CN102130342B - 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
- Publication number
- CN102130342B CN102130342B CN2010100345051A CN201010034505A CN102130342B CN 102130342 B CN102130342 B CN 102130342B CN 2010100345051 A CN2010100345051 A CN 2010100345051A CN 201010034505 A CN201010034505 A CN 201010034505A CN 102130342 B CN102130342 B CN 102130342B
- Authority
- CN
- China
- Prior art keywords
- solution
- noble metal
- tio
- titanium dioxide
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Catalysts (AREA)
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 nano fiber 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 preferably durability.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 at present is the alloy/C catalyst of platinum/C catalyst or platinum.The carbon of high-specific surface area is used for the platinum of nano-scale of load high dispersive, 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, such as next substituting such as multi-wall carbon nano-tube tube materials, because its hydrophobicity, above the Pt particle is difficult to be dispersed in.Therefore we as doing carrier material with conductive titanyl compound, come the life-span of extending catalyst-carrier with changing carrier material.Titanium dioxide (TiO
2) the commercial Chinese white that mainly is used as, because it has large 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 good crystallite size (less than 100 nanometers) and the titanium oxide of high-specific surface area, because its unique optics, electricity and catalytic property attract wide attention.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, affects 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.
The activity of catalyst can strengthen by the amount that increases the per unit volume surface area catalyst.Compare with Powdered, fibrous titanium dioxide is owing to have large specific surface and be convenient to that reactant is carried and product release causes widely interest of people.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 is the key that improves noble metal granule decentralization in the compound on the fiber.The method of the catalyst of the preparation noble-metal-supported that generally uses at present 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, Photodeposition etc., the time that often needs to grow allows 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 avoided the hot conduction and convection in the traditional heating to conduct heat, 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 to be carried out carbon nano-tube complicated pre-treatment.Therefore prepare fast the efficient Pt/TiO that is applicable to fuel cell system
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 nano fiber complex and preparation method thereof and application.
The method for preparing noble metal-titanium dioxide nano fiber complex provided by the invention comprises the steps:
1) with the solution mixing of the solution of titanate esters and polyvinylpyrrolidone as electrostatic spinning raw material solution, 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 nano fiber complex after the drying.
The step 1 of said method) in, 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 acetic acid is in this mixed liquor, the volume ratio of ethanol and acetic acid 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 raw material solution 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 raw material solution, control extruding of described electrostatic spinning raw material solution 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, the voltage of described power supply 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-titanium dioxide nano fiber complex for preparing according to the method described above; and the application of this noble metal-titanium dioxide nano fiber 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 form, utilize the Fast Heating of microwave so that the generating rate of particle is better than the growth rate of particle on the one hand, utilize on the other hand TiO
2Nanofiber disperses the noble metal nano particles of generation.The method preparation process is simple; do not need to add any protective agent, course of reaction is quick, and productive rate is high; can prepare in enormous quantities; the particle diameter of gained noble metal-titanium dioxide nano fiber 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-titanium dioxide nano fiber complex provided by the invention, for the innovation of the material of fuel cell oxidizing electrode eelctro-catalyst provides the foundation, significant at fuel cell electrode material preparation and application facet.
Description of drawings
Fig. 1 is Pt content that the embodiment of the invention 1 prepares when being 20%, high dispersive Pt/TiO
2The TEM photo of nanofiber complex.
Fig. 2 is Pt content that the embodiment of the invention 1 prepares when being 20%, 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. 3 is Pt content that the embodiment of the invention 2 prepares when being 30%, high dispersive Pt/TiO
2The TEM photo of nanofiber complex.
Fig. 4 is Pt content that the embodiment of the invention 2 prepares when being 30%, 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 that reference Pt plate electrode is to the cyclic voltammetry curve of 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 acetic acid, fully stir, then 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.The mixed solution of gained is sucked in the plastic injector, flow control is 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, to remove the organic substance in the product, namely obtained TiO
2Fiber product.
Then get the above-mentioned gained TiO of 0.2g
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, namely obtain the product of black, products obtained therefrom is aging, washing, 2 hours dryings of 80 ℃ of lower bakings 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 to the methyl alcohol electro-catalysis of the Pt plate electrode of Fig. 5, 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 acetic acid, fully stir, then 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.The mixed solution of gained is sucked in the plastic injector, flow control is 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, to remove the organic substance in the product, namely obtained TiO
2Fiber product.
Then get the above-mentioned gained TiO of 0.2g
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, namely obtain the product of black, products obtained therefrom is aging, washing, 2 hours dryings of 80 ℃ of lower bakings 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 to the methyl alcohol electro-catalysis of the Pt plate electrode of Fig. 5, 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 3
The positive tetraethyl titanate of 1.5g is joined in the mixed solution of 5ml ethanol and 5ml acetic acid, fully stir, then join in the 9ml ethanol that is dissolved with 0.78g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 25 minutes.The mixed solution of gained is sucked in the plastic injector, flow control is 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, to remove the organic substance in the product, namely obtained TiO
2Fiber product.
