CN103055891A - Method for preparing nano porous titanium dioxide thin film doped with Pd by constant voltage dealloying method on amorphous alloy stripe - Google Patents
Method for preparing nano porous titanium dioxide thin film doped with Pd by constant voltage dealloying method on amorphous alloy stripe Download PDFInfo
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Abstract
The invention discloses a method for preparing a nano porous titanium dioxide thin film doped with Pd by a constant voltage dealloying method on a Ti-Cu-Pd amorphous alloy stripe, in order to provide a novel Pd-TiO2 composite electrode catalyst. A nano porous thin film structure with uniform pore distribution is prepared by steps of adopting a traditional electrochemical three-electrode system, using nitric acid solution as an electrolyte solution, and respectively applying a constant voltage to the amorphous alloy stripe to realize constant voltage electrochemical corrosion by Gamry Reference 600 electrochemical workstation. The method is low in implementation cost, simple and convenient to operate, strong in controllability, good in repeatability and low in reaction temperature, so that the method is an efficient and economic synthesis method.
Description
Technical field
The present invention relates to a kind of preparation method of New-type nano porous film electrode, more particularly, relate in particular to a kind of nanoporous TiO that is applied to the high catalytic activity in electro-catalysis field
2The preparation method of membrane electrode.
Background technology
At present, because energy shortage is day by day serious, the fresh fuel that people begin to seek green high-efficient substitutes traditional energy.DMFC has high-energy-density, and low cost is stored the advantages such as easy to carry, is considered to the very promising energy of a class, can be used for the fields such as portable electric appts and electronic vehicle.Pt is catalyst based to be the most frequently used catalyst of methanol oxidation, but its easily adsorption and oxidation intermediate product such as CO and cause catalyst poisoning in course of reaction, and the cost of Pt is higher, has limited its commercial application.Catalyst based being proved to be of Pd has excellent catalytic performance in direct alcohol fuel cell and direct methanoic acid fuel cell, and relatively inexpensive.Yet the activity that Pd is catalyst based and stability still need larger raising, because Pd is rare, expensive, the utilization ratio that how to improve it also becomes the difficult problem that people are badly in need of solving simultaneously.Researchers improve the catalyst based catalytic performance of Pd, wherein Pd-TiO by the mode that adds other metal, metal oxide or metal carbides usually
2The type composite catalyst both can improve the catalyst based catalytic activity of Pd and stability, can reduce again the use amount of precious metals pd simultaneously, thereby improved the precious metals pd utilization ratio.And in precious metals pd is deposition modified, the noble metal of too high load capacity or aggregate can become the complex centre in light induced electron and hole, and the noble metal granule of simple physical load and adhesion more weak, in use come off easily, thereby cause catalytic capability to descend.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the nanoporous TiO that a kind of cost is low, controllability is strong, preparation process simply prepares doping Pd on Ti-Cu-Pd non-crystaline amorphous metal surface is provided
2The method of membrane electrode, it is the nanoporous noble metal that utilizes constant voltage to take off alloyage to prepare the perforated that the aperture is little, porosity is high, be evenly distributed-metal oxide compound electrode material, use the Ti-Cu-Pd non-crystaline amorphous metal to be original material, adopt constant voltage to take off the nanoporous TiO that alloyage prepares doped precious metal Pd
2Thin-film material, the precious metals pd cluster that forms by original position improves the stability of catalyst, and improves its electrocatalysis characteristic.
Technical purpose of the present invention is achieved by following technical proposals:
A kind ofly adopt constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, carry out according to following step:
With behind the amorphous state Ti-Cu-Pd alloy strip cleaning-drying at its dual coating silica gel, reserve active length (for example 3cm-4cm) when applying silica gel, treat the silica gel sclerosis, the preparation mass fraction is that the aqueous solution of nitric acid of 20%-50% is poured in the reaction utensil, and reaction utensil placed the water-bath that sets temperature, there is the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating, utilize Gamry Reference600 electrochemical workstation to carry out the dealloying corrosion process, the potential value that constant voltage takes off alloy is 0.5V-1.5V, take off the time 3600s-10800s of alloy, 50 ℃-80 ℃ of reaction temperatures.
The potential value that described constant voltage takes off alloy is 1.0V-1.5V, takes off the time 5400s-7200s of alloy, 60 ℃-70 ℃ of reaction temperatures.
The aperture that finally obtains the nanoporous in the material is 20-100nm(for example 50-100nm), and hole wall is 50-100nm, and ligament is of a size of 50 ± 25nm, and nano aperture and ligament evenly distribute.
