CN102593476B - Nano-porous PtSi material and preparation method thereof - Google Patents

Nano-porous PtSi material and preparation method thereof Download PDF

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CN102593476B
CN102593476B CN201210067748.4A CN201210067748A CN102593476B CN 102593476 B CN102593476 B CN 102593476B CN 201210067748 A CN201210067748 A CN 201210067748A CN 102593476 B CN102593476 B CN 102593476B
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nano
porous
ptsi
foundry alloy
electrode
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CN102593476A (en
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余金山
周新贵
张长瑞
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National University of Defense Technology
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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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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a nano-porous PtSi material and a preparation method thereof. The nano-porous PtSi material mainly comprises a PtSi compound, wherein three-dimensional connected nano pores are uniformly distributed in the nano-porous PtSi material. The preparation method of the nano-porous PtSi material includes the following steps: feeding a platinum sheet and silicon powder in an inert gas atmosphere and heating and melting; maintaining the temperature for 30-60 minutes until a melt is uniform, then cooling the melt to room temperature and obtaining a PtmSi100-m master alloy, wherein m is 10-40; re-melting the PtmSi100-m master alloy; preparing a PtmSi100-m master alloy strip by adopting a single-roller strip-casting method, wherein the rotating speed of the roller is 300-6000r/min; and with the PtmSi100-m master alloy strip as a work electrode, establishing an electromechanical work station by adopting a tri-electrode method, and dissolving a Si matrix by adopting an anodic oxidation method to obtain the nano-porous PtSi material. The nano-porous PtSi material can be used as an anode catalyst of a methanol fuel cell and has the advantages of simple process, short period, low cost, favorable effect and the like.

Description

Nano-porous PtSi material and preparation method thereof
Technical field
The present invention relates to porous nanometer material field, particularly relate to a kind of nano-porous PtSi material and its preparation method and application.
Background technology
Direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) be the one of Proton Exchange Membrane Fuel Cells, it is directly injected in fuel cell by methyl alcohol to carry out electro-catalysis generating, and need not first through any fuel reforming modifying apparatus, so there is not the preparation of hydrogen, storage, transport and security problems in DMFC; And it is simple to have structure, easy to operate, store easy to carry, fuel source enriches, and methyl alcohol is pollution-free after using, the advantages such as clean environment firendly, thus there is great competitive advantage in the fields such as Small Civil power supply and compact power such as notebook computers, have broad application prospects.
In the DMFC course of work, on anode and negative electrode, the electrocatalysis of catalyst is very crucial.Early stage fuel cell makees catalyst, so development slowly owing to will use a large amount of expensive metal platinum.Along with the development of nanometer technology; the Pt nanoparticle of carrier supported or the compound nano-particle of platinum are widely used as eelctro-catalyst; this catalyst decentralization and the more early stage catalyst of specific area improve greatly; thus fuel cell is in recent years the attracted interest of a large amount of researcher, development is rapidly.
At present, the anode catalyst of DMFC of business application does the Pt nanoparticle (Pt/C) of carrier with active carbon particle or platinum rhodium nanoparticles (Pt-Ru/C) is.Because platinum, rhodium are noble metal, expensive and resource-constrained, must adopt effective measures to reduce the consumption of platinum; In addition due to the unsteadiness of simple substance nano metal itself, easily reunite in the course of work and significantly reduce activity and the specific area of catalyst, thus catalyst was lost efficacy gradually.On the other hand, simple metal platinum has very strong suction-operated to Methanol Decomposition intermediate CO, has adsorbed the platinum meeting " poisoning " of CO and has lost electrocatalysis.Therefore, how to reduce the consumption of platinum, improve catalyst chemical stability, prevent platinosis, seek the eelctro-catalyst of the Methanol Anode oxidation of high efficiency, low cost, improve the speed of Methanol Anode oxidation, the loss reducing anode catalyst is one of important directions of DMFC application study.
Nano-porous materials is a kind of nano material with three-dimensional communication nano-pore structure.This nano material has very large specific area and surface activity, and its exclusive three-dimensional connected porous structure allows liquid phase medium to flow freely wherein, is suitable for very much the electrochemical catalyst of fuel cell.But simple substance nanoporous noble metal also faces electrochemical stability sex chromosome mosaicism as fuel battery anode catalyst, namely reunite due to the huge surface area of nano material and high surface in use procedure.
Summary of the invention
Technical problem to be solved by this invention is: for prior art Problems existing, the invention provides that a kind of electrochemical stability is good, the nano-porous PtSi material with three-dimensional connected porous structure and preparation method thereof.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of nano-porous PtSi material, described nano-porous PtSi material mainly comprises PtSi compound, and (wherein the element composition of PtSi compound is generally Pt to be evenly equipped with the nanoaperture of three-dimensional communication in described nano-porous PtSi material msi 100-m, m is 10 ~ 40).
In above-mentioned nano-porous PtSi material, the aperture of nanoaperture is preferably 50 nm ~ 2000 nm.
Above-mentioned nano-porous PtSi material profile is preferably in flake.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned nano-porous PtSi material, comprises the following steps:
(1) melting Pt msi 100-mfoundry alloy: platinized platinum (be preferably 4N) and silica flour (be preferably polycrystalline silica flour, be preferably 4N, 200 orders) are placed in heating and melting under inert gas (being preferably high-purity argon gas) atmosphere, be incubated 30 ~ 60 minutes even to melt after, cool to room temperature, obtains Pt msi 100-mfoundry alloy; Wherein, m is 10 ~ 40;
(2) get rid of band method (melting-spinning) and prepare Pt msi 100-mfoundry alloy band: by described Pt msi 100-mfoundry alloy refuse, adopts melt spinning to prepare Pt msi 100-mfoundry alloy band, roller rotating speed is 2000 r/min ~ 6000 r/min;
(3) electrochemical method selective dissolution Si matrix: with obtained Pt msi 100-mfoundry alloy band is work electrode, adopts three-electrode method to set up electrochemical workstation, adopts anode oxidation method by described Pt msi 100-msi matrix dissolution in foundry alloy band, obtains described nano-porous PtSi material.
In above-mentioned preparation method, described electrochemical workstation is preferably with hydrofluoric acid (preferred 0.1ml/L) for electrolyte, is to electrode, with silver electrode/silver chloride electrode for reference electrode with platinum black electrode.Adopt described anode oxidation method to dissolve before Si after setting up described electrochemical workstation, first preferably adopt cyclic voltammetry to determine anodised current potential, on described work electrode, then to load the voltage that forms this current potential with by described Si matrix dissolution.
In above-mentioned preparation method, the voltage of described loading is preferably 0.5v ~ 0.8v, dissolves duration and is preferably 500s ~ 2000s.
In above-mentioned preparation method, the Pt that described step (2) is obtained msi 100-mfoundry alloy beam thickness is preferably 10 μm ~ 50 μm, width 1 mm ~ 2mm.
In above-mentioned preparation method, described Pt msi 100-mm in foundry alloy preferably gets 30.
Compared with prior art, the invention has the advantages that:
1, nano-porous PtSi material of the present invention, be the nano material with three-dimensional connected porous structure, it is conducive to medium and flows in hole, can improve the catalytic efficiency of material.This material is made up of PtSi compound, Stability Analysis of Structures also effectively can lower the consumption of Pt, there is electrochemical stability more better than simple substance Pt nanoparticle catalyst, and PtSi has the better catalytic action of methyl alcohol than simple substance Pt, can be used as methanol fuel cell anode catalyzer, without the need to carrier supported, electrochemical catalysis activity is high.Due to the existence of Si in material, effectively reduce the consumption of precious metals pt, reduce material cost.
2, the preparation method of nano-porous PtSi material of the present invention, makes the compound of separating out 3-D nano, structure in alloy by rapid solidification, dissolves away matrix, obtain the nano-porous materials without the need to carrier supported with chemistry or electrochemical method.Its technical process is simple, and equipment requirement is low, and process equipment used mainly contains vacuum melting furnace, gets rid of carrying device, electrochemical workstation and electrolysis tank etc., and its process route is simple, and process cycle is short, environmentally safe in preparation process and technique versatility is good.
Accompanying drawing explanation
Fig. 1 gets rid of the standby Pt of band legal system in the embodiment of the present invention 1 30si 70x-ray diffraction (XRD) collection of illustrative plates of foundry alloy band.
Fig. 2 is Pt in the embodiment of the present invention 1 30si 70the ESEM microphoto of foundry alloy band.
Fig. 3 is the ESEM microphoto of nano-porous PtSi material obtained in the embodiment of the present invention 1.
Fig. 4 is Pt in the embodiment of the present invention 2 30si 70the ESEM microphoto of foundry alloy band.
Fig. 5 is the ESEM microphoto of nano-porous PtSi material obtained in the embodiment of the present invention 2.
Fig. 6 is the Pt prepared in comparative example of the present invention 30si 70the ESEM microphoto of foundry alloy band.
Fig. 7 be in the embodiment of the present invention 2 nano-porous PtSi material and commercial Pt nanoparticle catalyst to methanol oxidation effect contrast curve synoptic diagram.
Fig. 8 be in the embodiment of the present invention 2 nano-porous PtSi material first time volt-ampere circulation and 500 volt-ampere circulate after volt-ampere curve correlation curve schematic diagram.
Fig. 9 be in the embodiment of the present invention 2 the first time volt-ampere circulation of commercial Pt nanoparticle catalyst and 500 volt-ampere circulate after volt-ampere curve correlation curve schematic diagram.
Embodiment
Below with reference to Figure of description and specific embodiment, the present invention is described in further details.
embodiment 1:
A kind of nano-porous PtSi material of the present invention, mainly comprises PtSi compound, and outward appearance is in flake.Be evenly equipped with the nanoaperture of three-dimensional communication in nano-porous PtSi material, aperture be 800 nm ~ 2000 nm(wherein PtSi compound element composition be generally Pt 30si 70).
The nano-porous PtSi material of the present embodiment prepares mainly through following steps:
(1) melting Pt 30si 70foundry alloy:
High-purity platinized platinum (99.98%) and polycrystalline silica flour (99.998%) are placed in crucible after ethanol purge, under high-purity argon gas atmosphere, be placed in induction heating vacuum furnace heating and melting, be incubated 30 minutes to melt evenly after, cool to room temperature under high-purity argon gas atmosphere, obtained Pt 30si 70foundry alloy.
(2) band legal system is got rid of for Pt 30si 70foundry alloy band:
By Pt 30si 70foundry alloy melts again under high-purity argon gas atmosphere, adopts melt spinning to prepare Pt 30si 70foundry alloy band, roller rotating speed is 4000 r/min; Obtained Pt 30si 70foundry alloy beam thickness is 20 μm, width 1 mm ~ 2mm.This Pt 30si 70as shown in Figure 2, as seen from Figure 2, its structure is distributed network shape PtSi precipitate in black Si matrix to the ESEM microphoto of foundry alloy band; Its X-ray diffraction (XRD) collection of illustrative plates as shown in Figure 1, visible Pt 30si 70foundry alloy band composition is PtSi compound and Si matrix mutually.
(3) electrochemical method selective dissolution Si matrix:
With 0.1ml/L hydrofluoric acid for electrolyte, platinum black electrode is to electrode, and silver electrode or silver chloride electrode are reference electrode, Pt 30si 70foundry alloy band is work electrode, sets up electrochemical workstation.Adopt cyclic voltammetry to determine that the anodised current potential of Si is 0.7v, on foundry alloy band, then load the voltage of 0.7v by Pt 30si 70si matrix dissolution in foundry alloy band, dissolution time, for being about 1000s, obtains nano-porous PtSi material.
The ESEM microphoto of nano-porous PtSi material obtained above as shown in Figure 3, remove completely, obtains porous PtSi material by visible Si matrix, and its composition is PtSi compound, and aperture is 800 nm ~ 2000 nm.
embodiment 2:
A kind of nano-porous PtSi material of the present invention, it mainly comprises PtSi compound, and outward appearance is in flake.Be evenly equipped with the nanoaperture of three-dimensional communication in nano-porous PtSi material, aperture is 80 nm ~ 200 nm.
Nano-porous PtSi material of the present invention is mainly prepared by following steps:
(1) melting Pt 30si 70foundry alloy:
High-purity platinized platinum (99.98%) and polycrystalline silica flour (99.998%) are placed in crucible after ethanol purge, under high-purity argon gas atmosphere, be placed in induction heating vacuum furnace heating and melting, be incubated 30 minutes to melt evenly after, cool to room temperature under high-purity argon gas atmosphere, obtained Pt 30si 70foundry alloy.
(2) band legal system is got rid of for Pt 30si 70foundry alloy band:
By Pt 30si 70foundry alloy melts again under high-purity argon gas atmosphere, adopts melt spinning to prepare Pt 30si 70foundry alloy band, roller rotating speed is 6000 r/min, obtained Pt 30si 70foundry alloy beam thickness is 20 μm, width 1 mm ~ 2mm.This Pt 30si 70as shown in Figure 4, as seen from Figure 4, foundry alloy structure is distributed network shape PtSi precipitate in black Si matrix to the ESEM microphoto of foundry alloy band, and precipitate is evenly tiny.
(3) electrochemical method selective dissolution Si matrix:
With 0.1ml/L hydrofluoric acid for electrolyte, platinum black electrode is to electrode, and silver electrode or silver chloride electrode are reference electrode, Pt 30si 70foundry alloy band is work electrode, sets up electrochemical workstation.Adopt cyclic voltammetry to determine that the anodised current potential of Si is 0.7v, on foundry alloy band, then load the voltage of 0.7v by Pt 30si 70si matrix dissolution in foundry alloy band, dissolution time is about 1000s, obtains nano-porous PtSi material.
As shown in Figure 5, visible Si matrix dissolves the ESEM microphoto of nano-porous PtSi material obtained above completely, obtains porous PtSi material, and its composition is PtSi compound, and aperture is 80 nm ~ 200 nm.
Nano-porous PtSi material obtained above and existing commercial Pt nanoparticle catalyst are carried out testing methanol oxidation effect contrast, acquired results as shown in Figure 7.Can find out that nano-porous PtSi material is lower to Methanol Anode oxidizing potential, illustrate that nano-porous PtSi material of the present invention has than commercial Pt nanoparticle catalyst the better electrocatalysis of methyl alcohol.
Nano-porous PtSi material obtained above and existing commercial Pt nanoparticle catalyst (Pt/C catalyst) are carried out electrochemical stability contrast test, test with 1mol/L sulfuric acid as electrolyte, carry out the electrochemical stability of assessment material with the volt-ampere curve contrast after first time volt-ampere circulation and 500 volt-ampere circulations, acquired results as shown in Figure 8, Figure 9.Fig. 8 is the volt-ampere curve contrast after porous PtSi material obtained above first time volt-ampere circulation and 500 volt-ampere circulate; Fig. 9 is the volt-ampere curve contrast after the first time volt-ampere circulation of commercial Pt nanoparticle catalyst and 500 volt-ampere circulate.As seen from the figure, porous PtSi compound obviously has the electrochemical stability more much higher than commercial Pt nanoparticle catalyst.Be furnished with the nano-porous PtSi material of the nanoaperture of three-dimensional communication, its composition is PtSi compound.
comparative example:
A kind of comparative example of the present invention, carry out following steps successively:
(1) melting Pt 30si 70foundry alloy: step is identical with embodiment 1.
(2) band legal system is got rid of for Pt 30si 70foundry alloy band:
By Pt 30si 70foundry alloy melts again under high-purity argon gas atmosphere, adopts melt spinning to prepare Pt 30si 70foundry alloy band, roller rotating speed is 2000 r/min; Obtained Pt 30si 70foundry alloy beam thickness is 20 μm, width 1 mm ~ 2mm.
Pt obtained above 30si 70the ESEM microphoto of foundry alloy band is as shown in Figure 6, as seen from Figure 6, low owing to getting rid of tape speed as seen from Figure 6, and aluminium alloy setting rate is slow, and the PtSi compound of precipitation is very thick, does not also form three-dimensional connected porous tissue.Therefore, can not for the preparation of nano-porous PtSi material of the present invention.
In sum, nano-porous PtSi material preparation process of the present invention is simple, and equipment requirement is low, simple, and process cycle is short, environmentally safe in preparation process.PtSi material of the present invention, is made up of PtSi compound, has electrochemical stability more better than simple substance Pt nanoparticle catalyst, and PtSi has the better catalytic action of methyl alcohol than simple substance Pt, as methanol fuel cell anode catalyzer, without the need to carrier supported, electrochemical catalysis activity is high.Meanwhile, the present invention can also study the porous silicon compound preparing other noble metals to those skilled in the art and provide research direction and enlightenment.
Below be only the preferred embodiment of the present invention, protection scope of the present invention be not only confined to above-described embodiment, conceives various process programs without substantial differences all in protection scope of the present invention with the present invention.

Claims (4)

1. a preparation method for nano-porous PtSi material, comprises the following steps:
(1) melting Pt msi 100-mfoundry alloy: platinized platinum and silica flour are placed in heating and melting under inert gas atmosphere, be incubated 30 minutes ~ 60 minutes to melt evenly after, cool to room temperature, obtained Pt msi 100-mfoundry alloy; Wherein, m is 30 ~ 40;
(2) Pt is prepared msi 100-mfoundry alloy band: by described Pt msi 100-mfoundry alloy refuse, adopts melt spinning to prepare Pt msi 100-mfoundry alloy band, roller rotating speed is 4000 r/min ~ 6000 r/min;
(3) selective dissolution Si matrix: with obtained Pt msi 100-mfoundry alloy band is work electrode, adopts three-electrode method to set up electrochemical workstation, adopts anode oxidation method by described Pt msi 100-msi matrix dissolution in foundry alloy band, obtains described nano-porous PtSi material;
Adopt described anode oxidation method to dissolve before Si after setting up described electrochemical workstation, first adopt cyclic voltammetry to determine anodised current potential, on described work electrode, then to load the voltage that forms this current potential with by described Si matrix dissolution;
The voltage of described loading is 0.7v ~ 0.8v, and dissolving duration is 1000s ~ 2000s.
2. the preparation method of nano-porous PtSi material according to claim 1, is characterized in that, described electrochemical workstation take hydrofluoric acid as electrolyte, is to electrode, with silver electrode/silver chloride electrode for reference electrode with platinum black electrode.
3. the preparation method of nano-porous PtSi material according to claim 1 and 2, is characterized in that, the Pt that described step (2) is obtained msi 100-mfoundry alloy beam thickness is 10 μm ~ 50 μm, width 1 mm ~ 2mm.
4. the preparation method of nano-porous PtSi material according to claim 1 and 2, is characterized in that, described Pt msi 100-mm in foundry alloy gets 30.
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