Then get the above-mentioned gained TiO of 0.2g
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, namely obtain the product of black, products obtained therefrom is aging, washing, 2 hours dryings of 80 ℃ of lower bakings 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 acetic acid, fully stir, then join in the 12ml ethanol that is dissolved with 0.85g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 50 minutes.The mixed solution of gained is sucked in the plastic injector, flow control is 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, to remove the organic substance in the product, namely obtained TiO
2Fiber product.
Then get the above-mentioned gained TiO of 0.3g
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, namely obtain the product of black, products obtained therefrom is aging, washing, 2 hours dryings of 80 ℃ of lower bakings 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 acetic acid, fully stir, then join in the 8ml ethanol that is dissolved with 0.25g polyvinylpyrrolidone (PVP number-average molecular weight 1,300,000) magnetic agitation 30 minutes.The mixed solution of gained is sucked in the plastic injector, flow control is 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, to remove the organic substance in the product, namely obtained TiO
2Fiber product.
Then get the above-mentioned gained TiO of 0.1g
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, namely obtain the product of black, products obtained therefrom is aging, washing, 80 ℃ of lower bakings were drying to obtain Au/TiO in 2 hours
2Composite fibre, this moment, the decentralization of Au particle was relatively poor.
Claims (9)
1. a method for preparing noble metal-titanium dioxide nano fiber complex comprises the steps:
1) with the solution mixing of the solution of titanate esters and polyvinylpyrrolidone as electrostatic spinning raw material solution, 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 nano fiber complex after the drying;
Described step 1) in, in the described electrostatic spinning step, the flow velocity of electrostatic spinning raw material solution 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.
2. method according to claim 1 is characterized in that: 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 acetic acid; In the solution of described polyvinylpyrrolidone, solvent is 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, it 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. arbitrary described method according to claim 1-3, it is characterized in that: described step 1), the mass ratio of titanate esters and polyvinylpyrrolidone is 2: 1-5: 1, in the mixed liquor of described ethanol and acetic acid, the volume ratio of ethanol and acetic acid 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, it is characterized in that: 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. method according to claim 1, it is characterized in that: 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.
7. the noble metal-titanium dioxide nano fiber complex that obtains of the arbitrary described preparation method of claim 1-6.
8. the application of the described noble metal-titanium dioxide nano fiber complex of claim 7 in the electrode electrocatalyst materials of preparation fuel cell.
9. application according to claim 8 is characterized in that: described fuel cell is Proton Exchange Membrane Fuel Cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100345051A CN102130342B (en) | 2010-01-19 | 2010-01-19 | Noble metal-titanium dioxide nano fiber complex and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100345051A CN102130342B (en) | 2010-01-19 | 2010-01-19 | Noble metal-titanium dioxide nano fiber complex and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102130342A CN102130342A (en) | 2011-07-20 |
| CN102130342B true CN102130342B (en) | 2013-04-10 |
Family
ID=44268296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010100345051A Expired - Fee Related CN102130342B (en) | 2010-01-19 | 2010-01-19 | Noble metal-titanium dioxide nano fiber complex and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102130342B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977779B (en) * | 2014-06-03 | 2016-03-30 | 东南大学 | Aluminum oxide titanium white hetero-junctions nano fibre carrier and its preparation method and application in anti-sintering noble metal catalyst system |
| CN105280939A (en) * | 2014-07-09 | 2016-01-27 | 中国第一汽车股份有限公司 | Device and method for preparing multi-layer composite nanofiber proton exchange membrane |
| CN106205762B (en) * | 2016-06-24 | 2018-06-29 | 四川艾尔法泰克科技有限公司 | Metal-based titanium oxide nanofiber composited contact material and preparation method thereof |
| CN106519848B (en) * | 2016-11-17 | 2019-08-09 | 重庆文理学院 | A kind of preparation method of the net aldehyde nanometer texture paint of photocatalysis |
| CN107185511B (en) * | 2017-04-05 | 2020-05-12 | 中国地质大学（北京） | TiO 22Nano-sheet modified TiO2Preparation method of nanofiber membrane |
| CN107344097A (en) * | 2017-06-20 | 2017-11-14 | 海安县中山合成纤维有限公司 | A kind of Ag, Au and TiO2Composite chemical fibre material |
| CN108448126B (en) * | 2018-02-09 | 2020-09-04 | 中南大学 | PtAuTi nanowire catalytic material, preparation method thereof and application of PtAuTi nanowire catalytic material as fuel cell catalyst |
