CN106450359B - Preparation method of oxide @ noble metal core-shell nanowire catalyst - Google Patents

Preparation method of oxide @ noble metal core-shell nanowire catalyst Download PDF

Info

Publication number
CN106450359B
CN106450359B CN201611136275.3A CN201611136275A CN106450359B CN 106450359 B CN106450359 B CN 106450359B CN 201611136275 A CN201611136275 A CN 201611136275A CN 106450359 B CN106450359 B CN 106450359B
Authority
CN
China
Prior art keywords
noble metal
catalyst
oxide
preparation
metal core
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
CN201611136275.3A
Other languages
Chinese (zh)
Other versions
CN106450359A (en
Inventor
初园园
张宁
司源
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.)
Tianjin Polytechnic University
Original Assignee
Tianjin Polytechnic 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 Tianjin Polytechnic University filed Critical Tianjin Polytechnic University
Priority to CN201611136275.3A priority Critical patent/CN106450359B/en
Publication of CN106450359A publication Critical patent/CN106450359A/en
Application granted granted Critical
Publication of CN106450359B publication Critical patent/CN106450359B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Catalysts (AREA)

Abstract

A preparation method of an oxide @ noble metal core-shell nanowire direct methanol fuel catalyst relates to a preparation method of a direct alcohol fuel cell catalyst. The invention solves the problems of nanometer catalyst Pt particle poisoning, alcohol fuel transmission obstruction and high catalyst preparation cost in the existing mechanism of direct alcohol fuel cell catalyst performance decline. The method comprises the following steps: the noble metal nanoparticle is protected by using mercaptoundecanoic acid as a passivating agent, a transition metal precursor is self-assembled on the protected nanoparticle, a surfactant is added, and hydrolysis is carried out to obtain the dispersive oxide @ noble metal nanoparticle catalyst. The catalyst prepared by the method is beneficial to alcohol fuel transmission, and has the advantages of low cost, strong product poisoning resistance, high activity and high stability. The product of the invention is mainly used as the catalyst of the methanol fuel cell.

Description

Preparation method of oxide @ noble metal core-shell nanowire catalyst
Technical Field
The invention relates to a preparation method of a direct alcohol fuel cell catalyst.
Background
Direct Alcohol Fuel Cells (DAFCs) are increasingly attracting the interest of scientists around the world due to their advantages of high energy density, simple structure, low operating temperature, etc. However, the problems of Pt particle poisoning of an active component, hindered alcohol fuel transmission, unstable carrier, easy corrosion and the like existing in the mechanism of performance attenuation of the existing direct alcohol fuel cell catalyst exist; in the case of methanol fuel, methanol oxidation begins with dehydrogenation of methanol to produce CH2A series of intermediate products such as OH and the like are further oxidized to generate formic acid and adsorbed COadsAnd the like, and the poisoning species occupy the active sites of Pt (make the Pt poisonous), so that the adsorption and oxidation of methanol are hindered.
Disclosure of Invention
The invention aims to solve the problems of nano-scale active component Pt particle poisoning, alcohol fuel transmission obstruction and high catalyst preparation cost in the existing mechanism of performance decline of the direct alcohol fuel cell catalyst, and provides a preparation method of an oxide @ noble metal core-shell nanowire catalyst
The preparation method of the oxide @ noble metal core-shell nanowire catalyst is realized according to the following steps: firstly, transferring anions of noble metal salt into dichloromethane by using a phase transfer agent, removing a water phase, adding acetone, sequentially adding MUA passivator and reducing agent to obtain a precipitate, washing, dissolving in an acidified organic solvent, and recovering particles. The organic solvent comprises tetrahydrofuran, diethyl ether, acetonitrile, acetone and methanol, and the reducing agent comprises sodium borohydride and lithium aluminum hydride. Dissolving cerium salt in methanol, adding decanol, dropwise adding methanol salt solution to obtain gas, bright yellow and white precipitates, mechanically stirring the mixture, dissolving an evaporation product in dichloromethane, repeatedly stirring and evaporating for many times, dissolving a final compound in dichloromethane, filtering out the white precipitates, and evaporating. The stirring time is 0.5 to 1.5 hours. And thirdly, adding the product obtained in the first step into the product obtained in the second step, and then adding a surfactant for hydrolysis, wherein the hydrolysis time is 3-5 hours. The core-shell nanowire structure of the oxide @ noble metal is obtained, and the catalyst prepared by the method is of the core-shell structure, rich in surface pores and high in specific surface area.
The preparation method of the oxide @ noble metal core-shell nanowire can be further realized according to the following steps: firstly, a two-phase Brust-Schrifrin method is adopted to prepare the dodecylamine protected noble metal nano-particles. Transfer of anions of noble metal salts to organic solvents (CH) using phase transfer agents2Cl2) The phases were separated, the aqueous phase was removed, dried, and then 12 equivalents of dodecylamine were added. Next, an excess of LiBEt was added to the solution3And H, violently stirring to form an opaque black solution, continuously stirring for 10-20 min, and washing, ultrasonically treating and centrifuging for three to four times. And II, ligand exchange. By co-dissolving dodecylamine-Pt nanoparticles and 11 mercaptoundecanoic acid in 3: 1CH2Cl2In THF solution to complete the replacement of dodecylamine with 11-mercaptoundecanoic acid. The solution was stirred at room temperature for 18 h. The solvent was removed in vacuo and the resulting black solid was suspended in CH2Cl2In (b), sonicated and centrifuged three times to remove excess dodecylamine. The black solid was then redissolved in THF and filtered. And thirdly, dropwise adding the product obtained in the second step into an organic solvent containing a metal precursor, and stirring vigorously, wherein 0.5-1.0 ml of water is dropwise added to hydrolyze the metal precursor and is dissolved in the organic solvent. The metal precursor comprises Ti (OBu)4、Zr(OBu)4、Ce(OBu)4。
Drawings
FIG. 1 is Pt @ CeO2Transmission electron micrographs.
Detailed Description
The present invention will be further described in detail with reference to examples for better understanding, but the scope of the present invention is not limited to the examples.
The first embodiment is as follows: the preparation method of the oxide @ noble metal core-shell nanowire in the embodiment is realized according to the following steps: firstly, synthesizing thiolate-protected metal nanoparticles by using 11-mercaptoundecanoic acid (MUA) as a passivating agent; transferring anions of noble metal salt into dichloromethane by using a phase transfer agent, removing a water phase, adding acetone, sequentially adding MUA passivator and a reducing agent to obtain a precipitate, washing, dissolving in an acidified organic solvent to recover particles, wherein the organic solvent comprises tetrahydrofuran, diethyl ether, acetonitrile, acetone and methanol, the reducing agent comprises sodium borohydride and lithium aluminum hydride, dissolving transition metal salt in methanol, adding decanol, dropwise adding a methanol salt solution to obtain gas, bright yellow and white precipitates, stirring and evaporating the mixture to dissolve a dichloromethane, stirring and evaporating for multiple times, dissolving a final compound in the dichloromethane, filtering out the white precipitate, and evaporating. The stirring time is 0.5 to 1.5 hours. And thirdly, adding the product obtained in the first step into the product obtained in the second step, and then adding a surfactant for hydrolysis, wherein the hydrolysis time is 3-5 hours. The core-shell nanowire structure of the oxide @ noble metal is obtained, and the catalyst prepared by the method is of the core-shell structure, rich in surface pores and high in specific surface area.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: step one, the noble metal salt is K2PdCl4、K2RhCl4、K2IrCl4、K2PtCl4. Other steps and parameters are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in step one, the ratio of dichloromethane to acetone is 1: 1. Other steps and parameters are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the mass fraction of the methoxide solution added in the second step is 20-40 wt%. Other steps and parameters are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the surfactant is stearic acid, oleic acid, lauric acid, sodium dodecyl sulfate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate or glycocholic acid. Other steps and parameters are the same as in one of the first to fourth embodiments. The sixth specific implementation mode: the preparation method of the oxide @ noble metal core-shell nanowire can be further realized according to the following steps: firstly, a two-phase Brust-Schrifrin method is adopted to prepare the dodecylamine protected noble metal nano-particles. Transfer of anions of noble metal salts to organic solvents (CH) using phase transfer agents2Cl2) The phases were separated, the aqueous phase was removed, dried, and then 12 equivalents of dodecylamine were added. Next, an excess of LiBEt was added to the solution3And H, violently stirring to form an opaque black solution, continuously stirring for 10-20 min, and washing, ultrasonically treating and centrifuging for three to four times. The organic solvent comprises dichloromethane, dichloroethane, dibromomethane and trichloroethylene. And II, ligand exchange. By co-dissolving dodecylamine-Pt nanoparticles and 11-mercaptoundecanoic acid in 3: 1CH2Cl2In THF solution to complete the replacement of dodecylamine with 11-mercaptoundecanoic acid. The solution was stirred at room temperature. The solvent was removed in vacuo and the resulting black solid was suspended in organic solvent, sonicated and centrifuged three times to remove excess dodecylamine. The black solid was then redissolved in THF and filtered. And thirdly, dropwise adding the product obtained in the second step into an organic solvent containing a metal precursor, and stirring vigorously, wherein 0.5-1.0 mL of water is dropwise added to hydrolyze the metal precursor, and the hydrolyzed metal precursor is dissolved in the organic solvent. The metal precursor comprises Ti (OBu)4、Zr(OBu)4、Ce(OBu)4。
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: step one, the noble metal salt is K2PdCl4、K2RhCl4、K2IrCl4、K2PtCl4. The other steps and parameters are the same as in embodiment six.
The specific implementation mode is eight: the present embodiment differs from the sixth to seventh embodiments in that: step one the centrifugal separation speed was 10000 rpm. The other steps and parameters are the same as those of the embodiments six to seven.
The specific implementation method nine: this embodiment differs from the seventh to eighth embodiments in that: and stirring the mixture for 16-20 h at room temperature in the second step, wherein other steps and parameters are the same as those of the seventh to eighth specific embodiments.

