CN100411732C - Method for preparing nano powder catalyst - Google Patents
Method for preparing nano powder catalyst Download PDFInfo
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- CN100411732C CN100411732C CNB2006100690784A CN200610069078A CN100411732C CN 100411732 C CN100411732 C CN 100411732C CN B2006100690784 A CNB2006100690784 A CN B2006100690784A CN 200610069078 A CN200610069078 A CN 200610069078A CN 100411732 C CN100411732 C CN 100411732C
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- 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
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- 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
Abstract
The present invention relates to a preparation method of nano powder body catalyst. It is characterized by that it uses a powdered inorganic compound of titanium as precursor reactant, uses an organic solution or aqueous solution containing compound of platinum family metal or/and transition family metal as precursor reactant solution. Said preparation method includes the following steps: firstly, soaking the powdered precursor reactant in said precursor reactant solution, uniformly stirring them, drying treatment, then making the obtained mixture undergo the processes of high-temperature oxidation, thermal decomposition, cooling and grinding so as to obtain a composite nano powder body containing titanium dioxide, then using said composite nano powder body as carrier, making one or several kinds of platinum family metals or trasition family metals be leaded on the surface of said composite nano powder body by means of chemical or physical deposition process so as to obtain the invented nano powder body catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of nano powder catalyst.
Background technology
Under the increasingly serious situation of global energy and environmental problem, hydrogen causes that as the development and utilization of energy carrier people more and more pay close attention to.Hydrogen is regarded as following optimal energy carrier because it is efficient, clean and be easy to produce and characteristics such as transportation.Use the fuel of hydrogen as the vehicles. will finish the history of the pollutant emissions such as greenhouse gases that cause because of traffic.The hydrogen energy source system comprises the generation of hydrogen, the storage of hydrogen and the utilization of hydrogen.The utilization of hydrogen valid approach the most is a fuel cell.Fuel cell is a kind of electrochemical TRT, be the process that the chemical energy of fuel directly is converted to electric energy, be not subjected to the restriction of Carnot cycle, energy conversion efficiency height (40%～60%), environment is not had harm, be considered to the cleaning of 21st century first-selection, generation technology efficiently.Wherein, Proton Exchange Membrane Fuel Cells (PEMFC) has become the main flow in all types of fuel cells.PEMFC can start fast in room temperature, and can change power output fast by load request, and it is electric motor car, do not rely on the submarine power source that air advances and the best candidate of various removable power supplys.
One of core component of PEMFC is a membrane electrode, and the core material that membrane electrode uses is a nano powder catalyst.The main component of this catalyst is platinum, support platinum or other platinum group metal and oxide thereof.Because use the platinum family noble metal,, also to consider electric conductivity, high-specific surface area, stability and the easily preparation of nano-powder simultaneously therefore at the consumption that will under the prerequisite that guarantees catalytic performance, reduce noble metal on the catalyst design as far as possible.The preparation method has very large influence to catalytic performance, noble metal carrying capacity and the noble metal utilization rate of catalyst.Main preparation methods at this field nano powder catalyst has at present: physical vaporous deposition, chemical vapour deposition technique, sluggish precipitation, direct precipitation method, sol-gel process, organic coordination compound precursor process, hydrothermal synthesis method, microemulsion method, solid phase method, coated method, radiation chemistry synthetic method, electrochemical deposition method, Adam's Si fusion casting, dipping-liquid phase reduction, gas phase reduction process, high-temperature alloy method and metallo-organic compound thermal decomposition method etc.The Pt/C that U.S. E-Tek company produces is adopted by the whole world a lot of research institution and company owing to its superior oxygen cathode reduction electrocatalysis characteristic.