The thickness of described amorphous state Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS is 10 μ m-30 μ m, and width is 15mm-20mm, and length is 5cm-8cm.
The alloying component of described amorphous state Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS is by atomic percent, and the content of Ti is that the content of 20%-50%, Cu is that the content of 50%-80%, Pd is 1%-10%.
The alloying component of described amorphous state Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS is by atomic percent, and the content that is preferably Ti is that the content of 30%, Cu is that the content of 65%-69%, Pd is 1%-5%.
Such as the SEM figure of accompanying drawing 1, Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS composition is Ti
30Cu
67Pd
3Electrolyte: mass fraction is 30% aqueous solution of nitric acid, the constant potential value is 1.0V, reaction time is 10800s, reaction temperature is the SEM photo of the nano-porous structure under 70 ℃, can find out that the sample surfaces microscopic appearance that obtains is the nano-porous structure of the ligament-hole of co-continuous, and hole and ligament evenly distribute, its mesoporous is 20-30nm, and ligament is of a size of 50 ± 25nm.Utilize the power spectrum probe (Genesis XM2EDAX energy disperse spectroscopy) of edax to carry out the test of EDS spectrogram, the result is as shown in the table, the element set that can find out sample surfaces becomes Ti, Cu, O and Pd, low than in the original non-crystaline amorphous metal of the atomic percentage conc of Cu element wherein, this shows that a part of Cu element is removed in taking off alloy process.
| Element | Percetage by weight wt% | Atomic percentage at% |
| OK | 2.93 | 10.21 |
| PdL | 5.54 | 2.90 |
| TiK | 22.74 | 26.48 |
| CuK | 68.79 | 60.40 |
| Matrix | Correction | ZAF |
Fig. 2 is the electro-catalysis cyclic voltammetry curve, and Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS composition is Ti
30Cu
67Pd
3, electrolyte: mass fraction is 30% salpeter solution, the constant potential value is 1.0V, the reaction time is 10800s, reaction temperature be under 70 ℃ nano-porous structure the electro-catalysis cyclic voltammetry curve, solution medium is 1.0M CH
3OH, the 0.5M KOH(aqueous solution), can find out that in alkaline medium this nano-porous structure is 0.7mA/cm to the oxidation peak current value of anodic oxidation of methanol
2, show that it has preferably electrocatalysis characteristic to methyl alcohol in alkaline medium.
Technical scheme of the present invention is at the nanoporous TiO of Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS surface preparation doping Pd
2Membrane electrode, implementation cost is low, easy and simple to handle, controllability strong (rate of dissolution of surface copper can directly be controlled, so indirectly control hole size and distribute), be a kind of preparation method of high-efficiency and economic.
Description of drawings
The doping Pd nanoporous TiO of Fig. 1 amorphous state Ti-Cu-Pd alloy surface preparation of the present invention
2(ESEM is S4800 to the SEM figure of membrane electrode; Hitachi, Japan)
Fig. 2 utilizes dopen Nano porous TiO of the present invention
2The electro-catalysis C-V figure (Gamry Reference 600 electrochemical workstations) of membrane electrode
The specific embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment
Embodiment 1: a kind of novel nano-porous materials is characterized in that: utilize constant voltage to take off alloyage at the nanoporous TiO of amorphous state Ti-Cu-Pd alloy strip surface preparation doping Pd
2Membrane electrode.
It is to utilize Gamry Reference600 electrochemical workstation that said constant voltage takes off alloyage, adopt traditional electrochemistry three-electrode system, wherein (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) is as reference electrode, applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry and take off alloy reaction and make.
The technological parameter that adopts in the constant voltage dealloying corrosion process is:
The composition of Ti-Cu-Pd amorphous alloy (alloy element component is by atomic percent): Ti:30%; Cu:69%; Pd:1%
Concentration of electrolyte: mass fraction is 30% aqueous solution of nitric acid
Electrolyte temperature: 70 ℃
Constant voltage current potential: 0.5V
Reaction time: 5400s
The area of sample: 0.6cm
2
Its step of the preparation method of above-mentioned said nano-porous materials is as follows:
Step 1, prepare amorphous state Ti-Cu-Pd alloy strip, in absolute ethyl alcohol behind the ultrasonic 5min, with washed with de-ionized water and in air drying with for subsequent use;
Step 2, amorphous state Ti-Cu-Pd alloy strip dual coating silica gel that drying is good, the coating thickness of silica gel is 0.3mm, reserves the active length of 4cm when applying silica gel; With coated sample drying, treat that silica gel sclerosis is placed in the vacuum desiccator to save backup;
Step 3, preparation mass fraction are that 30% salpeter solution is poured in the reaction utensil, and reaction utensil is placed water-bath, wait for that certain hour temperature to the reaction utensil reaches reaction temperature;
Step 4, there is the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating, utilize Gamry Reference600 electrochemical workstation to take off alloy process, adopt traditional electrochemistry three-electrode system, (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) has applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode as reference electrode; After taking off alloy process and finishing, obtain the nanoporous TiO of doping Pd at this Ti-Cu-Pd alloy strip
2Membrane structure;
Step 5, the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS that the taking-up removal alloying is processed from reaction utensil are cleaned with distilled water, at air drying.
Embodiment 2: a kind of novel nano-porous materials is characterized in that: utilize constant voltage to take off alloyage at the nanoporous TiO of amorphous state Ti-Cu-Pd alloy strip surface preparation doping Pd
2Membrane electrode.
It is to utilize Gamry Reference600 electrochemical workstation that said constant voltage takes off alloyage, adopt traditional electrochemistry three-electrode system, wherein (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) is as reference electrode, applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry and take off alloy reaction and make.
The technological parameter that adopts in the constant voltage dealloying corrosion process is:
The composition of Ti-Cu-Pd amorphous alloy (alloy element component is by atomic percent): Ti:30%; Cu:67%; Pd:3%
Concentration of electrolyte: mass fraction is 30% aqueous solution of nitric acid
Electrolyte temperature: 50 ℃
Constant voltage current potential: 1.5V
Reaction time: 3600s
The area of sample: 0.6cm
2
Its step of the preparation method of above-mentioned said nano-porous materials is as follows:
Step 1, prepare amorphous state Ti-Cu-Pd alloy strip, in absolute ethyl alcohol behind the ultrasonic 5min, with washed with de-ionized water and in air drying with for subsequent use;
Step 2, amorphous state Ti-Cu-Pd alloy strip dual coating silica gel that drying is good, the coating thickness of silica gel is 0.3mm, reserves the active length of 4cm when applying silica gel; With coated sample drying, treat that silica gel sclerosis is placed in the vacuum desiccator to save backup;
Step 3, preparation mass fraction are that 30% salpeter solution is poured in the reaction utensil, and reaction utensil is placed water-bath, wait for that certain hour temperature to the reaction utensil reaches reaction temperature;
Step 4, there is the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating, utilize Gamry Reference600 electrochemical workstation to take off alloy process, adopt traditional electrochemistry three-electrode system, (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) has applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode as reference electrode; After taking off alloy process and finishing, obtain the nanoporous TiO of doping Pd at this Ti-Cu-Pd alloy strip
2Membrane structure;
Step 5, the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS that the taking-up removal alloying is processed from reaction utensil are cleaned with distilled water, at air drying.
Embodiment 3: a kind of novel nano-porous materials is characterized in that: utilize constant voltage to take off alloyage at the nanoporous TiO of amorphous state Ti-Cu-Pd alloy strip surface preparation doping Pd
2Membrane electrode.
It is to utilize Gamry Reference600 electrochemical workstation that said constant voltage takes off alloyage, adopt traditional electrochemistry three-electrode system, wherein (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) is as reference electrode, applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry and take off alloy reaction and make.
The technological parameter that adopts in the constant voltage dealloying corrosion process is:
The composition of Ti-Cu-Pd amorphous alloy (alloy element component is by atomic percent): Ti:30%; Cu:67%; Pd:3%
Concentration of electrolyte: mass fraction is 30% aqueous solution of nitric acid
Electrolyte temperature: 80 ℃
Constant voltage current potential: 1.0V
Reaction time: 5400s
The area of sample: 0.6cm
2
Its step of the preparation method of above-mentioned said nano-porous materials is as follows:
Step 1, prepare amorphous state Ti-Cu-Pd alloy strip, in absolute ethyl alcohol behind the ultrasonic 5min, with washed with de-ionized water and in air drying with for subsequent use;
Step 2, amorphous state Ti-Cu-Pd alloy strip dual coating silica gel that drying is good, the coating thickness of silica gel is 0.3mm, reserves the active length of 4cm when applying silica gel; With coated sample drying, treat that silica gel sclerosis is placed in the vacuum desiccator to save backup;
Step 3, preparation mass fraction are that 30% salpeter solution is poured in the reaction utensil, and reaction utensil is placed water-bath, wait for that certain hour temperature to the reaction utensil reaches reaction temperature;
Step 4, there is the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating, utilize Gamry Reference600 electrochemical workstation to take off alloy process, adopt traditional electrochemistry three-electrode system, (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) has applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode as reference electrode; After taking off alloy process and finishing, obtain the nanoporous TiO of doping Pd at this Ti-Cu-Pd alloy strip
2Membrane structure;
Step 5, the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS that the taking-up removal alloying is processed from reaction utensil are cleaned with distilled water, at air drying.
Embodiment 4: a kind of novel nano-porous materials is characterized in that: utilize constant voltage to take off alloyage at the nanoporous TiO of amorphous state Ti-Cu-Pd alloy strip surface preparation doping Pd
2Membrane electrode.
It is to utilize Gamry Reference600 electrochemical workstation that said constant voltage takes off alloyage, adopt traditional electrochemistry three-electrode system, wherein (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) is as reference electrode, applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry and take off alloy reaction and make.
The technological parameter that adopts in the constant voltage dealloying corrosion process is:
The composition of Ti-Cu-Pd amorphous alloy (alloy element component is by atomic percent): Ti:30%; Cu:67%; Pd:3%
Concentration of electrolyte: mass fraction is 30% aqueous solution of nitric acid
Electrolyte temperature: 60 ℃
Constant voltage current potential: 1.0V
Reaction time: 7200s
The area of sample: 0.6cm
2
Its step of the preparation method of above-mentioned said nano-porous materials is as follows:
Step 1, prepare amorphous state Ti-Cu-Pd alloy strip, in absolute ethyl alcohol behind the ultrasonic 5min, with washed with de-ionized water and in air drying with for subsequent use;
Step 2, amorphous state Ti-Cu-Pd alloy strip dual coating silica gel that drying is good, the coating thickness of silica gel is 0.3mm, reserves the active length of 4cm when applying silica gel; With coated sample drying, treat that silica gel sclerosis is placed in the vacuum desiccator to save backup;
Step 3, preparation mass fraction are that 30% salpeter solution is poured in the reaction utensil, and reaction utensil is placed water-bath, wait for that certain hour temperature to the reaction utensil reaches reaction temperature;
Step 4, there is the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating, utilize Gamry Reference600 electrochemical workstation to take off alloy process, adopt traditional electrochemistry three-electrode system, (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) has applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode as reference electrode; After taking off alloy process and finishing, obtain the nanoporous TiO of doping Pd at this Ti-Cu-Pd alloy strip
2Membrane structure;
Step 5, the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS that the taking-up removal alloying is processed from reaction utensil are cleaned with distilled water, at air drying.
Embodiment 5: a kind of novel nano-porous materials is characterized in that: utilize constant voltage to take off alloyage at the nanoporous TiO of amorphous state Ti-Cu-Pd alloy strip surface preparation doping Pd
2Membrane electrode.
It is to utilize Gamry Reference600 electrochemical workstation that said constant voltage takes off alloyage, adopt traditional electrochemistry three-electrode system, wherein (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) is as reference electrode, applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry and take off alloy reaction and make.
The technological parameter that adopts in the constant voltage dealloying corrosion process is:
The composition of Ti-Cu-Pd amorphous alloy (alloy element component is by atomic percent): Ti:30%; Cu:65%; Pd:5%
Concentration of electrolyte: mass fraction is 30% aqueous solution of nitric acid
Electrolyte temperature: 70 ℃
Constant voltage current potential: 1.0V
Reaction time: 10800s
The area of sample: 0.6cm
2
Its step of the preparation method of above-mentioned said nano-porous materials is as follows:
Step 1, prepare amorphous state Ti-Cu-Pd alloy strip, in absolute ethyl alcohol behind the ultrasonic 5min, with washed with de-ionized water and in air drying with for subsequent use;
Step 2, amorphous state Ti-Cu-Pd alloy strip dual coating silica gel that drying is good, the coating thickness of silica gel is 0.3mm, reserves the active length of 4cm when applying silica gel; With coated sample drying, treat that silica gel sclerosis is placed in the vacuum desiccator to save backup;
Step 3, preparation mass fraction are that 30% salpeter solution is poured in the reaction utensil, and reaction utensil is placed water-bath, wait for that certain hour temperature to the reaction utensil reaches reaction temperature;
Step 4, there is the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating, utilize Gamry Reference600 electrochemical workstation to take off alloy process, adopt traditional electrochemistry three-electrode system, (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) has applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode as reference electrode; After taking off alloy process and finishing, obtain the nanoporous TiO of doping Pd at this Ti-Cu-Pd alloy strip
2Membrane structure;
Step 5, the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS that the taking-up removal alloying is processed from reaction utensil are cleaned with distilled water, at air drying.
Embodiment 6: a kind of novel nano-porous materials is characterized in that: utilize constant voltage to take off alloyage at the nanoporous TiO of amorphous state Ti-Cu-Pd alloy strip surface preparation doping Pd
2Membrane electrode.
It is to utilize Gamry Reference600 electrochemical workstation that said constant voltage takes off alloyage, adopt traditional electrochemistry three-electrode system, wherein (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) is as reference electrode, applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode, in salpeter solution, carried out electrochemistry and take off alloy reaction and make.
The technological parameter that adopts in the constant voltage dealloying corrosion process is:
The composition of Ti-Cu-Pd amorphous alloy (alloy element component is by atomic percent): Ti:30%; Cu:65%; Pd:5%
Concentration of electrolyte: mass fraction is 30% aqueous solution of nitric acid
Electrolyte temperature (reaction temperature): 70 ℃
Constant voltage current potential: 1.5V
Reaction time: 10800s
The area of sample: 0.6cm
2
Its step of the preparation method of above-mentioned said nano-porous materials is as follows:
Step 1, prepare amorphous state Ti-Cu-Pd alloy strip, in absolute ethyl alcohol behind the ultrasonic 5min, with washed with de-ionized water and in air drying with for subsequent use;
Step 2, amorphous state Ti-Cu-Pd alloy strip dual coating silica gel that drying is good, the coating thickness of silica gel is 0.3mm, reserves the active length of 4cm when applying silica gel; With coated sample drying, treat that silica gel sclerosis is placed in the vacuum desiccator to save backup;
Step 3, preparation mass fraction are that 30% salpeter solution is poured in the reaction utensil, and reaction utensil is placed water-bath, wait for that certain hour temperature to the reaction utensil reaches reaction temperature;
Step 4, there is the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating, utilize Gamry Reference600 electrochemical workstation to take off alloy process, adopt traditional electrochemistry three-electrode system, (2cm * 2cm) is as to electrode for Pt net electrode, saturated calomel electrode (SCE) has applied the Ti-Cu-Pd noncrystalline alloy strip of silica gel as working electrode as reference electrode; After taking off alloy process and finishing, obtain the nanoporous TiO of doping Pd at this Ti-Cu-Pd alloy strip
2Membrane structure;
Step 5, the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS that the taking-up removal alloying is processed from reaction utensil are cleaned with distilled water, at air drying.
More than the present invention has been done exemplary description; should be noted that; in 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 (7)
1. one kind is adopted constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, it is characterized in that, carries out according to following step:
(1) with behind the amorphous state Ti-Cu-Pd alloy strip cleaning-drying at its dual coating silica gel, reserve active length when applying silica gel, treat the silica gel sclerosis
(2) the preparation mass fraction is that the aqueous solution of nitric acid of 20%-50% is poured in the reaction utensil, and reaction utensil is placed the water-bath that sets temperature, has the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS of silica gel to be fixed in the reaction utensil electrode system and above-mentioned dual coating
(3) utilize electrochemical workstation to carry out the dealloying corrosion process, the potential value that constant voltage takes off alloy is 0.5V-1.5V, takes off the time 3600s-10800s of alloy, 50 ℃-80 ℃ of reaction temperatures.
2. according to claim 1ly a kind ofly adopt constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, it is characterized in that, the potential value that described constant voltage takes off alloy is 1.0V-1.5V, take off the time 5400s-7200s of alloy, 60 ℃-70 ℃ of reaction temperatures.
3. according to claim 1ly a kind ofly adopt constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, it is characterized in that, the alloying component of described amorphous state Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS is by atomic percent, the content of Ti is 20%-50%, the content of Cu is that the content of 50%-80%, Pd is 1%-10%.
4. according to claim 3ly a kind ofly adopt constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, it is characterized in that, the alloying component of described amorphous state Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS is by atomic percent, the content that is preferably Ti is 30%, the content of Cu is that the content of 65%69%, Pd is 1%-5%.
5. according to claim 1ly a kind ofly adopt constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, it is characterized in that, the thickness of described amorphous state Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS is 10 μ m-30 μ m, width is 15mm-20mm, and length is 5cm-8cm.
6. according to claim 1ly a kind ofly adopt constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, it is characterized in that the active length of described step (1) is 3cm-4cm.
7. according to claim 1ly a kind ofly adopt constant voltage to take off the method that alloyage prepares the nano porous titanium dioxide film of doping Pd in the Ti-Cu-Pd AMORPHOUS ALLOY RIBBONS, it is characterized in that, the aperture that finally obtains the nanoporous in the material is 20-100nm(for example 50-100nm), hole wall is 50-100nm, and ligament is of a size of 50 ± 25nm and nano aperture and ligament and evenly distributes.
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