CN102626617B - Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst - Google Patents

Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst Download PDF

Info

Publication number
CN102626617B
CN102626617B CN201210074930.2A CN201210074930A CN102626617B CN 102626617 B CN102626617 B CN 102626617B CN 201210074930 A CN201210074930 A CN 201210074930A CN 102626617 B CN102626617 B CN 102626617B
Authority
CN
China
Prior art keywords
porous silicon
preparation
dimensional platinum
nano catalyst
platinum nano
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.)
Active
Application number
CN201210074930.2A
Other languages
Chinese (zh)
Other versions
CN102626617A (en
Inventor
王晓红
王玫
刘理天
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN201210074930.2A priority Critical patent/CN102626617B/en
Publication of CN102626617A publication Critical patent/CN102626617A/en
Application granted granted Critical
Publication of CN102626617B publication Critical patent/CN102626617B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a preparation method of a porous silicon supported three-dimensional platinum nanometer catalyst, which belongs to the fields of micro energy supplies and the catalytic technology. The chemical plating preparation method of the porous silicon supported three-dimensional platinum nanometer catalyst comprises the following three parts: 1, preparing a porous silicon film; 2, modifying the surface of the porous silicon film through utilizing ICP and HF preprocessing; and 3, chemically plating the surface-modified porous silicon film with a three-dimensional platinum nanometer catalyst. The preparation method which overcomes technological condition rigor and difficult quality control defects existing in the preparation of the catalyst of the prior art through utilizing sputtering and electrochemical plating methods has the advantages of simple operation technology and easy quality control, and is especially suitable for a production technology of micro direct methanol fuel cells.

Description

The preparation method of the three-dimensional platinum nano catalyst of porous silicon load
Technical field
The invention belongs to micro power source and catalysis technical field, particularly the preparation method of the three-dimensional platinum nano catalyst of porous silicon load.
Technical field
Along with the development of portable type electronic product and radio sensing network, its requirement to micro power source is more and more higher.Traditional lithium battery can not meet growing energy demand.Micro direct methanol fuel battery based on MEMS technology (DMFC) becomes the best candidate power supply of following portable set and micro-system with advantages such as its high-energy utilization rate, low pollution, low costs.What yet the PEM of DMFC was multiplex greatly at present is Nafion film, the micro fabrication of it and standard is incompatible, and shape changes along with the variation of water content, thereby cause catalyst to come off, battery performance declines, T.Pichonat for this reason, B.G.Manuel and D.Hauden, Deng at " A new proton-conducting porous silicon membrane for small fuel cells, " < < Chem.Eng.J.vol.101, 2004, pp.107-111 > >. and K.L.Chu, M.A.Shannon, and R.I.Masel, Deng at " An improved miniature direct formic acid fuel cell based on nanoporous silicon for portable power generation, " < < J.Electrochem.Soc.vol.153, 2006, in pp.A1562-A1567 > >. propose to utilize porous silicon to fill and can carry out the material of proton conducting as the PEM of DMFC.Yet for this micro direct methanol fuel battery based on porous silicon, how on porous silicon surface, the efficient catalyst of load becomes a huge challenge.
T.Pichonat ]deng people at " Mesoporous silicon-based miniature fuel cells for nomadic and chip-scale systems, " < < Microsyst.Technol., vol.12, 2006, pp.330-334. in > >, propose to utilize Nafion solution to make solvent, Pt/C does solute, the Nafion solution of having prepared Pt/C, and utilize the method for spraying that catalyst is uploaded on porous silicon-base PEM, yet catalyst prepared by this method and the adhesion of backing material are not strong, catalyst can come off along with the carrying out of course of reaction, and in spraying process, exist a large amount of noble metal wasting phenomenons.T.Pichonat ]deng people also at " A Porous Silicon-Based Ionomer-Free Membrane Electrode Assembly for Miniature Fuel Cells, " < < Fuel cells, vol.5, 2006, in the follow-up research of pp.323-325 > >, utilize again the method Kaolinite Preparation of Catalyst of sputter and electrochemistry plating: first sputter forms Pt Seed Layer on porous silicon, the method of recycling electrochemistry plating by catalyst cupport to porous silicon, yet this method must strictly be controlled sputtering condition, the hole of porous silicon because the blocked up meeting of the Seed Layer of sputter results in blockage, hinder the transmission of proton, the very few words of carrying capacity can affect the catalytic performance of catalyst.So how utilizing simple method is the subject matter that research exists at present at the efficient nanocatalyst of porous silicon surface load.
Summary of the invention
The preparation method who the object of this invention is to provide the three-dimensional platinum nano catalyst of a kind of porous silicon load, is characterized in that: described preparation method is that concrete technology is as follows at the three-dimensional platinum nano catalyst of porous silicon surface chemical plating:
A. be first the preparation of porous silicon film:
(1) at n +the two-sided dry oxide growth SiO of type silicon chip 2layer, at SiO 2lPCVD on layer (Low Pressure Chemical Vapor Deposition) prepares Si 3n 4layer;
(2) at Si 3n 4upper sputter Cr/Au is as anodised masking layer;
(3) will be at Si 3n 4the n of sputter Cr/Au film on layer +two-sided conventional photoetching, the formation figure of carrying out of type silicon chip;
(4) adopt KOH wet etching, at n +silicon fiml in the middle of the two-sided formation of type silicon chip;
(5) anodic oxidation generates porous silicon;
B. be secondly to utilize ICP (inductively coupled plasma) and HF Precondition on Porous Silicon film to carry out finishing: first carry out ICP etching, etch away the silicon of anodic oxidation remainder, porous silicon surface is modified, at porous silicon surface, form defective bit; Then the HF aqueous solution of putting into 40% (v/v) concentration soaks 2s and carries out the pretreatment of HF solution, at porous silicon surface, forms Si-H key;
C. be finally the three-dimensional platinum nano catalyst of chemical plating on the process porous silicon film of finishing, concrete technology condition is as follows: by the porous silicon through finishing, at precursor liquid, be 0.5-3.5mM H 2ptCl 6in the aqueous solution, under 18-25 ℃ of reaction temperature, soak 30min-2h; On porous silicon surface, form three-dimensional platinum nano catalyst.
Described two-sided dry oxide growth SiO 2layer is as Si 3n 4cushion, Si thereon 3n 4layer is as the masking layer of KOH corrosion.
The condition of described employing KOH corrosion is: KOH concentration: 33wt%, temperature is 78-81 ℃.
The process conditions that described anodic oxidation generates porous silicon are: in double flute anodic oxidation equipment, adding is 40% (v/v) HF by volume: straight alcohol=2: 1 solution; Current density: 180-250mA/cm 2; Etching time: 10-15min.
In described step B, ICP etching condition is plasma power: 400W; Accelerating power: 10W; SF 6: 70sccm; O 2: 0-5sccm.
The invention has the beneficial effects as follows the process conditions harshness that the present invention adopts three-step approach to utilize the method Kaolinite Preparation of Catalyst of sputter and electrochemistry plating to exist in the technique of the three-dimensional platinum nano catalyst of porous silicon surface chemical plating overcomes prior art, the defect that is difficult to quality control, operating procedure is simple, quality control is easy, is particularly suitable for the production technology of micro direct methanol fuel battery.
Accompanying drawing explanation
Fig. 1 is the porous silicon surface AFM figure through ICP etching
Fig. 2 is at 3.5mM H 2ptCl 6in the aqueous solution, soak after 30min the shape appearance figure of the platinum that porous silicon initial surface and the face of processing through ICP form, the Pt nanoparticle that wherein (a) forms for porous silicon initial surface, the three-dimensional platinum nano catalyst (b) forming for the face of processing through ICP.
The specific embodiment
The invention provides the preparation method of the three-dimensional platinum nano catalyst of a kind of porous silicon load.Below in conjunction with drawings and Examples, be explained.
The present invention is directed to the problem of porous silicon-base proton exchange membrane catalyst, design has realized a kind of chemically plating Preparation Method of uploading three-dimensional platinum nano catalyst at porous silicon surface.Experimentation is divided into three parts, is first the preparation of porous silicon film; Next is to utilize ICP and HF Precondition on Porous Silicon film to carry out finishing; It is finally the three-dimensional platinum nano catalyst of chemical plating on the process porous silicon film of finishing.
Embodiment mono-
1. the preparation of porous silicon film:
1) adopt the n of resistivity < 0.02 Ω cm +two (100) silicon chips of throwing of type, sheet is thick is 500um, the SiO of two-sided dry oxide growth 100nm 2layer, as Si 3n 4cushion, use Low Pressure Chemical Vapor Deposition (LPCVD) growth Si thereon 3n 4, thickness 160nm, as the masking layer of KOH corrosion;
2) at Si 3n 4upper sputter Cr/Au, thickness is 20nm/160nm, as anodised masking layer;
3) dual surface lithography: form figure.
4) wet etching: adopt KOH corrosion, etching condition is: KOH concentration: 33wt%, 80 ℃ of temperature, corrosion depth two sides is respectively 200um, the silicon fiml that in the middle of forming, thickness is 100um;
5) anodic oxidation generation porous silicon process conditions are: double flute anodic oxidation equipment; The HF of 40% (v/v): straight alcohol=2: 1 (volume ratio); Current density: 200mA/cm 2; Etching time: 15min.
2. the modification of porous silicon film:
Modification for porous silicon film is divided into two processes, and the one, inductively coupled plasma (ICP) etching, the pretreatment of the 2nd, HF solution.
1) ICP etching: ICP has two effects here, the one, etch away the silicon of anodic oxidation remainder, the 2nd, play the effect that porous silicon surface is modified, at porous silicon surface, form defective bit; As a comparison, only ICP etching is carried out in the porous silicon back side, ICP etching condition is as follows: plasma power: 400W; Accelerating power: 10W; SF 6: 70sccm; O 2: 5sccm.
Porous silicon surface pattern after ICP etching, as Fig. 1, in the scope in 10um*10um region, carries out to porous silicon surface the pattern that AFM scanning obtains in diagram, can find out that porous silicon surface has formed a lot of defective bit.
2) HF pretreatment: the porous silicon of processing through ICP is put into the HF aqueous solution soaking 2s of 40% (v/v), this is that it can restore platinum as the reducing agent of chemical plating from precursor liquid in order to form Si-H key at porous silicon surface.
3. the three-dimensional platinum nano catalyst of chemical plating:
Concrete technology condition is as follows: by the porous silicon through finishing, at precursor liquid, be 3.5mM H 2ptCl 6in the aqueous solution, under 20 ℃ of reaction temperatures, soak 30min-2h; On porous silicon surface, form three-dimensional platinum nano catalyst.
Fig. 2 has shown the H at 3.5mM 2ptCl 6in the aqueous solution, soak after 30min the pattern of the platinum that porous silicon initial surface and the face of processing through ICP form, the Pt nanoparticle that wherein (a) forms for porous silicon initial surface, the three-dimensional platinum nano catalyst (b) forming for the face of processing through ICP.
Embodiment bis-
1. the preparation of porous silicon film:
1) adopt the n of resistivity < 0.02 Ω cm +two (100) silicon chips of throwing of type, sheet is thick is 500um, the SiO of two-sided dry oxide growth 100nm 2layer, as Si 3n 4cushion, use Low Pressure Chemical Vapor Deposition (LPCVD) growth Si thereon 3n 4, thickness 160nm, as the masking layer of KOH corrosion;
2) at Si 3n 4upper sputter Cr/Au, thickness is 20nm/160nm, as anodised masking layer;
3) dual surface lithography: form figure.
4) wet etching: adopt KOH corrosion, etching condition is: KOH concentration: 33wt%, 78 ℃ of temperature, corrosion depth two sides is respectively 200um, the silicon fiml that in the middle of forming, thickness is 100um;
5) anodic oxidation generation porous silicon process conditions are: double flute anodic oxidation equipment; The HF of 40% (v/v): straight alcohol=2: 1 (volume ratio); Current density: 180mA/cm 2; Etching time: 15min.
2. the modification of porous silicon film:
Modification for porous silicon film is divided into two processes, the one, ICP (inductively coupled plasma) etching, the pretreatment of the 2nd, HF solution.
1) ICP etching: ICP has two effects here, the one, etch away the silicon of anodic oxidation remainder, the 2nd, play the effect that porous silicon surface is modified, at porous silicon surface, form defective bit; As a comparison, only ICP etching is carried out in the porous silicon back side.ICP etching condition is as follows: plasma power: 400W; Accelerating power: 10W; SF 6: 70sccm; O 2: 5sccm.
2) HF pretreatment: the porous silicon of processing through ICP is put into the HF aqueous solution soaking 2s of 40% (v/v), this is in order to form Si-H key at porous silicon surface.It can restore platinum as the reducing agent of chemical plating from precursor liquid.
3. the three-dimensional platinum nano catalyst of chemical plating:
Concrete technology condition is as follows: by the porous silicon through finishing, at precursor liquid, be 1mM H 2ptCl 6in the aqueous solution, under 18 ℃ of reaction temperatures, soak 30min-2h; On porous silicon surface, form three-dimensional platinum nano catalyst.
Embodiment tri-
1. the preparation of porous silicon film:
1) adopt the n of resistivity < 0.02 Ω cm +two (100) silicon chips of throwing of type, sheet is thick is 500um, the SiO of two-sided dry oxide growth 100nm 2layer, as Si 3n 4cushion, use Low Pressure Chemical Vapor Deposition (LPCVD) growth Si thereon 3n 4, thickness 160nm, as the masking layer of KOH corrosion;
2) at Si 3n 4upper sputter Cr/Au, thickness is 20nm/160nm, as anodised masking layer;
3) dual surface lithography: form figure.
4) wet etching: adopt KOH corrosion, etching condition is: KOH concentration: 33wt%, temperature: 81 ℃, corrosion depth two sides is respectively 200um, the silicon fiml that in the middle of forming, thickness is 100um;
5) anodic oxidation generation porous silicon process conditions are: double flute anodic oxidation equipment; The HF of 40% (v/v): straight alcohol=2: 1 (volume ratio); Current density: 250mA/cm 2; Etching time: 10min.
2. the modification of porous silicon film:
Modification for porous silicon film is divided into two processes, the one, ICP (inductively coupled plasma) etching, the pretreatment of the 2nd, HF solution.
1) ICP etching: ICP has two effects here, the one, etch away the silicon of anodic oxidation remainder, the 2nd, play the effect that porous silicon surface is modified, at porous silicon surface, form defective bit; As a comparison, only ICP etching is carried out in the porous silicon back side.ICP etching condition is as follows: plasma power: 400W; Accelerating power: 10W; SF 6: 70sccm, O 2: 5sccm.
2) HF pretreatment: the porous silicon of processing through ICP is put into the HF aqueous solution soaking 2s of 40% (v/v), this is that it can restore platinum as the reducing agent of chemical plating from precursor liquid in order to form Si-H key at porous silicon surface.
3. the three-dimensional platinum nano catalyst of chemical plating,
Concrete technology condition is as follows: by the porous silicon through finishing, at precursor liquid, be 0.5mM H 2ptCl 6in the aqueous solution, under 25 ℃ of reaction temperatures, soak 30min-2h; On porous silicon surface, form three-dimensional platinum nano catalyst.

Claims (5)

1. a preparation method for the three-dimensional platinum nano catalyst of porous silicon load, is characterized in that: described preparation method is as follows at the processing step of the three-dimensional platinum nano catalyst of porous silicon surface chemical plating:
A. be first the preparation of porous silicon film:
(1) at n +the two-sided dry oxide growth SiO of type silicon chip 2layer, at SiO 2on layer, LPCVD prepares Si 3n 4layer;
(2) at Si 3n 4upper sputter Cr/Au is as anodised masking layer;
(3) will be at Si 3n 4the n of sputter Cr/Au film on layer +two-sided conventional photoetching, the formation figure of carrying out of type silicon chip;
(4) adopt KOH wet etching, at n +silicon fiml in the middle of the two-sided formation of type silicon chip;
(5) anodic oxidation generates porous silicon;
B. be secondly to utilize ICP and HF Precondition on Porous Silicon film to carry out finishing: first carry out ICP etching, etch away the silicon of anodic oxidation remainder, porous silicon surface is modified, at porous silicon surface, form defective bit; Then the HF aqueous solution of putting into 40% (v/v) concentration soaks 2s and carries out the pretreatment of HF solution, at porous silicon surface, forms Si-H key;
C. be finally the three-dimensional platinum nano catalyst of chemical plating on the process porous silicon film of finishing, concrete technology condition is as follows: by the porous silicon through finishing, at precursor liquid, be 0.5-3.5mM H 2ptCl 6in the aqueous solution, under 18-25 ℃ of reaction temperature, soak 30min-2h; On porous silicon surface, form three-dimensional platinum nano catalyst.
2. the preparation method of the three-dimensional platinum nano catalyst of porous silicon load according to claim 1, is characterized in that: described two-sided dry oxide growth SiO 2layer is as Si 3n 4cushion, Si thereon 3n 4layer is as the masking layer of KOH wet etching.
3. the preparation method of the three-dimensional platinum nano catalyst of porous silicon load according to claim 1, is characterized in that: the condition of described employing KOH wet etching is: KOH concentration: 33wt%, temperature is 78-81 ℃.
4. the preparation method of the three-dimensional platinum nano catalyst of porous silicon load according to claim 1, is characterized in that: the process conditions that described anodic oxidation generates porous silicon are: in double flute anodic oxidation equipment, adding is the solution of 40% (v/v) HF: straight alcohol=2:1 by volume; Current density: 180-250mA/cm 2; Etching time: 10-15min.
5. the preparation method of the three-dimensional platinum nano catalyst of porous silicon load according to claim 1, is characterized in that: in described step B, ICP etching condition is plasma power: 400W; Accelerating power: 10W; SF 6: 70sccm; O 2: 0-5sccm.
CN201210074930.2A 2012-03-20 2012-03-20 Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst Active CN102626617B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210074930.2A CN102626617B (en) 2012-03-20 2012-03-20 Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210074930.2A CN102626617B (en) 2012-03-20 2012-03-20 Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst

Publications (2)

Publication Number Publication Date
CN102626617A CN102626617A (en) 2012-08-08
CN102626617B true CN102626617B (en) 2014-03-05

Family

ID=46585117

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210074930.2A Active CN102626617B (en) 2012-03-20 2012-03-20 Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst

Country Status (1)

Country Link
CN (1) CN102626617B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102983344B (en) * 2012-11-23 2014-11-26 清华大学 Method for preparing porous silicon-based proton exchange membrane
CN107876107B (en) * 2017-09-29 2020-08-14 海南汉地阳光石油化工有限公司 Petroleum hydrogenation catalyst and preparation method thereof
CN111744472A (en) * 2020-06-19 2020-10-09 湖北工业大学 Preparation method and application of porous silicon platinum nano enzyme material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101533922A (en) * 2009-03-31 2009-09-16 清华大学 Micro direct methanol fuel cell of integrated temperature control system and manufacturing method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012024745A (en) * 2010-07-28 2012-02-09 Hitachi Ltd Catalyst material and method of manufacturing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101533922A (en) * 2009-03-31 2009-09-16 清华大学 Micro direct methanol fuel cell of integrated temperature control system and manufacturing method thereof

Also Published As

Publication number Publication date
CN102626617A (en) 2012-08-08

Similar Documents

Publication Publication Date Title
Park et al. Ultra-low loading of IrO2 with an inverse-opal structure in a polymer-exchange membrane water electrolysis
CN103280583B (en) Method for preparing catalytic layer structure of proton exchange membrane fuel cell
CN105734606B (en) A kind of SPE water electrolysis structure of ultra-thin membrane electrode and its preparation and application
CN102157741B (en) Manufacturing method of membrane electrode of novel ultrathin proton exchange membrane fuel cell
CN107634231B (en) Preparation method of proton exchange membrane fuel cell
CN102806093B (en) Preparation method of high-efficiency low-platinum catalyst for direct methanol fuel cell
CN107681163A (en) A kind of fuel cell membrane electrode and its preparation method and application
CN103943877A (en) Membrane electrode of direct alcohol type fuel battery and preparation method thereof
Kang et al. Performance improvement induced by membrane treatment in proton exchange membrane water electrolysis cells
CN103769086B (en) A kind of preparation method of fuel-cell catalyst
CN106816614B (en) The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application
CN105047963B (en) A kind of fuel cell preparation method based on graphene thermal electricity management level
Pu et al. Performance improvement of passive direct methanol fuel cells with surface-patterned Nafion® membranes
CN102626617B (en) Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst
CN103531826A (en) Direct-methanol fuel cell nano-porous structural film electrode construction method based on sacrificial template method
Yu et al. The construction of integrated Si-based micro proton exchange membrane fuel cells with improved performances
CN104037428A (en) Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof
CN103779582B (en) A kind of method for preparing fuel cell membrane electrode
CN103367768B (en) A kind of method preparing double-catalyst-layestructure structure of proton exchange membrane fuel cell
CN101997123B (en) Nano porous alloy fuel battery catalyst and preparation method thereof
CN107086316A (en) A kind of on-vehicle fuel laminated construction membrane electrode and preparation method thereof
CN103326032B (en) Method for preparing platinum gradient-distribution catalyst layer structure of proton exchange membrane fuel cell
CN105413679B (en) A kind of preparation method of graphene two-dimensional noble metal cluster composite
JP2006140134A (en) Membrane electrode assembly for fuel cell, its manufacturing method, and fuel cell
Zhang et al. Effects of the nanoimprint pattern on the performance of a MEMS-based micro direct methanol 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
GR01 Patent grant
GR01 Patent grant