CN102130342A - Noble metal-titanium dioxide nano fiber complex and preparation method and application thereof - Google Patents
Noble metal-titanium dioxide nano fiber complex and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a noble metal-titanium dioxide nano fiber complex and a preparation method and application thereof. The method comprises the following steps of: 1) mixing solution of titanate and solution of polyvinyl pyrrolidone uniformly to form electrostatic spinning stock solution, performing electrostatic spinning to obtain TiO2 nano fibers, and calcining the TiO2 nano fibers to obtain anatase TiO2 nano fibers; and 2) dispersing the anatase TiO2 nano fibers into alcohol, adding noble metal salt solution, mixing the solution uniformly, and performing intermittent microwave heating to obtain the noble metal-titanium dioxide nano fiber complex. The noble metal-titanium dioxide nano fiber complex provided by the invention has small granule diameter (5 nanometers) and narrow granule distribution, the granules are dispersed high and aggregated, the noble metal content can be randomly controlled from 5 to 60 percent, and the complex has high electric catalytic activity and can be used as an electric catalyst for a fuel cell oxide electrode.
Description
Technical field
The invention belongs to the preparation field of fuel-cell catalyst, relate to a kind of noble metal-titanium dioxide nanofiber complex and preparation method thereof and application.
Background technology
Proton Exchange Membrane Fuel Cells (PEM fuel cell) can be under relatively low temperature (about 80 ℃) operation, allow to start fast (needing shorter warm-up time), so the system element wearing and tearing are few, have durability preferably.The electro-catalysis process of PEM fuel cells applications is the reduction of airborne oxygen on the oxidation of the hydrogen on the anode and the negative electrode.The eelctro-catalyst that generally uses in the PEM fuel cell system is the alloy/C catalyst of platinum/C catalyst or platinum at present.The carbon of high-specific surface area is used for the platinum of nano-scale of load high dispersive, the reactant and the product of smooth transportation fuel cell reaction, and have good electric conductivity.Before the motor vehicle fuel battery technology becomes actual available, large-scale production, have to be noted that at oxidizing electrode to have oxidative instability (dynamics is slow, but feasible on the thermodynamics) as the carbon of catalyst carrier.Although a lot of researchers have been expanded multi-form carbon, wait to substitute as the multi-wall carbon nano-tube tube material, because its hydrophobicity, above the Pt particle is difficult to be dispersed in.Therefore we as doing carrier material with conductive titanyl compound, prolong the life-span of catalyst-carrier with changing carrier material.Titanium dioxide (TiO
2) the commercial Chinese white that mainly is used as, because it has big light scattering and little light absorption, be nontoxic, chemical inertness, have the very ceramic material of high-k.The physics of titanium dioxide, chemical property can be controlled by granular size and pattern.Have the good crystallite size (less than 100 nanometers) and the titanium oxide of high-specific surface area, because its unique optics, electricity and catalytic property have caused extensive concern.Magneli in the titanium oxide family Ti that is consistent
nO
2n-1General formula, wherein n can be 4-10.Patent WO97/27344 and EP 0 572 559 propose Magneli phase oxidation titanium and can be used on the electrode of fuel cell.Yet Magneli phase oxidation titanium is the anoxic attitude, and being used on the oxidizing electrode still can the eremacausis along with the carrying out of cell reaction, influences the performance of battery.Therefore we adopt more stable anatase phase titanic oxide as catalyst carrier, and improve the Pt/TiO that is used for Proton Exchange Membrane Fuel Cells
2The key of the electrocatalysis characteristic of compound is to improve based on TiO
2The decentralization of Pt in the electric conductivity of carrier and the compound.
Activity of such catalysts can strengthen by the amount that increases the per unit volume surface area catalyst.Compare with Powdered, fibrous titanium dioxide is owing to have big specific surface and be convenient to that reactant is carried and product release causes people's extensive interest.Electrostatic spinning technique be can prepare long size, that diameter is evenly distributed, composition is diversified, it is solid both can be, also can be the simplest method of hollow nanofiber, and it is simple that electrospinning has equipment, easy and simple to handle, the productive rate advantages of higher is the unique method of preparation continuous nano-fibre.
How noble metal granule is loaded to the TiO of electrospinning
2It on the fiber key that improves noble metal granule decentralization in the compound.At present the method for the catalyst of the preparation noble metal load of generally using is for soaking a year method, but the bullion content of the method load often lower (below 10%) is not suitable for fuel cell system.Method such as chemical deposition that other are commonly used, light deposition method etc. often need the long time allow noble metal granule " seed " growth and aging.Microwave is the electromagnetic wave of wavelength between 1mm～1m, owing to the micro-wave dielectric thermal effect is that a kind of " interior heating " mechanism has been avoided heat conduction and the convective heat transfer in the traditional heating, thereby be a kind of evenly, mode of heating rapidly.The existing more report of metal nanoparticle that the applied microwave reducing process prepares polymer protection with microwave reduction method supporting Pt particle on carbon nano-tube report is arranged also, but the method need be carried out carbon nano-tube complicated pre-treatment.Therefore prepare the efficient Pt/TiO that is applicable to fuel cell system fast
2The key of catalyst is how microwave reduction method and electrospinning method to be combined.
Summary of the invention
The purpose of this invention is to provide noble metal-titanium dioxide nanofiber complex and preparation method thereof and application.
The method for preparing noble metal-titanium dioxide nanofiber complex provided by the invention comprises the steps:
1) with the solution mixing of the solution of titanate esters and polyvinylpyrrolidone as electrostatic spinning stoste, carry out electrostatic spinning, obtain TiO
2Nanofiber is again to described TiO
2Nanofiber is calcined, and obtains Detitanium-ore-type TiO
2Nanofiber;
2) with described Detitanium-ore-type TiO
2Nanofiber is scattered in the alcohol, adds the precious metal salt solution mixing again, carries out the intermittent type microwave heating, leaves standstill, and washing obtains described noble metal-titanium dioxide nanofiber complex after the drying.
In the step 1) of said method, described titanate esters is selected from wherein a kind of in positive tetraethyl titanate, positive isopropyl titanate and the positive butyl titanate; The mass ratio of titanate esters and polyvinylpyrrolidone is 2-5: 1, specifically can be 2.5-4: 1,2.9-4: 1,2.5-3.5: 1,2.9-3.3: 1,1.9-4: 1,1.5-4: 1 or 1.5-3.5: 1, preferred 3.3: 1, in the solution of described titanate esters, the mixed liquor of solvent preferred alcohol and acetate is in this mixed liquor, the volume ratio of ethanol and acetate is 1: 1, the number-average molecular weight of described polyvinylpyrrolidone is preferably 1,300, and 000; In the solution of described polyvinylpyrrolidone, solvent is preferably ethanol, and the consumption of solvent only need guarantee that polyvinylpyrrolidone dissolves fully and get final product.In the described electrostatic spinning step, the flow velocity of electrostatic spinning stoste is 4-20ml/h, specifically can be 4-15ml/h, 5-20ml/h, 5-10ml/h, 4-10ml/h, 10-20ml/h, 15-20ml/h or 10-15ml/h; In the described calcining step, temperature is 400-500 ℃, and preferred 500 ℃, the time is 3-8 hour, preferred 4 hours.This electrostatic spinning step specifically can be: with the organic solution of titanate esters and the organic solution mixing of polyvinylpyrrolidone, as electrostatic spinning stoste, control extruding of described electrostatic spinning stoste by microinjection apparatus, the spout of described microinjection apparatus links to each other with the negative electrode of power supply, the metallic plate that is coated with aluminium foil layer that links to each other with described power anode is as the spinning receiving system, carry out electrostatic spinning, obtain TiO
2Nanofiber; Wherein, described power source voltage is ten thousand volts of 2-4, and the described distance that is coated with the metallic plate of aluminium foil layer of the jet opening distance of described microinjection apparatus is 15-30 centimetre.
Described step 2) in, it is 2～10 monohydric alcohol and in the dihydroxylic alcohols any one that described alcohol is selected from carbon number, any one in preferred alcohol, propyl alcohol, butanols, ethylene glycol and the glycerol.In the described precious metal salt, precious metal element is selected from least a in gold, platinum and the palladium; In the solution of described precious metal salt, it is 2～10 monohydric alcohol and in the dihydroxylic alcohols any one that solvent is selected from water and carbon number, any one in preferred water, ethanol, propyl alcohol, butanols, ethylene glycol and the glycerol.Described Detitanium-ore-type TiO
2The amount ratio of nanofiber, described alcohol and described precious metal salt solution is 0.2-2g: 20-300mL: 2-20mL, specifically can be 0.2g: 20-100mL: 2-10mL, 0.2-0.3g: 20-100mL: 2-10mL or 0.2g: 20-45mL: 2.5-4mL, preferred 0.2g: 30mL: 3mL, the concentration of described precious metal salt solution is 0.05-0.10mol/L, specifically can be 0.07mol/L, 0.07-0.09mol/L, 0.05-0.09mol/L, 0.05-0.08mol/L, 0.07-0.09mol/L or 0.07-0.08mol/L, preferred 0.07mol/L.Described intermittent type microwave heating steps is every microwave heating 10-30 after second, suspends 5-15 second; The total time of described intermittent type microwave heating is 2-60 minute, specifically can be 2-20 minute, 4-20 minute, 4-15 minute, 10-15 minute, 2-50 minute, 10-50 minute, 10-40 minute or 5-20 minute; In the described intermittent type microwave heating steps, microwave frequency is 2000-3000MHz, preferred 2450MHz, and microwave power is 80～1000W, specifically can be 500-800W, 500-750W, 600-800W or 700-800W, preferred 650-800W; In the described washing step, cleaning solution is selected from least a in deionized water and the ethanol; In the described drying steps, temperature is 80-200 ℃, and preferred 80 ℃, the time is 1-3 hour, preferred 2 hours.
The noble metal for preparing according to the method described above-titanium dioxide nanofiber complex; and the application of this noble metal-titanium dioxide nanofiber complex in the electrode electrocatalyst materials of preparation fuel cell; especially prepare the application in the electrode electrocatalyst materials of Proton Exchange Membrane Fuel Cells, also belong to protection scope of the present invention.
Preparation method provided by the invention is with TiO
2In the compound system that nanofiber, alcoholic solution and noble metal precursor liquid solution are formed, utilize the Fast Heating of microwave to make the generating rate of particle be better than the growth rate of particle on the one hand, utilize TiO on the other hand
2Nanofiber disperses the noble metal nano particles of generation.This method preparation process is simple; do not need to add any protective agent, course of reaction is quick, the productive rate height; can prepare in enormous quantities; the particle diameter of gained noble metal-titanium dioxide nanofiber complex little (5nm), narrowly distributing, the particle high dispersive is not assembled; bullion content can be controlled arbitrarily by 5%-60%; have high electrocatalytic active, can be used as the eelctro-catalyst of fuel cell oxidizing electrode, replace the unsettled C catalyst carrier of electrochemistry.Noble metal provided by the invention-titanium dioxide nanofiber complex, for the innovation of the material of fuel cell oxidizing electrode eelctro-catalyst provides the foundation, significant in the preparation and the application facet of fuel cell electrode material.
Description of drawings
The Pt content that Fig. 1 prepares for the embodiment of the invention 1 is 20% o'clock, high dispersive Pt/TiO
2The TEM photo of nanofiber complex.
The Pt content that Fig. 2 prepares for the embodiment of the invention 1 is 20% o'clock, Pt/TiO
2The nanofiber complex is to the cyclic voltammetry curve (Pt/TiO of methyl alcohol electro-catalysis
2Nano-fibre supported on the Au electrode slice, wherein the load capacity of Pt is 3.5mg/cm
2).
The Pt content that Fig. 3 prepares for the embodiment of the invention 2 is 30% o'clock, high dispersive Pt/TiO
2The TEM photo of nanofiber complex.
The Pt content that Fig. 4 prepares for the embodiment of the invention 2 is 30% o'clock, Pt/TiO
2The nanofiber complex is to the cyclic voltammetry curve (Pt/TiO of methyl alcohol electro-catalysis
2Nano-fibre supported on the Au electrode slice, wherein the load capacity of Pt is 3.5mg/cm
2).
Fig. 5 is the cyclic voltammetry curve of reference Pt plate electrode to the methyl alcohol electro-catalysis.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1
The positive isopropyl titanate of 1.5g is joined in the mixed solution of 3ml ethanol and 3ml acetate, fully stir, join in the 7.5ml ethanol that is dissolved with 0.45g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 15 minutes then.The mixed solution of gained is sucked in the plastic injector, flow velocity is controlled to be 4ml/h, and the stainless steel syringe needle links to each other with the negative electrode of high voltage source, and the metallic plate that is coated with aluminium platinum that receives body as product links to each other with the anode of high voltage source, voltage is set to 30,000 volts, and syringe needle is 25cm to the distance of dash receiver.After reaction is finished, fibrofelt 500 degree that obtain were calcined 4 hours,, promptly obtained TiO to remove the organic substance in the product
2Fiber product.
Get the above-mentioned gained TiO of 0.2g then
2Fiber product is dispersed in the 27.2ml ethylene glycol solution, adds the H of 2.72ml 0.0772mol/L again
2PtCl
6Solution stirs.Place microwave oven to heat the suspension-turbid liquid of gained, frequency is 2450MHz, and power is 750W, and heating process is heating in 20 seconds, 10 seconds stop, and 3 minutes so repeatedly, promptly obtain the product of black, products obtained therefrom is aging, washing, 80 ℃ are dried by the fire 2 hours dryings down, obtain Pt/TiO provided by the invention
2The nanofiber complex.Gained Pt/TiO
2In the nanofiber complex, Pt grain diameter size is 5nm, and high dispersive is in TiO
2Fiber surface, as shown in Figure 1.With this Pt/TiO
2Fiber composite loads on the gold plaque electrode, and wherein the load capacity of Pt is 3.5mg/cm
2, in 1mol/L methyl alcohol and 1mol/L sulfuric acid mixed solution, do cyclic voltammetry scan, obtain curve as shown in Figure 2, with the cyclic voltammetry curve contrast of the Pt plate electrode of Fig. 5 to the methyl alcohol electro-catalysis, as can be known, Pt/TiO provided by the invention
2Fiber composite improves 2 orders of magnitude with the current density at methanol oxidation peak.
Embodiment 2
The positive isopropyl titanate of 1.5g is joined in the mixed solution of 3ml ethanol and 3ml acetate, fully stir, join in the 7.5ml ethanol that is dissolved with 0.45g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 15 minutes then.The mixed solution of gained is sucked in the plastic injector, flow velocity is controlled to be 4ml/h, and the stainless steel syringe needle links to each other with the negative electrode of high voltage source, and the metallic plate that is coated with aluminium platinum that receives body as product links to each other with the anode of high voltage source, voltage is set to 30,000 volts, and syringe needle is 25cm to the distance of dash receiver.After reaction is finished, fibrofelt 500 degree that obtain were calcined 4 hours,, promptly obtained TiO to remove the organic substance in the product
2Fiber product.
Get the above-mentioned gained TiO of 0.2g then
2Fiber product is dispersed in the 40.9ml ethylene glycol solution, adds the H of 4.1ml 0.0772mol/L again
2PtCl
6Solution stirs.Place microwave oven to heat the suspension-turbid liquid of gained, frequency is 2450MHz, and power is 750W, and heating process is heating in 20 seconds, 10 seconds stop, and 4 minutes so repeatedly, promptly obtain the product of black, products obtained therefrom is aging, washing, 80 ℃ are dried by the fire 2 hours dryings down, obtain Pt/TiO provided by the invention
2The nanofiber complex.Gained Pt/TiO
2In the nanofiber complex, Pt grain diameter size is 5nm, and high dispersive is in TiO
2Fiber surface, as shown in Figure 2.With this Pt/TiO
2Fiber composite loads on the gold plaque electrode, and wherein the load capacity of Pt is 3.5mg/cm
2, in 1mol/L methyl alcohol and 1mol/L sulfuric acid mixed solution, do cyclic voltammetry scan, obtain curve as shown in Figure 4, with the cyclic voltammetry curve contrast of the Pt plate electrode of Fig. 5, Pt/TiO provided by the invention as can be known to the methyl alcohol electro-catalysis
2Fiber composite improves 2 orders of magnitude with the current density at methanol oxidation peak.
Embodiment 3
The positive tetraethyl titanate of 1.5g is joined in the mixed solution of 5ml ethanol and 5ml acetate, fully stir, join in the 9ml ethanol that is dissolved with 0.78g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 25 minutes then.The mixed solution of gained is sucked in the plastic injector, flow velocity is controlled to be 6ml/h, and the stainless steel syringe needle links to each other with the negative electrode of high voltage source, and the metallic plate that is coated with aluminium platinum that receives body as product links to each other with the anode of high voltage source, voltage is set to 2.5 ten thousand volts, and syringe needle is 18cm to the distance of dash receiver.After reaction is finished, fibrofelt 500 degree that obtain were calcined 4 hours,, promptly obtained TiO to remove the organic substance in the product
2Fiber product.
Get the above-mentioned gained TiO of 0.2g then
2Fiber product is dispersed in the 20ml glycerol solution, adds the H of 2.5ml0.07mol/L again
2PdCl
4Solution stirs.Place microwave oven to heat the suspension-turbid liquid of gained, frequency is 2450MHz, and power is 600W, and heating process is heating in 30 seconds, 10 seconds stop, and 10 minutes so repeatedly, promptly obtain the product of black, products obtained therefrom is aging, washing, 80 ℃ are dried by the fire 2 hours dryings down, obtain Pd/TiO provided by the invention
2The nanofiber complex.Gained Pd/TiO
2In the nanofiber complex, Pd grain diameter size is 3nm, and high dispersive is in TiO
2Fiber surface, the quality percentage composition of Pd is 9.4%.
Embodiment 4
The positive butyl titanate of 2.5g is joined in the mixed solution of 7ml ethanol and 7ml acetate, fully stir, join in the 12ml ethanol that is dissolved with 0.85g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 50 minutes then.The mixed solution of gained is sucked in the plastic injector, flow velocity is controlled to be 5ml/h, and the stainless steel syringe needle links to each other with the negative electrode of high voltage source, and the metallic plate that is coated with aluminium platinum that receives body as product links to each other with the anode of high voltage source, voltage is set to 3.5 ten thousand volts, and syringe needle is 25cm to the distance of dash receiver.After reaction is finished, fibrofelt 500 degree that obtain were calcined 4 hours,, promptly obtained TiO to remove the organic substance in the product
2Fiber product.
Get the above-mentioned gained TiO of 0.3g then
2Fiber product is dispersed in the 84ml butanol solution, adds the H of the 0.08mol/L of 10ml again
2PdCl
4Solution stirs.Place microwave oven to heat the suspension-turbid liquid of gained, frequency is 2450MHz, and power is 800W, and heating process is heating in 15 seconds, 8 seconds stop, and 30 minutes so repeatedly, promptly obtain the product of black, products obtained therefrom is aging, washing, 80 ℃ are dried by the fire 2 hours dryings down, obtain Pd/TiO provided by the invention
2The nanofiber complex.Gained Pd/TiO
2In the nanofiber complex, Pd grain diameter size is 3nm, and high dispersive is in TiO
2Fiber surface, the quality percentage composition of Pd is 28%.
Embodiment 5
The positive isopropyl titanate of 1g is joined in the mixed solution of 5ml ethanol and 5ml acetate, fully stir, join in the 8ml ethanol that is dissolved with 0.25g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 30 minutes then.The mixed solution of gained is sucked in the plastic injector, flow velocity is controlled to be 4ml/h, and the stainless steel syringe needle links to each other with the negative electrode of high voltage source, and the metallic plate that is coated with aluminium platinum that receives body as product links to each other with the anode of high voltage source, voltage is set to 20,000 volts, and syringe needle is 15cm to the distance of dash receiver.After reaction is finished, fibrofelt 400 degree that obtain were calcined 5 hours,, promptly obtained TiO to remove the organic substance in the product
2Fiber product.
Get the above-mentioned gained TiO of 0.1g then
2Fiber product is dispersed in the 18ml ethylene glycol solution, adds the chlorauric acid solution of 2ml0.09mol/L again, stirs.Place microwave oven to heat the suspension-turbid liquid of gained, frequency is 2450MHz, and power is 500W, and heating process is heating in 15 seconds, 5 seconds stop, and 10 minutes so repeatedly, promptly obtain the product of black, products obtained therefrom is aging, washing, 80 ℃ of following bakings were drying to obtain Au/TiO in 2 hours
2Composite fibre, this moment, the decentralization of Au particle was relatively poor.
Claims (10)
1. a method for preparing noble metal-titanium dioxide nanofiber complex comprises the steps:
1) with the solution mixing of the solution of titanate esters and polyvinylpyrrolidone as electrostatic spinning stoste, carry out electrostatic spinning, obtain TiO
2Nanofiber is again to described TiO
2Nanofiber is calcined, and obtains Detitanium-ore-type TiO
2Nanofiber;
2) with described Detitanium-ore-type TiO
2Nanofiber is scattered in the alcohol, adds the solution mixing of precious metal salt again, carries out the intermittent type microwave heating, leaves standstill, and washing obtains described noble metal-titanium dioxide nanofiber complex after the drying.
2. method according to claim 1 is characterized in that: in the described step 1), described titanate esters is selected from least a in positive tetraethyl titanate, positive isopropyl titanate and the positive butyl titanate; The number-average molecular weight of described polyvinylpyrrolidone is 1,300,000; In the solution of described titanate esters, solvent is the mixed liquor of ethanol and acetate; In the solution of described polyvinylpyrrolidone, solvent is an ethanol;
Described step 2) in, it is 2～10 monohydric alcohol and in the dihydroxylic alcohols any one that described alcohol is selected from carbon number; In the described precious metal salt, precious metal element is selected from least a in gold, platinum and the palladium; In the solution of described precious metal salt, it is 2～10 monohydric alcohol and in the dihydroxylic alcohols any one that solvent is selected from water and carbon number.
3. method according to claim 2 is characterized in that: described step 2), described alcohol is ethanol, propyl alcohol, butanols, ethylene glycol or glycerol; In the solution of described precious metal salt, solvent is water, ethanol, propyl alcohol, butanols, ethylene glycol or glycerol.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: in the described step 1), the mass ratio of titanate esters and polyvinylpyrrolidone is 2: 1-5: 1, and in the mixed liquor of described ethanol and acetate, the volume ratio of ethanol and acetate is 1: 1;
Described step 2) in, described Detitanium-ore-type TiO
2The amount ratio of nanofiber, described alcohol and described precious metal salt solution is 0.2-2g: 20-300mL: 2-20mL, and the concentration of described precious metal salt solution is 0.05-0.10mol/L.
5. method according to claim 4 is characterized in that: in the described step 1), the mass ratio of titanate esters and polyvinylpyrrolidone is 4: 1;
Described step 2) in, described Detitanium-ore-type TiO
2The amount ratio of nanofiber, described alcohol and described precious metal salt solution is 0.2g: 30mL: 3mL, and the concentration of described precious metal salt solution is 0.07mol/L.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: in the described step 1), in the described electrostatic spinning step, the flow velocity of electrostatic spinning stoste is 4-20ml/h; In the described calcining step, temperature is 400-500 ℃, and the time is 3-8 hour;
Described step 2) in, described intermittent type microwave heating steps is every microwave heating 10-30 after second, suspends 5-15 second; The total time of described intermittent type microwave heating is 2-60 minute; In the described intermittent type microwave heating steps, microwave frequency is 2000-3000MHz, and microwave power is 80～1000W; In the described washing step, cleaning solution is selected from least a in deionized water and the ethanol; In the described drying steps, temperature is 80-200 ℃, and the time is 1-3 hour.
7. method according to claim 6 is characterized in that: in the described step 1), in the described calcining step, temperature is 500 ℃, and the time is 4 hours;
Described step 2) in, in the described intermittent type microwave heating steps, microwave frequency is 2450MHz, and microwave power is 650-800W; In the described drying steps, temperature is 80 ℃, and the time is 2 hours.
8. noble metal-titanium dioxide nanofiber complex of obtaining of the arbitrary described preparation method of claim 1-7.
9. the application of the described noble metal of claim 8-titanium dioxide nanofiber complex in the electrode electrocatalyst materials of preparation fuel cell.
10. application according to claim 9 is characterized in that: described fuel cell is a Proton Exchange Membrane Fuel Cells.
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