Although obtained very big progress, adopt prior preparation method still to be difficult to satisfied combination property requirement to nano powder catalyst at these field international counterparts.In the PEMFC field, nano-carbon powder is considered to best platinum carrier all the time, but recently a lot of research work shows that also there is certain problem in its long-term serviceability.Traditional PEMFC eelctro-catalyst is that nano particle Pt is carried on the Vulcan-XC72 carbon black, Vulcan-XC72 contains S element and other impurity of trace, and the adhesion of Pt and carbon dust a little less than, in that for a long time the catalyst granules that causes in service is coalescent or poison, in addition in preparation catalyst process because carbon black support is an amorphous structure, it can cause the structural disordering of nano-metal particle, has therefore subdued the ratio of active crystal face in the catalyst to a certain extent.Asahi Glass company thinks and has generated H at the oxygen of negative electrode with after the hydrogen that anode infiltration is come reacts
2O
2, and generated H at the hydrogen of anode with after the air that the negative electrode infiltration is come reacts
2O
2, the hydroxy that generates when hydrogen peroxide decomposes on carbon carrier or platinum/carbon eelctro-catalyst has quickened near the ager process of the dielectric film catalyst carrier and the carrier.Therefore, in the low noble metal carrying capacity that realizes nano powder catalyst, have under the prerequisite of good electrocatalysis characteristic and performance steady in a long-term, the preparation method that exploitation has the nano powder catalyst of low manufacturing cost becomes the key issue that present urgent need solves.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano powder catalyst, it can satisfy the demand of prior art.
A kind of preparation method of nano powder catalyst, it is characterized in that the inorganic compound with the titanium of powdery is a precursor reagent, to contain the platinum group metal or/and the organic solution of the compound of magnesium-yttrium-transition metal or the aqueous solution are the presoma reaction solution, at first the powdery precursor reagent be impregnated in the presoma reaction solution, stir, then dry the processing, the mixture that obtains after again drying being handled carries out the high-temperature oxydation thermal decomposition process, cooling, grind, obtain a kind of composite nano powder that contains titanium dioxide, be carrier with the composite nano powder that makes again, the platinum group metal or/and the method for one or more of magnesium-yttrium-transition metal by chemistry or physical deposition is supported on the surface of composite nano powder, is finally obtained a kind of nano powder catalyst.
The preparation method of nano powder catalyst of the present invention has and makes simple and easyly, and the noble metal carrying capacity is low, and the electro catalytic activity height conducts electricity very well, and stability is excellent, long service life, the advantage that production cost is low.
Description of drawings
Accompanying drawing 1 is at SnO
2-TiO
2Composite nano powder is uploaded the transmission electron microscope photo of the nano powder catalyst of platinum.
Accompanying drawing 2 is at SnO
2-TiO
2The nano powder catalyst that composite nano powder is uploaded platinum is prepared into the polarization curve of membrane electrode in PEMFC.
The specific embodiment
Embodiment one
Preparation method according to nano powder catalyst of the present invention, at first stannous chloride, n-butanol, concentrated hydrochloric acid are mixed by certain volume ratio during preparation, get certain amount of mixed solution dipping TiN nano-powder (Hefei Kaier Nano Technology Development Co., Ltd, particle mean size 14nm, specific area 80m
2/ g, purity is greater than 97%), stir, in 120 ℃ of baking ovens, dry 45min, sintering 15min in 450 ℃ and air atmosphere takes out air cooling, grinds, and repeats above-mentioned steps again, to Sn: the Ti mol ratio is 1: 8, and sintering 1h in 450 ℃ and air atmosphere makes SnO for the last time
2-TiO
2Composite nano powder; Then adopt dipping-liquid phase reduction to support platinum on this powder, the mass fraction that makes Pt is 20% Pt/SnO
2-TiO
2Nano powder catalyst A.
Embodiment two
Preparation method according to nano powder catalyst of the present invention, at first stannous chloride, chloro-iridic acid, water, concentrated hydrochloric acid are mixed by certain volume ratio during preparation, get certain amount of mixed solution dipping TiC nano-powder (Hefei Kaier Nano Technology Development Co., Ltd, particle mean size 12nm, specific area 120m
2/ g, purity is greater than 97%), stir, in 90 ℃ of baking ovens, dry 75min, sintering 15min in 250 ℃ and oxidizing atmosphere, vacuum cooled is ground, and repeats above-mentioned steps again, to Sn: Ir: the Ti mol ratio is 2: 1: 6, sintering 1h in 250 ℃ and oxidizing atmosphere for the last time, annealing in process 1h in 300 ℃ and oxidizing atmosphere makes SnO again
2-IrO
x-TOi
2Composite nano powder; Then adopt sluggish precipitation to support platinum and ruthenium on this powder, the mass fraction that makes Pt and Ru is respectively 20% and 10% PtRu/SnO
2-IrO
x-TiO
2Nano powder catalyst B.
Embodiment three
According to the preparation method of nano powder catalyst of the present invention, at first chloro-iridic acid, isopropyl alcohol, concentrated hydrochloric acid are mixed by certain volume ratio during preparation, get certain amount of mixed solution dipping TiB
2Nano-powder (Hefei Kaier Nano Technology Development Co., Ltd, particle mean size 14nm, specific area 100m
2/ g, purity is greater than 97%), stir, in 50 ℃ of baking ovens, dry 120min, sintering 15min in 700 ℃ and air atmosphere, take out air cooling, grind, repeat above-mentioned steps again, to Ir: the Ti mol ratio is 1: 9, sintering 1h in 700 ℃ and air atmosphere for the last time, annealing in process 1h in 900 ℃ and oxidizing atmosphere makes IrO again
x-TiO
2Composite nano powder; Then adopt gas phase reduction process to support platinum and tin on this powder, the mass fraction that makes Pt and Sn is respectively 20% and 10% PtSn/IrO
x-TiO
2Nano powder catalyst C.
According to the preparation method of nano powder catalyst of the present invention, with the Pt/SnO that makes
2-TiO
2Nano powder catalyst A is that example is estimated result of use.The Pt/SnO that makes
2-TiO
2The transmission photo of nano powder catalyst A as shown in Figure 1.Be uniform-distribution with the granule of particle diameter less than 5nm as seen from Figure 1 on bulky grain, the granule of gained is a metal platinum, and bulky grain is corresponding to rutile phase SnO
2-TiO
2Solid solution.Fig. 2 is at SnO
2-TiO
2The nano powder catalyst that composite nano powder is uploaded platinum is prepared into the polarization curve of membrane electrode in PEMFC, and test condition is that the platinum carrying capacity of cathode and anode is 0.4mgcm at normal temperature, normal pressure with not under the condition of humidification
-2As can be seen from Figure 2, at 0.1A/cm
2Voltage under the current density is 0.68V, has shown extraordinary electrocatalysis characteristic.
The inorganic compound of the titanium of the powdery described in the present invention can be the nitride of titanium or in boride or carbide or the oxide one or more, and the granularity size is 1nm～10 μ m; The presoma reaction solution contains one or more platinums group metal or/and the compound of magnesium-yttrium-transition metal, wherein the platinum group metal can be Ru, Rh, Pd, Os, Ir or Pt, and magnesium-yttrium-transition metal can be Sn, Co, Sb, Mn, Ni, Fe, Cu, W, V, Mo, Cr, Pb or Cd; The dry temperature of handling is 20 ℃～150 ℃; The temperature of high-temperature oxydation thermal decomposition process is 200 ℃～800 ℃, and this processing procedure can be carried out in air, also can be controlled in certain oxidizing atmosphere and carry out; The composite nano powder that obtains further be impregnated in the presoma reaction solution, stir, then dry the processing, the mixture that obtains after dry the processing carries out the high-temperature oxydation thermal decomposition process, cooling, grind, recycle above-mentioned preparation process: dipping-stirring-drying-high-temperature oxydation thermal decomposition-cooling-grinding, until obtaining a kind ofly containing a certain proportion of platinum group metal or/and the composite nano powder of the thermal decomposition product of magnesium-yttrium-transition metal compound and titanium dioxide; As required, also can further this composite nano powder be carried out The high temperature anneal, the annealing in process temperature is 200 ℃～1000 ℃; Be carrier with the above-mentioned composite nano powder that makes again, or/and the method for one or more of magnesium-yttrium-transition metal by chemistry or physical deposition is supported on the surface of composite nano powder, the chemistry of these routines or the method for physical deposition can be physical vaporous depositions with the platinum group metal, chemical vapour deposition technique, sluggish precipitation, direct precipitation method, sol-gel process, the organic coordination compound precursor process, hydrothermal synthesis method, microemulsion method, solid phase method, coated method, the radiation chemistry synthetic method, electrochemical deposition method, Adam's Si fusion casting, dipping-liquid phase reduction, gas phase reduction process, high-temperature alloy method or metallo-organic compound thermal decomposition method.
The nano powder catalyst that utilizes preparation method of the present invention to obtain can be widely used in a lot of industrial circles such as Electrochemical Engineering, water electrolysis, fuel cell, photocatalysis.
Claims (7)
1. the preparation method of a nano powder catalyst, it is characterized in that the inorganic compound with the titanium of powdery is a precursor reagent, the inorganic compound of described titanium is the nitride of titanium, boride or carbide, the granularity size is 1nm～10 μ m, to contain the platinum group metal or/and the organic solution of the compound of Sn or the aqueous solution are the presoma reaction solution, at first the powdery precursor reagent be impregnated in the presoma reaction solution, stir, then dry the processing, the mixture that obtains after again drying being handled carries out the high-temperature oxydation thermal decomposition process, the temperature of high-temperature oxydation thermal decomposition process is 200 ℃～800 ℃, cooling, grind, obtain a kind of composite nano powder that contains titanium dioxide, be carrier with the composite nano powder that makes again, the platinum group metal or/and the method for Sn by chemistry or physical deposition is supported on the surface of composite nano powder, is finally obtained a kind of nano powder catalyst.
2. the preparation method of the described nano powder catalyst of claim 1 is characterized in that described platinum group metal is Ru, Rh, Pd, Os, Ir or Pt.
3. the preparation method of nano powder catalyst according to claim 1 is characterized in that the described dry temperature of handling is 20 ℃～150 ℃.
4. the preparation method of nano powder catalyst according to claim 1 is characterized in that the process of described high-temperature oxydation thermal decomposition process is carried out in oxidizing atmosphere.
5. the preparation method of nano powder catalyst according to claim 1, it is characterized in that described composite nano powder be impregnated in the presoma reaction solution, stir, then dry the processing, the mixture that obtains after dry the processing carries out the high-temperature oxydation thermal decomposition process, cooling, grind, recycle above-mentioned preparation process: dipping-stirring-drying-high-temperature oxydation thermal decomposition-cooling-grinding, until obtaining a kind ofly containing the platinum group metal or/and the composite nano powder of the thermal decomposition product of the compound of Sn and titanium dioxide.
6. the preparation method of nano powder catalyst according to claim 1 or 5 is characterized in that described composite nano powder is carried out The high temperature anneal, and the annealing in process temperature is 200 ℃～1000 ℃.
7. the preparation method of nano powder catalyst according to claim 1, the method that it is characterized in that described chemistry or physical deposition is physical vaporous deposition, chemical vapour deposition technique, sluggish precipitation, direct precipitation method, sol-gel process, organic coordination compound precursor process, hydrothermal synthesis method, microemulsion method, solid phase method, coated method, radiation chemistry synthetic method, electrochemical deposition method, Adam's Si fusion casting, dipping-liquid phase reduction, gas phase reduction process, high-temperature alloy method or metallo-organic compound thermal decomposition method.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100690784A CN100411732C (en) | 2006-09-22 | 2006-09-22 | Method for preparing nano powder catalyst |
| US12/441,880 US8946116B2 (en) | 2006-09-22 | 2007-09-14 | Nanometer powder catalyst and its preparation method |
| PCT/CN2007/070689 WO2008040222A1 (en) | 2006-09-22 | 2007-09-14 | Nanometer powder catalyst and its prepartion method |
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| CNB2006100690784A CN100411732C (en) | 2006-09-22 | 2006-09-22 | Method for preparing nano powder catalyst |
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| CN100411732C true CN100411732C (en) | 2008-08-20 |
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| CN100438972C (en) * | 2006-09-22 | 2008-12-03 | 中国海洋大学 | Method for preparation of nano powder |
| US20150364772A1 (en) * | 2014-05-30 | 2015-12-17 | GM Global Technology Operations LLC | Method to prepare alloys of platinum-group metals and early transition metals |
| CN104988535A (en) * | 2015-05-22 | 2015-10-21 | 东南大学 | Mixed metal oxide coating electrode and preparation method thereof |
| CN110676474B (en) * | 2018-07-02 | 2021-08-24 | 北京大学 | Pt-based metal nanocluster-metal oxide nanocomposite and preparation method and application thereof |
| CN109499597B (en) * | 2018-11-20 | 2022-04-01 | 浙江理工大学上虞工业技术研究院有限公司 | Preparation method of porous titanium dioxide/carbon nitride nanoparticle composite material |
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