CN105261763A - Nanotube/porous Ti/W/Ni oxide thin film catalytic electrode in-site loaded with platinum/palladium nanoparticles and preparation method therefor - Google Patents
Nanotube/porous Ti/W/Ni oxide thin film catalytic electrode in-site loaded with platinum/palladium nanoparticles and preparation method therefor Download PDFInfo
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- H01M4/90—Selection of catalytic material
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Abstract
The invention relates to a tubular (porous) Ti/W/Ni oxide thin film catalytic electrode in-site loaded with platinum (palladium) nanoparticles and a preparation method therefor, and belongs to the technical field of energy materials and electro-catalysis, for solving technical problems by providing the nano-tubular (porous) Ti/W/Ni oxide thin film catalytic electrode in-site loaded with the platinum (palladium) nanoparticles, having a simple preparation process, high possibility of large-scale industrial production without using noble metal salts and strong reducing agents in the production process, and low environmental harm, and the preparation method therefor; for fulfilling the purpose, the invention adopts the technical scheme as follows: depositing a Ti/W/Ni-Pt/Pd alloy thin film into a titanium sheet, a tungsten sheet, a nickel titanium alloy sheet or the surface of a conductive glass, then taking the metal sheet or the conductive glass deposited with the Ti/W/Ni-Pt/Pd alloy thin film as the positive electrode, and taking a graphite rod/sheet or a platinum filament/sheet as the negative electrode for performing an anodic oxidation treatment to obtain the nanotube/porous Ti/W/Ni oxide thin film catalytic electrode in-site loaded with the platinum/palladium nanoparticles, wherein the metal Pt/Pd in the electrode is in-site embedded in the nanotube/porous wall of the nanotube/porous Ti/W/Ni oxide and exists in the form of the metal-state nanoparticles.
Description
Technical field
The present invention relates to and a kind ofly can be used for nanotube (hole) shape Ti/W/Ni oxide in-situ Supported Pt Nanoparticles (palladium) nanometer particle film catalysis electrode of the liquid fuel electrocatalysis oxidation reactions such as formic acid, methyl alcohol, ethanol and preparation method thereof, belong to energy and material and electro-catalysis technical field.
Background technology
Direct alcohols and aminic acid fuel battery combining efficient rate, pollution-free, noiseless, applied widely, the advantages such as continuous operation, have broad application prospects in mobile device power supply.The catalyst layer chemical energy of the fuel such as methyl alcohol, ethanol, formic acid being directly converted to efficiently electric energy is the core work parts of fuel cell, redox reaction is there is in fuel molecule on the avtive spot of catalyst surface, and then generation electronics transports at external circuit, exports electric energy.As everyone knows, platinum group metal has good catalytic activity to fuel cell electrode reaction.Catalyst common is at present generally form platinum (palladium) nano particle by electronation or Microwave-assisted Reduction method and to load to specific area large and on the carrier that chemical stability is good, and this process relates to the use of the dissolving of precious metal salt (potassium chloroplatinate, ammonium chloroplatinate, chloroplatinic acid, chlorine palladium acid etc.), reducing agent (sodium borohydride, natrium citricum, ascorbic acid etc.) and kinds of surface activating agent.Platinum group metal salt has higher toxicity, and a large amount of uses of the chemical reagent such as reducing agent and surfactant will produce great problem of environmental pollution, can cause much potential harm to the health of people.
Current modal catalyst carrier is Vulcan-72R nanoscale carbon dust, under sour environment and alkaline environment, all show excellent chemical stability; Reported again the carrier material of the nanoscales such as such as oxide, carbide, nitride afterwards successively, the nano-powders such as such as titanium oxide, manganese oxide, cobalt oxide, titanium carbide, titanium nitride, research finds produce strong interaction between this kind of carrier material and nanoparticles of platinum group metal, has obvious facilitation to the electrochemical stability and activity improving catalyst.Owing to having high specific area and excellent chemical stability, nanotube-shaped titanium oxide is also in the news and can be used as the excellent carrier material of platinum metal catalysts, but first main employing prepares titanium oxide nanotubes at present, then with it for carrier, adopt electronation or Microwave-assisted Reduction method to make corresponding precious metal salt and reducing agent generation chemical reaction thereon, make the noble metal nano particles of formation be attached to the surface of nanotube; Because nanotube caliber is little, generally be in tens to tens nanometers, thus to make the noble metal nano particles of reduction acquisition be distributed in its nanometer mouth of pipe neighbouring and surperficial more, the distribution of tube chamber inside is few, this kind of precious metal salt that utilizes greatly reduces the utilance of the inner large-area nano tube wall of film at the composite catalyzing electrode that the electronation of titanium oxide tube-surface obtains, and adhesion between noble metal nano particles and titanium dioxide carrier is more weak, both are easily separated, and cause the instability in the course of work and activity decrease.
Summary of the invention
For the deficiency that prior art exists, the object of this invention is to provide a kind of preparation process easy, be easy to large-scale industrial production, and do not relate to the use of noble metal salt and strong reductant in production process, nanotube (hole) shape Ti/W/Ni oxide in-situ Supported Pt Nanoparticles (palladium) nanometer particle film catalysis electrode that environmental hazard is little and preparation method thereof.
To achieve these goals, the technical solution used in the present invention is: a kind of nanotube/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, first design and prepare suitable magnetron sputtering with inlaying or Ti/W/Ni-Pt (Pd) target (preferably inlaying target) of alloy, by magnetron sputtering technique, Ti/W/Ni-Pt (Pd) alloy firm be deposited on corrosion-resistant and be polished to bright metal or conductive glass surface, the thickness of alloy firm is 30-1000 micron, and wherein platinum (palladium) content is 0.1-5%.Then will deposit the sheet metal of Ti/W/Ni-palladium (platinum) film or glass as anode, graphite rod/sheet or platinum filament/sheet are as negative electrode, and the ethylene glycol electrolyte be placed in containing fluorine ion carries out anodized, and two inter-electrode voltages are 30-80V.In anode oxidation process, along with Ti/W/Ni in film changes the oxide porous layer of nanotube (hole) shape gradually into, precious metals pt (Pd) atom contained in alloy-layer be released and original position potting on the oxide tube wall formed or hole wall, exist with metallic state nano particle, finally form the film catalyst electrode of nanotube (hole) shape Ti/W/Ni oxide in-situ Supported Pt Nanoparticles (palladium) nano particle.Ti/W/Ni constituent element is titanium, tungsten, the combination of any one in nickel or two/tri-kinds; Wherein, in the alloy firm obtained, Ti/W/Ni constituent element component content is 95-99.9%, and platinum (palladium) content is 0.1-5%.
A preparation method for nanotube/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, specifically comprises the steps:
A. design inlay target for the preparation of magnetron sputtering plating, discoid Ti/W/Ni is base target, and diameter is 30-100mm, and thickness is 3-10mm, and purity is 98-99.9%; Evenly inlay being alternately distributed of a kind of in platinum filament (rod) or palladium silk (rod) or two kinds along magnetic line of force close quarters in the course of work thereon, diameter is 0.2-5mm, and the purity of platinum (palladium) silk (rod) is 98-99.9%.Platinum (palladium) silk (rod) length of inlaying runs through whole base target thickness; Platinum (palladium) silk (rod) inlayed is kept to be combined closely with base target, surfacing; Then be placed on the target position of magnetron sputtering stove;
B. selected sputtering base material is the titanium sheet of purity 99.9%, leaf, Nitinol sheet or electro-conductive glass, and thickness is 0.5-10mm, needs polished flat by metallic substrates specimen surface and be polished to light before magnetron sputtering; Be positioned on the sample stage of magnetron sputtering stove, voltage that magnetron sputtering plating applies is 200-700V, and electric current is 0.2-10A, and sputtering time is about 20min-10h, vacuum degree 10 in chamber
-3-10
-5pa, substrate temperature controls at 30-400 DEG C;
The sample that c. will sputter Ti/W/Ni-platinum (palladium) alloy firm takes out, and draws copper conductor, then protect its back side and lateral parts with insulative water-proof glue from the sample back side;
D. the anodic oxidation electrolyte prepared is the mixed solution of ethylene glycol, deionized water, fluoride salt, wherein ethylene glycol volume is 90-99.5%, deionized water volume is 0.5-10%, and the salt of fluoride used is the combination of one or more in ammonium fluoride, sodium fluoride, potassium fluoride; In anode oxidation process, electrolyte temperature remains on 0-25 DEG C; Do electrode (negative electrode) with carbon-point or platinized platinum, the working face of work electrode is with staggered relatively to electrode, be spaced apart 5-50mm, on work electrode, sputtering has the face of Ti/W/Ni-platinum (palladium) alloy firm to be working face, the high potential interface of wire connecting power is drawn at the back side of work electrode, and the work electrode back side and the lateral parts insulative water-proof glue that are immersed in electrolyte are protected; It is 30-80V that two interpolars add direct voltage, and anodizing time is 20min-24h; After anodic oxidation, sample deionized water is rinsed repeatedly, until sample wash is clean, dry up under inert atmosphere (nitrogen or argon gas); Obtain nanotube (hole) shape Ti/W/Ni oxide in-situ Supported Pt Nanoparticles (palladium) nanometer particle film catalysis electrode.
In preparation process, the magnetron sputtering target of designed processing can be inlay target or alloy target material.
Compared with prior art the present invention has following beneficial effect.
1. first the present invention prepares Ti/W/Ni-palladium (platinum) presoma alloy firm by magnetron sputtering technique, then utilize anode oxidation process, obtain the film catalyst electrode that noble metal platinum (palladium) nano particle in situ is embedded in nanotube (hole) shape oxidation property management (hole) wall; Compare in the catalysis electrode of Ti/W/Ni-Ox film surface with method of fractional steps carried noble metal nano particle, preparation process technique of the present invention is simple, and do not relate to the use of precious metal salt and strong reductant, environmental pollution is little, involved noble metal exists with metallic state always, and utilance is high.
2. in nanotube (hole) shape oxide in-situ Supported Pt Nanoparticles (palladium) the nanometer particle film catalysis electrode prepared by the present invention, Ti/W/Ni-Ox and platinum (palladium) combine closely, show excellent structural stability and strong cooperative effect, change the electronic structure of platinum group metal, thus improve anti-poisoning capability and the durability of catalyst further; Platinum (palladium) nano particle is oxidized property management (hole) wall at Ti/W/Ni-OX and is evenly distributed, and improves the active surface sum service efficiency of noble metal; Overcome traditional method of fractional steps acquisition oxide nano film carried noble metal nanoparticle catalyst easily to come off, be separated, thus cause stability not good, the shortcoming that catalyst life is low.
3. in nanotube prepared by the present invention (hole) shape oxide in-situ Supported Pt Nanoparticles (palladium) nanometer particle film catalysis electrode, the carrying capacity of platinum (palladium) nano particle can carry out flexible modulation by the amount of institute's platiniferous (palladium) in Ti/W/Ni-platinum (palladium) presoma alloy firm, and then can be designed by initial sputter composite target material and splash-proofing sputtering process parameter regulates and controls.In addition, by the voltage in control anode oxidation process and temperature, obtain oxide in-situ Supported Pt Nanoparticles (palladium) the nanometer particle film catalysis electrode of different oxidation property management (hole) shape.
4. the inventive method is simple, and operating procedure is simple, and easy suitability for industrialized production, is suitable for preparing oxide in-situ carried noble metal nanometer particle film catalytic electrode material on a large scale.
accompanying drawing illustrates:
Fig. 1 is the sputtering target material design drawing of embodiment 1.
Fig. 2 is nanotube (hole) the shape titanium oxide original position supported platinum nano particle film catalysis electrode structural representation of embodiment 1.
Fig. 3 is magnetron sputtering titanium platinum alloy film surface ESEM (SEM) photo of embodiment 1.
Fig. 4 is that the magnetron sputtering titanium platinum alloy film surface EDX of embodiment 1 can spectrogram.
Nanotube (hole) shape titanium oxide original position supported platinum nano particle film catalytic electrode surface ESEM (SEM) photo of Fig. 5 prepared by embodiment 1.
Nanotube (hole) the shape titanium oxide original position supported platinum nano particle film catalytic electrode surface EDX of Fig. 6 prepared by embodiment 1 can spectrogram.
Nanotube (hole) the shape titanium oxide original position supported platinum nano particle film catalysis electrode cyclic voltammetry curve in 0.5M sulfuric acid solution of Fig. 7 prepared by embodiment 1.
Nanotube (hole) the shape titanium oxide original position supported platinum nano particle film catalysis electrode cyclic voltammetry curve in 1.0M sulfuric acid and 1.0M alcohol mixed solution of Fig. 8 prepared by embodiment 1.
Nanotube (hole) the shape titanium oxide original position supported platinum nano particle film catalysis electrode cyclic voltammetry curve in 0.5M sulfuric acid and 0.5M formic acid mixed solution of Fig. 9 prepared by embodiment 1.
Embodiment
The technological means realized for making the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with embodiment, setting forth the present invention further.
Embodiment 1:
A kind of nanotube (hole) shape Ti/W/Ni oxide in-situ Supported Pt Nanoparticles (palladium) nanometer particle film catalysis electrode and preparation method thereof, in the membrane electrode formed, Pt nanoparticle original position is embedded in pipe (hole) wall of generated titanium oxide pipe (hole) shape nanostructure, and its structural representation as shown in Figure 1; Its preparation method is as follows:
Step one, first multi-element sputtering target to be designed, here discoid titanium target is adopted to be base target, purity is 99.5%, platinum filament is inlayed thereon along the densely distributed region of magnetic line of force during magnetron sputtering, titanium target diameter used is 100mm, thickness is 5mm, and it is 1mm that platinum filament diameter is inlayed by institute, and length is 5mm; The titanium platinum composite target schematic diagram of design processing as shown in Figure 2; Platinum (palladium) silk (rod) inlayed is kept to be combined closely with base target, surfacing; Then the composite target material processed is placed on the target position of magnetron sputtering stove.
Step 2, selected sputtering base material are the titanium disk of purity 99.9%, and thickness is 2mm, and diameter is 10mm; Need before magnetron sputtering plating titanium substrate surface is polished flat and is polished to light; And carry out ultrasonic process 10min with deionized water, then dry up with nitrogen, be positioned over after being disposed on the sample stage of magnetron sputtering stove.
When step 3, magnetron sputtering plating, the voltage that applies is 300V, and electric current is 0.5A, and sputtering time is about 3h, vacuum degree 10 in chamber
-4pa, substrate temperature controls at 60 DEG C, the titanium platinum alloy film surface appearance formed as shown in Figure 3, form obvious columanar structure, its chemical composition energy spectrogram as shown in Figure 4, the alloy firm that sputtering obtains is primarily of titanium and platinum element composition, and wherein titanium is major components, and the ratio of titanium and platinum is 97%:3%.
Step 4, by the sample of complete for surface sputtering titanium-platinum alloy film take out, from the sample back side draw copper conductor, then with insulative water-proof glue, its back side and lateral parts are protected.
The anodic oxidation electrolyte of step 5, preparation is the mixed solution of ethylene glycol, deionized water, fluoride salt, and wherein ethylene glycol volume is 95%, and deionized water volume is 5%, and fluoride used is ammonium fluoride, and addition is 2g/L; In anode oxidation process, electrolyte temperature remains on 10 DEG C; Do electrode (negative electrode) with carbon-point, the working face of work electrode, with staggered relatively to electrode, is spaced apart 20mm; It is 40V that two interpolars add direct voltage, and anodizing time is 3h; After anodic oxidation, sample deionized water is rinsed repeatedly, until sample wash is clean, dry up with nitrogen; Obtain nanotube (hole) shape titanium oxide original position supported platinum nano particle film catalysis electrode.Its surface topography as shown in Figure 5, shows as vesicular texture; As shown in Figure 6, primarily of titanium oxide and platinum composition, wherein titanium oxide is major components to its EDX energy spectrogram, and wherein the chemical percents of titanium oxide and platinum is roughly 97%:3%, consistent with the ratio of two elements in initial alloy film.
Adopt traditional three-electrode system, saturated calomel electrode is reference electrode, platinum plate electrode is auxiliary electrode, prepared nanotube (hole) shape titanium oxide original position supported platinum nano particle film catalysis electrode is work electrode, carry out electro-chemical test, Fig. 7 provides its cyclic voltammetry curve in 0.5M sulfuric acid solution, and sweep speed is 50mVs
-1, as can be seen from the figure obvious platinum oxidation reduction current peak.Fig. 8 provides its cyclic voltammetry curve in 1.0M ethanol and 1.0M sulfuric acid mixed solution, and as can be seen from the figure prepared nanotube (hole) shape titanium oxide original position supported platinum nano particle film catalysis electrode shows the activity of obvious catalytic oxidation ethanol.Fig. 9 provides its cyclic voltammetry curve in 0.5M formic acid and 0.5M sulfuric acid mixed solution, and as can be seen from the figure prepared nanotube (hole) shape titanium oxide original position supported platinum nano particle film catalysis electrode shows the activity of obvious catalytic oxidation formic acid.
Embodiment 2:
A kind of nanotube (hole) shape tungsten oxide original position supported platinum nano particle film catalysis electrode and preparation method thereof, in the membrane electrode formed, Pt nanoparticle original position is embedded in pipe (hole) wall of generated tungsten oxide pipe (hole) shape nanostructure, and its preparation method is as follows:
Step one, first multi-element sputtering target to be designed, here discoid tungsten target is adopted to be base target, purity is 99.9%, platinum filament is inlayed thereon along the densely distributed region of magnetic line of force during magnetron sputtering, tungsten target material diameter used is 100mm, thickness is 3mm, and it is 1mm that platinum filament diameter is inlayed by institute, and length is 3mm; Then the composite target material processed is placed on the target position of magnetron sputtering stove.
Step 2, selected sputtering base material are the titanium disk of purity 99.9%, and thickness is 3mm, and diameter is 12mm; Need before magnetron sputtering plating titanium substrate surface is polished flat and is polished to light; And carry out ultrasonic process 10min with deionized water, then dry up with nitrogen, be positioned over after being disposed on the sample stage of magnetron sputtering stove.
When step 3, magnetron sputtering plating, the voltage that applies is 400V, and electric current is 1A, and sputtering time is about 3h, vacuum degree 10 in chamber
-4pa, substrate temperature controls at 80 DEG C.
Step 4, by the sample of complete for surface sputtering tungsten-platinum alloy film take out, from the sample back side draw copper conductor, then with insulative water-proof glue, its back side and lateral parts are protected.
The anodic oxidation electrolyte of step 5, preparation is the mixed solution of ethylene glycol, deionized water, fluoride salt, and wherein ethylene glycol volume is 95%, and deionized water volume is 5%, and fluoride used is ammonium fluoride, and addition is 1.5g/L; In anode oxidation process, electrolyte temperature remains on 20 DEG C; Do electrode (negative electrode) with platinized platinum, the working face of work electrode, with staggered relatively to electrode, is spaced apart 30mm; It is 50V that two interpolars add direct voltage, and anodizing time is 3h; After anodic oxidation, sample deionized water is rinsed repeatedly, until sample wash is clean, dry up with nitrogen; Obtain nanotube (hole) shape tungsten oxide original position supported platinum nano particle film catalysis electrode.
Embodiment 3:
A kind of nanotube (hole) shape tungsten oxide original position supported palladium nanometer particle film catalysis electrode and preparation method thereof, in the membrane electrode formed, palladium nano-particles original position is embedded in pipe (hole) wall of generated tungsten oxide pipe (hole) shape nanostructure, and its preparation method is as follows:
Step one, first multi-element sputtering target to be designed, here discoid tungsten target is adopted to be base target, purity is 99.9%, palladium silk is inlayed thereon along the densely distributed region of magnetic line of force during magnetron sputtering, tungsten target material diameter used is 100mm, thickness is 3mm, and it is 1mm that palladium filament diameter is inlayed by institute, and length is 3mm; Then the composite target material processed is placed on the target position of magnetron sputtering stove.
Step 2, selected sputtering base material are the titanium disk of purity 99.9%, and thickness is 1.5mm, and diameter is 10mm; Need before magnetron sputtering plating titanium substrate surface is polished flat and is polished to light; And carry out ultrasonic process 10min with deionized water, then dry up with nitrogen, be positioned over after being disposed on the sample stage of magnetron sputtering stove.
When step 3, magnetron sputtering plating, the voltage that applies is 600V, and electric current is 1A, and sputtering time is about 2.5h, vacuum degree 10 in chamber
-5pa, substrate temperature controls at 100 DEG C.
Step 4, by the sample of complete for surface sputtering tungsten-palldium alloy film take out, from the sample back side draw copper conductor, then with insulative water-proof glue, its back side and lateral parts are protected.
The anodic oxidation electrolyte of step 5, preparation is the mixed solution of ethylene glycol, deionized water, fluoride salt, and wherein ethylene glycol volume is 98%, and deionized water volume is 2%, and fluoride used is ammonium fluoride, and addition is 1.0g/L; In anode oxidation process, electrolyte temperature remains on 25 DEG C; Do electrode (negative electrode) with platinized platinum, the working face of work electrode, with staggered relatively to electrode, is spaced apart 30mm; It is 50V that two interpolars add direct voltage, and anodizing time is 3h; After anodic oxidation, sample deionized water is rinsed repeatedly, until sample wash is clean, dry up with nitrogen; Obtain nanotube (hole) shape tungsten oxide original position supported palladium nanometer particle film catalysis electrode.
Embodiment 4:
A kind of nanotube (hole) shape titanium oxide nickel original position supported platinum nano particle film catalysis electrode and preparation method thereof, in the membrane electrode formed, Pt nanoparticle original position is embedded in pipe (hole) wall of generated titanium oxide nickel pipe (hole) shape nanostructure, and its preparation method is as follows:
Step one, first multi-element sputtering target to be designed, here discoid Ti-Ni alloy target is adopted to be base target, titanium and nickel element ratio are 51%:49%, palladium silk is inlayed thereon along the densely distributed region of magnetic line of force during magnetron sputtering, Ti-Ni alloy target diameter used is 100mm, thickness is 3mm, and it is 1mm that platinum filament diameter is inlayed by institute, and length is 3mm; Then the composite target material processed is placed on the target position of magnetron sputtering stove.
Step 2, selected sputtering base material are the titanium disk of purity 99.9%, and thickness is 1.5mm, and diameter is 10mm; Need before magnetron sputtering plating titanium substrate surface is polished flat and is polished to light; And carry out ultrasonic process 10min with deionized water, then dry up with nitrogen, be positioned over after being disposed on the sample stage of magnetron sputtering stove.
When step 3, magnetron sputtering plating, the voltage that applies is 600V, and electric current is 1A, and sputtering time is about 2.5h, vacuum degree 10 in chamber
-5pa, substrate temperature controls at 100 DEG C.
Step 4, by the sample of complete for surface sputtering titanium nickel-platinum alloy film take out, from the sample back side draw copper conductor, then with insulative water-proof glue, its back side and lateral parts are protected.
The anodic oxidation electrolyte of step 5, preparation is the mixed solution of ethylene glycol, deionized water, fluoride salt, and wherein ethylene glycol volume is 98%, and deionized water volume is 2%, and fluoride used is ammonium fluoride, and addition is 1.0g/L; In anode oxidation process, electrolyte temperature remains on 1 DEG C; Do electrode (negative electrode) with platinized platinum, the working face of work electrode, with staggered relatively to electrode, is spaced apart 30mm; It is 50V that two interpolars add direct voltage, and anodizing time is 3h; After anodic oxidation, sample deionized water is rinsed repeatedly, until sample wash is clean, dry up with nitrogen; Obtain nanotube (hole) shape titanium oxide nickel original position supported platinum nano particle film catalysis electrode.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought explanation of the present invention and can not limit invention, claims indicate scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Claims (6)
1. nanotube/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, it is characterized in that, Ti/W/Ni-Pt/Pd alloy firm be deposited on corrosion-resistant and be polished to bright titanium sheet, leaf, Nitinol sheet or conductive glass surface, then the titanium sheet of Ti/W/Ni-Pt/Pd alloy firm will be deposited, leaf, Nitinol sheet or electro-conductive glass are as anode, graphite rod/sheet or platinum filament/sheet are as negative electrode, carry out anodized, obtain described nanotube/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, Pt metal in described electrode/Pd atom original position potting is oxidized on property management/hole wall in nanotube/poroid Ti/W/Ni, exist with metallic state nano particle, described Ti/W/Ni-platinum (palladium) alloy firm is deposited on titanium sheet by magnetron sputtering coating method, leaf, the surface of Nitinol sheet or electro-conductive glass, described Ti/W/Ni constituent element is titanium, tungsten, the combination of any one in nickel or two/tri-kinds, described, the thickness of alloy firm is 30-1000 micron, in alloy firm, Ti/W/Ni constituent element component content is 95-99.9%, platinum (palladium) content is 0.1-5%.
2. the preparation method of a kind of nanotube according to claim 1/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, is characterized in that, specifically comprise the steps:
A. design inlay target for the preparation of magnetron sputtering plating, discoid Ti/W/Ni is base target, and diameter is 30-100mm, and thickness is 3-10mm, and purity is 98-99.9%; Being alternately distributed of a kind of in platinum filament (rod) or palladium silk (rod) or two kinds is evenly inlayed thereon along magnetic line of force close quarters in the course of work, diameter is 0.2-5mm, the purity of platinum (palladium) silk (rod) is 98-99.9%, platinum (palladium) silk (rod) length of inlaying runs through whole base target thickness, platinum (palladium) silk (rod) inlayed is kept to be combined closely with base target, surfacing; Then be placed on the target position of magnetron sputtering stove;
B. by selected sputtering base material titanium sheet, leaf, Nitinol sheet or electro-conductive glass, be positioned on the sample stage of magnetron sputtering stove, carry out magnetron sputtering;
The sample that c. will sputter Ti/W/Ni-platinum (palladium) alloy firm takes out, and draws copper conductor, then protect its back side and lateral parts with insulative water-proof glue from the sample back side;
D. anodized is carried out, the anodic oxidation electrolyte of preparation is the mixed solution of ethylene glycol, deionized water, fluoride salt, in anode oxidation process, electrolyte temperature remains on 0-25 DEG C, to the titanium sheet of Ti/W/Ni-Pt/Pd alloy firm, leaf, Nitinol sheet or electro-conductive glass be deposited as anode, do electrode (negative electrode) with carbon-point or platinized platinum, the working face of work electrode, with staggered relatively to electrode, is spaced apart 5-50mm; It is 30-80V that two interpolars add direct voltage, and anodizing time is 20min-24h; After anodic oxidation, sample deionized water is rinsed repeatedly, until sample wash is clean, dry up under inert atmosphere (nitrogen or argon gas); Obtain nanotube (hole) shape Ti/W/Ni oxide in-situ Supported Pt Nanoparticles (palladium) nanometer particle film catalysis electrode.
3. the preparation method of a kind of nanotube according to claim 2/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, is characterized in that, the magnetron sputtering target of designed processing is for inlaying target or alloy target material.
4. the preparation method of a kind of nanotube according to claim 2/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, it is characterized in that, selected magnetron sputtering base material is the titanium sheet of purity 99.9%, leaf, Nitinol sheet or electro-conductive glass, thickness is 0.5-10mm, needs metallic substrates specimen surface to polish flat and polishing before magnetron sputtering.
5. the preparation method of a kind of nanotube according to claim 2/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, it is characterized in that, in described magnetron sputtering process, voltage that magnetron sputtering plating applies is 200-700V, electric current is 0.2-10A, sputtering time is about 20min-10h, vacuum degree 10 in chamber
-3-10
-5pa, substrate temperature controls at 30-400 DEG C.
6. the preparation method of a kind of nanotube according to claim 2/poroid Ti/W/Ni oxide in-situ Supported Pt Nanoparticles/palladium nano-particles film catalyst electrode, it is characterized in that, described anodic oxidation electrolyte wherein ethylene glycol volume is 90-99.5%, deionized water volume is 0.5-10%, and the salt of fluoride used is the combination of one or more in ammonium fluoride, sodium fluoride, potassium fluoride.
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