| CN109888316B (en) * | 2019-03-14 | 2021-01-15 | 内蒙古科技大学 | Method for preparing catalyst by using nitrogen-doped graphene, working electrode and preparation method of working electrode |
| CN109943917A (en) * | 2019-04-08 | 2019-06-28 | 南京威安新材料科技有限公司 | A kind of titanium dioxide nanofiber preparation method and device |
| CN112952121A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Electrode material with fiber structure, preparation and application |
| CN111575833B (en) * | 2020-05-18 | 2022-10-04 | 湖北工程学院 | Preparation method of titanium dioxide nanofiber negative electrode material |
| CN114225934A (en) * | 2021-12-28 | 2022-03-25 | 上海第二工业大学 | Pt atom loaded nano TiO2Dense foam and method of making same |
| CN116672901B (en) * | 2023-08-04 | 2023-10-27 | 西安金沃泰环保科技有限公司 | Nanofiltration material for acid-containing waste gas and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219377A (en) * | 2008-01-11 | 2008-07-16 | 山东大学 | Precious metal/one-dimensional titanium dioxide nanostructure composite material and method for producing the same |
| CN101306839A (en) * | 2008-07-10 | 2008-11-19 | 长春理工大学 | Process for preparing titanium dioxide nano-belts |
| CN101428852A (en) * | 2008-12-05 | 2009-05-13 | 中国科学院化学研究所 | Method for producing ultra-dewatering titanium dioxide film with electrostatic spinning |
-
2010
- 2010-01-19 CN CN2010100345051A patent/CN102130342B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219377A (en) * | 2008-01-11 | 2008-07-16 | 山东大学 | Precious metal/one-dimensional titanium dioxide nanostructure composite material and method for producing the same |
| CN101306839A (en) * | 2008-07-10 | 2008-11-19 | 长春理工大学 | Process for preparing titanium dioxide nano-belts |
| CN101428852A (en) * | 2008-12-05 | 2009-05-13 | 中国科学院化学研究所 | Method for producing ultra-dewatering titanium dioxide film with electrostatic spinning |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102130342A (en) | 2011-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102130342B (en) | Noble metal-titanium dioxide nano fiber complex and preparation method and application thereof | |
| Xu et al. | Novel Pd/β-MnO2 nanotubes composites as catalysts for methanol oxidation in alkaline solution | |
| Lee et al. | Progress in the synthesis of carbon nanotube-and nanofiber-supported Pt electrocatalysts for PEM fuel cell catalysis | |
| CN103441287B (en) | The preparation method of a kind of direct methanol fuel cell membrane electrode | |
| Rajesh et al. | Carbon nanotubes generated from template carbonization of polyphenyl acetylene as the support for electrooxidation of methanol | |
| KR101349068B1 (en) | Method for manufacturing core-shell type surpported catalysts for fuel cell | |
| CN101733094B (en) | Pt-CeO2/graphene electro-catalyst and preparation method thereof | |
| Chen et al. | Electrooxidation of methanol on Pt@ Ni bimetallic catalyst supported on porous carbon nanofibers | |
| Guo et al. | Multi-walled carbon nanotubes modified by sulfated TiO2–A promising support for Pt catalyst in a direct ethanol fuel cell | |
| Li et al. | Porous ceramic nanofibers as new catalysts toward heterogeneous reactions | |
| WO2006054636A1 (en) | Carbon fiber, porous support-carbon fiber composite, process for producing them, catalyst structure, electrode for solid polymer fuel cell and solid polymer fuel cell | |
| CN101745384A (en) | Platinum/graphene nano electro-catalyst and preparation method thereof | |
| Wu et al. | Improved kinetics of methanol oxidation on Pt/hollow carbon sphere catalysts | |
| CN101874131A (en) | Process for production of carbon nanofiber carrying metal microparticles | |
| CN101740786A (en) | PtRu/graphene nano electro-catalyst and preparation method thereof | |
| CN100464841C (en) | Noble metal electrocatalyst based on nano carbon fiber and its preparing method | |
| Abbas et al. | Decorated carbon nanofibers with mixed nickel− manganese carbides for methanol electro-oxidation in alkaline solution | |
| CN101249435B (en) | Surface treating method of carbon nano-tube and loading type catalyst of carbon nano-tube | |
| CN114068955A (en) | Fuel cell membrane electrode and preparation method thereof | |
| KR20100124149A (en) | Metal-impregnated carbon nanofibers and preparation method of the same, and fuel cell and filter using the metal-impregnated carbon nanofibers | |
| CN106140162A (en) | A kind of preparation method of the copper nano-particle for electrocatalytic hydrogen evolution/carbon nano-fiber hybrid material | |
| Long et al. | Improving the electrical catalytic activity of Pt/TiO 2 nanocomposites by a combination of electrospinning and microwave irradiation | |
| CN103212422A (en) | Preparation method of carbon nanofiber composite material loaded with palladium-cobalt alloy nanometer particles and electro-catalytic oxidation method for formic acid or methyl alcohol | |
| CN1185738C (en) | Preparation method of nano catalyst for low-temp. fuel cell | |
| CN106784894A (en) | A kind of method for preparing the graphene-based anode electrocatalyst of direct alcohol fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130410 Termination date: 20210119 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |