
The temperature of said electrolytic solution is preferably 60 ℃-70 ℃
In the said non-crystalline state Ti-Cu alloy, by atomic percent, the content of Ti is 20%-50%, and the content of Cu is 50%-80%.
Technical scheme of the present invention places electrolytic solution with the Ti-Cu AMORPHOUS ALLOY RIBBONS; Alloy is taken off in the reaction of utilization three-electrode system, thereby prepares the nano-porous film structure of even pore distribution, and implementation cost is low, easy and simple to handle; Temperature of reaction is low, is a kind of compound method of highly economical.The titanium deoxid film of preparing has the nano-porous film structure of even pore distribution; Nanoporous in the film demonstrates the bicontinuous structure pattern of mutual perforation; Nano aperture is 50-100nm, and nanoporous is evenly distributed, and (shown in accompanying drawing 1, ESEM is S4800; Hitachi, Japan).(RIGAKU/DMAX2500 Japan) analyzes and can know that the titanium oxide after the preparation is shown as and takes off titanium ore type titanium oxide, and can know bound energy at 464.3eV and 458.7eV by Fig. 2 (a), proves that then Ti is+4 valencys through XPS (X-ray photoelectron spectroscopic analysis) and XRD; Can know bound energy at 530.0eV by Fig. 2 (b), prove that O is-divalent.Utilize Gamry Ref600 electrochemical workstation that the nano porous titanium dioxide film of preparation is carried out electrochemical Characterization; Shown in accompanying drawing 4; In the ethylene glycol medium of alkalescence; Terepthaloyl moietie has shown certain oxidisability when voltage forward scan, visible nano-porous structure is obvious for the katalysis of oxidation of glycol.
Description of drawings
Fig. 1 nanoporous Ti0 2SEM pattern photo (ESEM is S4800; Hitachi, Japan; Electrolytic solution: massfraction is 30% salpeter solution, and constant current density is 1.5mA/cm 2, the reaction times is 7200s, temperature of reaction is 70 ℃) and Fig. 2 X-ray photoelectron spectroscopic analysis spectrogram (XPS is the AXIS Ultra xps energy spectrum appearance of Britain Kratos company),
Wherein (a) figure is Ti, and (b) figure is O
The XRD spectra of Fig. 3 nano porous titanium dioxide (RIGAKU/DMAX2500, Japan)
Fig. 4 nanoporous TiO 2The electrocatalysis cyclic voltammetry curve, solution medium is a water, is 1.0mol/L terepthaloyl moietie and 1mol/LNaOH specifically, electrochemical workstation is a Gamry Ref600 electrochemical workstation
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment; Wherein galvanostatic method is utilized the GamryRef600 electrochemical workstation, adopts three-electrode system, and promptly gauze platinum electrode is as counter electrode; SCE is as reference electrode, and non-crystalline state Ti-Cu alloy is a working electrode.
Embodiment 1
Concentration of electrolyte: massfraction is 30% aqueous nitric acid
Electrolyte temperature: 70 ℃
Constant current density: 1mA/cm 2
Reaction times: 5400s
The area of sample: 0.6cm 2
Step 1, preparation non-crystalline state Ti 30Cu 70Alloy strip (atomic percent that is titanium and copper is 30% and 70%) in the absolute ethyl alcohol behind the excusing from death 5min, cleans in the deionized water and subsequent use in air drying;
Step 2, non-crystalline state Ti that drying is good 30Cu 70Alloy strip dual coated silica gel, the coating thickness of silica gel are 0.3mm, reserve the working length of 4cm when applying silica gel; With coated sample drying, treat the silica gel sclerosis;
Step 3, preparation aqueous nitric acid are poured in the reaction utensil, and put reaction utensil in 70 ℃ of water-baths, wait for that temperature reaches 70 ℃ in certain hour to the reaction utensil;
Step 4, there is the Ti-Cu AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coated; Utilize Gamry REF600 electrochemical workstation to take off alloy process; Wherein, the electrodes use three-electrode system, gauze platinum electrode is as counter electrode; SCE has applied the Ti of silica gel as reference electrode 30Cu 70The amorphous alloy band is as working electrode; After taking off the alloy process completion, on this Ti-Cu alloy strip, obtain nanoporous TiO 2Membrane structure;
Step 5, from reaction utensil, take out and have nanoporous TiO 2The Ti-Cu AMORPHOUS ALLOY RIBBONS of film is cleaned with zero(ppm) water, at air drying.
Embodiment 2
Concentration of electrolyte: massfraction is 20% aqueous nitric acid
Electrolyte temperature: 80 ℃
Constant current density: 1.5mA/cm 2
Reaction times: 3600s
The area of sample: 0.6cm 2
Step 1, preparation non-crystalline state Ti 50Cu 50Alloy strip (atomic percent that is titanium and copper is 50% and 50%) in the absolute ethyl alcohol behind the excusing from death 5min, cleans in the deionized water and subsequent use in air drying;
Step 2, non-crystalline state Ti that drying is good 50Cu 50Alloy strip dual coated silica gel, the coating thickness of silica gel are 0.3mm, reserve the working length of 4cm when applying silica gel; With coated sample drying, treat the silica gel sclerosis;
Step 3, preparation salpeter solution are poured in the reaction utensil, and put reaction utensil in 80 ℃ of water-baths, wait for that temperature reaches 80 ℃ in certain hour to the reaction utensil;
Step 4, electrode system and above-mentioned dual coated there is the Ti of silica gel 50Cu 50AMORPHOUS ALLOY RIBBONS is fixed in the reaction utensil, utilizes Gamry REF600 electrochemical workstation to take off alloy process, wherein, the electrodes use three-electrode system, gauze platinum electrode is as counter electrode, and SCE has applied the Ti of silica gel as reference electrode 50Cu 50The amorphous alloy band is as working electrode; After taking off the alloy process completion, at this Ti 50Cu 50Obtain nanoporous TiO on the alloy strip 2Membrane structure;
Step 5, from reaction utensil, take out and have nanoporous TiO 2The Ti of film 50Cu 50AMORPHOUS ALLOY RIBBONS is cleaned with zero(ppm) water, at air drying.
Embodiment 3
Concentration of electrolyte: massfraction is 35% aqueous nitric acid
Electrolyte temperature: 50 ℃
Constant current density: 0.8mA/cm 2
Reaction times: 10800s
The area of sample: 0.6cm 2
Step 1, preparation non-crystalline state Ti 20Cu 80Alloy strip in the absolute ethyl alcohol behind the excusing from death 5min, cleans in the deionized water and subsequent use in air drying;
Step 2, non-crystalline state Ti that drying is good 20Cu 80Alloy strip dual coated silica gel, the coating thickness of silica gel are 0.3mm, reserve the working length of 4cm when applying silica gel; With coated sample drying, treat the silica gel sclerosis;
Step 3, preparation salpeter solution are poured in the reaction utensil, and put reaction utensil in 50 ℃ of water-baths, wait for that temperature reaches 50 ℃ in certain hour to the reaction utensil;
Step 4, electrode system and above-mentioned dual coated there is the Ti of silica gel 20Cu 80AMORPHOUS ALLOY RIBBONS is fixed in the reaction utensil, utilizes Gamry REF600 electrochemical workstation to take off alloy process, wherein, the electrodes use three-electrode system, gauze platinum electrode is as counter electrode, and SCE has applied the Ti of silica gel as reference electrode 20Cu 80The amorphous alloy band is as working electrode; After taking off the alloy process completion, on this Ti-Cu alloy strip, obtain nanoporous TiO 2Membrane structure;
Step 5, from reaction utensil, take out and have nanoporous TiO 2The Ti-Cu AMORPHOUS ALLOY RIBBONS of film is cleaned with zero(ppm) water, at air drying.
Embodiment 4
Concentration of electrolyte: massfraction is 25% aqueous nitric acid
Electrolyte temperature: 60 ℃
Constant current density: 2mA/cm 2
Reaction times: 5000s
The area of sample: 0.6cm 2
Step 1, preparation non-crystalline state Ti 40Cu 60Alloy strip in the absolute ethyl alcohol behind the excusing from death 5min, cleans in the deionized water and subsequent use in air drying;
Step 2, non-crystalline state Ti that drying is good 40Cu 60Alloy strip dual coated silica gel, the coating thickness of silica gel are 0.3mm, reserve the working length of 4cm when applying silica gel; With coated sample drying, treat the silica gel sclerosis;
Step 3, preparation salpeter solution are poured in the reaction utensil, and put reaction utensil in 60 ℃ of water-baths, wait for that temperature reaches 60 ℃ in certain hour to the reaction utensil;
Step 4, electrode system and above-mentioned dual coated there is the Ti of silica gel 40Cu 60AMORPHOUS ALLOY RIBBONS is fixed in the reaction utensil, utilizes Gamry REF600 electrochemical workstation to take off alloy process, wherein, the electrodes use three-electrode system, gauze platinum electrode is as counter electrode, and SCE has applied the Ti of silica gel as reference electrode 40Cu 60The amorphous alloy band is as working electrode; After taking off the alloy process completion, at this Ti 40Cu 60Obtain nanoporous TiO on the alloy strip 2Membrane structure;
Step 5, from reaction utensil, take out and have nanoporous TiO 2The Ti of film 40Cu 60AMORPHOUS ALLOY RIBBONS is cleaned with zero(ppm) water, at air drying.
Embodiment 5
Concentration of electrolyte: massfraction is 50% aqueous nitric acid
Electrolyte temperature: 65 ℃
Constant current density: 1.2mA/cm 2
Reaction times: 10000s
The area of sample: 0.6cm 2
Step 1, preparation non-crystalline state Ti 30Cu 70Alloy strip in the absolute ethyl alcohol behind the excusing from death 5min, cleans in the deionized water and subsequent use in air drying;
Step 2, non-crystalline state Ti that drying is good 30Cu 70Alloy strip dual coated silica gel, the coating thickness of silica gel are 0.3mm, reserve the working length of 4cm when applying silica gel; With coated sample drying, treat the silica gel sclerosis;
Step 3, preparation salpeter solution are poured in the reaction utensil, and put reaction utensil in 65 ℃ of water-baths, wait for that temperature reaches 65 ℃ in certain hour to the reaction utensil;
Step 4, electrode system and above-mentioned dual coated there is the Ti of silica gel 30Cu 70AMORPHOUS ALLOY RIBBONS is fixed in the reaction utensil, utilizes Gamry REF600 electrochemical workstation to take off alloy process, wherein, the electrodes use three-electrode system, gauze platinum electrode is as counter electrode, and SCE has applied the Ti of silica gel as reference electrode 30Cu 70The amorphous alloy band is as working electrode; After taking off the alloy process completion, at this Ti 30Cu 70Obtain nanoporous TiO on the alloy strip 2Membrane structure;
Step 5, from reaction utensil, take out and have nanoporous TiO 2The Ti of film 30Cu 70AMORPHOUS ALLOY RIBBONS is cleaned with zero(ppm) water, at air drying.
Embodiment 6
Concentration of electrolyte: massfraction is 40% aqueous nitric acid
Electrolyte temperature: 60 ℃
Constant current density: 1.8mA/cm 2
Reaction times: 7200s
The area of sample: 0.6cm 2
Step 1, preparation non-crystalline state Ti 30Cu 70Alloy strip in the absolute ethyl alcohol behind the excusing from death 5min, cleans in the deionized water and subsequent use in air drying;
Step 2, non-crystalline state Ti that drying is good 30Cu 70Alloy strip dual coated silica gel, the coating thickness of silica gel are 0.3mm, reserve the working length of 4cm when applying silica gel; With coated sample drying, treat the silica gel sclerosis;
Step 3, preparation salpeter solution are poured in the reaction utensil, and put reaction utensil in 65 ℃ of water-baths, wait for that temperature reaches 65 ℃ in certain hour to the reaction utensil;
Step 4, electrode system and above-mentioned dual coated there is the Ti of silica gel 30Cu 70AMORPHOUS ALLOY RIBBONS is fixed in the reaction utensil, utilizes Gamry REF600 electrochemical workstation to take off alloy process, wherein, the electrodes use three-electrode system, gauze platinum electrode is as counter electrode, and SCE has applied the Ti of silica gel as reference electrode 30Cu 70The amorphous alloy band is as working electrode; After taking off the alloy process completion, at this Ti 30Cu 70Obtain nanoporous TiO on the alloy strip 2Membrane structure;
Step 5, from reaction utensil, take out and have nanoporous TiO 2The Ti of film 30Cu 70AMORPHOUS ALLOY RIBBONS is cleaned with zero(ppm) water, at air drying.
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.

Claims (8)

1. a titanium dioxide nano-film matrix material is characterized in that, prepares according to following step:
Select for use non-crystalline state Ti-Cu alloy to place electrolytic solution; Utilize three-electrode system to adopt galvanostatic method to take off alloy process, gauze platinum electrode is as counter electrode, and SCE is as reference electrode; Amorphous alloy Ti-Cu is as working electrode, and current density is 0.8mA/cm 2-2mA/cm 2, the time of taking off alloy is 3600s-10800s, and electrolytic solution is the aqueous nitric acid of 20%-50wt%, and the temperature of electrolytic solution is 50 ℃-80 ℃.
2. a kind of titanium dioxide nano-film matrix material according to claim 1 is characterized in that, in the said non-crystalline state Ti-Cu alloy, by atomic percent, the content of Ti is 20%-50%, and the content of Cu is 50%-80%.
3. a kind of titanium dioxide nano-film matrix material according to claim 1 is characterized in that said current density is preferably 1.2mA/cm 2-1.8mA/cm 2Saidly take off the alloy time and be preferably 5000s-10000s.
4. a kind of titanium dioxide nano-film matrix material according to claim 1 is characterized in that said electrolytic solution is preferably the aqueous nitric acid of 25%-35wt%; The temperature of said electrolytic solution is preferably 60 ℃-70 ℃.
5. method of utilizing constant potential to prepare the titanium dioxide nano-film matrix material; It is characterized in that, prepare: select for use non-crystalline state Ti-Cu alloy to place electrolytic solution, utilize three-electrode system to adopt galvanostatic method to take off alloy process according to following step; Gauze platinum electrode is as counter electrode; SCE is as reference electrode, and amorphous alloy Ti-Cu is as working electrode, and current density is 0.8mA/cm 2-2mA/cm 2, the time of taking off alloy is 3600s-10800s, and electrolytic solution is the aqueous nitric acid of 20%-50wt%, and the temperature of electrolytic solution is 50 ℃-80 ℃.
6. a kind of method of utilizing constant potential to prepare the titanium dioxide nano-film matrix material according to claim 5 is characterized in that, in the said non-crystalline state Ti-Cu alloy, by atomic percent, the content of Ti is 20%-50%, and the content of Cu is 50%-80%.
7. a kind of method of utilizing constant potential to prepare the titanium dioxide nano-film matrix material according to claim 5 is characterized in that said current density is preferably 1.2mA/cm 2-1.8mA/cm 2Saidly take off the alloy time and be preferably 5000s-10000s.
8. a kind of method of utilizing constant potential to prepare the titanium dioxide nano-film matrix material according to claim 5 is characterized in that said electrolytic solution is preferably the aqueous nitric acid of 25%-35wt%; The temperature of said electrolytic solution is preferably 60 ℃-70 ℃.
CN201210011172XA 2012-01-14 2012-01-14 Titanium dioxide nano thin film composite material and constant-current preparation method thereof Pending CN102534742A (en)

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CN103055891A (en) * 2012-12-03 2013-04-24 天津大学 Method for preparing nano porous titanium dioxide thin film doped with Pd by constant voltage dealloying method on amorphous alloy stripe
US20150017418A1 (en) * 2013-07-12 2015-01-15 City University Of Hong Kong Porous framework and method for its manufacture
CN106448823A (en) * 2015-08-10 2017-02-22 三星电子株式会社 Transparent electrode using amorphous alloy and method of manufacturing the same
CN110146531A (en) * 2019-05-22 2019-08-20 中山大学 A kind of large scale co-continuous porous foam bismuth and preparation method thereof
US10991952B2 (en) 2016-10-26 2021-04-27 3M Innovative Properties Company Catalyst
US11196055B2 (en) 2016-10-26 2021-12-07 3M Innovative Properties Company Nanoporous oxygen reduction catalyst material
US11258074B2 (en) 2016-10-26 2022-02-22 3M Innovative Properties Company Pt—Ni—Ir catalyst for fuel cell

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Publication number Priority date Publication date Assignee Title
CN103055891A (en) * 2012-12-03 2013-04-24 天津大学 Method for preparing nano porous titanium dioxide thin film doped with Pd by constant voltage dealloying method on amorphous alloy stripe
US20150017418A1 (en) * 2013-07-12 2015-01-15 City University Of Hong Kong Porous framework and method for its manufacture
CN105359316A (en) * 2013-07-12 2016-02-24 香港城市大学 Porous framework and method for its manufacture
CN106448823A (en) * 2015-08-10 2017-02-22 三星电子株式会社 Transparent electrode using amorphous alloy and method of manufacturing the same
US10991952B2 (en) 2016-10-26 2021-04-27 3M Innovative Properties Company Catalyst
US11196055B2 (en) 2016-10-26 2021-12-07 3M Innovative Properties Company Nanoporous oxygen reduction catalyst material
US11258074B2 (en) 2016-10-26 2022-02-22 3M Innovative Properties Company Pt—Ni—Ir catalyst for fuel cell
US11936050B2 (en) 2016-10-26 2024-03-19 3M Innovative Properties Company Pt—Ni—Ir catalyst for fuel cell
CN110146531A (en) * 2019-05-22 2019-08-20 中山大学 A kind of large scale co-continuous porous foam bismuth and preparation method thereof

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Application publication date: 20120704