Claims (3)

1. The preparation method of the oxide @ noble metal core-shell nanowire catalyst is characterized by comprising the following steps of: firstly, transferring anions of noble metal salt into dichloromethane by using a phase transfer agent, removing a water phase, adding acetone, sequentially adding an 11-mercaptoundecanoic acid passivator and a reducing agent to obtain a precipitate, washing, dissolving in an acidified organic solvent, and recovering particles; the organic solvent comprises tetrahydrofuran, diethyl ether, acetonitrile, acetone or methanol, and the reducing agent comprises sodium borohydride or lithium aluminum hydride; dissolving cerium salt in methanol, adding decanol, dropwise adding a methanol salt solution to obtain gas and generate a mixture of bright yellow precipitate and white precipitate, mechanically stirring the mixture, dissolving an evaporation product in dichloromethane, repeatedly stirring and evaporating for many times, dissolving a final compound in dichloromethane, filtering out the white precipitate, and evaporating; the stirring time is 0.5h to 1.5 h; and thirdly, adding the product obtained in the first step into the product obtained in the second step, and adding dodecanoic acid for hydrolysis for 3-5 hours to obtain the oxide @ noble metal core-shell nanowire structure.
2. The preparation method of the oxide @ noble metal core-shell nanowire catalyst as claimed in claim 1, wherein the noble metal salt in step one is K2PdCl4、K2RhCl4、K2IrCl4Or K2PtCl4。
3. The preparation method of the oxide @ noble metal core-shell nanowire catalyst as claimed in claim 1 or 2, wherein the mass fraction of the methoxide solution added in the second step is 20-40 wt%.
CN201611136275.3A 2016-12-08 2016-12-08 Preparation method of oxide @ noble metal core-shell nanowire catalyst Active CN106450359B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611136275.3A CN106450359B (en) 2016-12-08 2016-12-08 Preparation method of oxide @ noble metal core-shell nanowire catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611136275.3A CN106450359B (en) 2016-12-08 2016-12-08 Preparation method of oxide @ noble metal core-shell nanowire catalyst

Publications (2)

Publication Number Publication Date
CN106450359A CN106450359A (en) 2017-02-22
CN106450359B true CN106450359B (en) 2019-12-31

Family

ID=58216458

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611136275.3A Active CN106450359B (en) 2016-12-08 2016-12-08 Preparation method of oxide @ noble metal core-shell nanowire catalyst

Country Status (1)

Country Link
CN (1) CN106450359B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111146453B (en) * 2019-12-27 2021-01-15 大连理工大学 Carbon-supported noble metal-transition metal oxide composite electrocatalyst and preparation method and application thereof
CN114497603B (en) * 2021-12-17 2023-07-11 深圳航天科技创新研究院 Catalyst for fuel cell, preparation method of catalyst and fuel cell

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966144A (en) * 2006-09-06 2007-05-23 大连理工大学 Method for preparing loading type nano Pd/C catalyst from colloidal solution
CN103285880A (en) * 2013-05-28 2013-09-11 浙江科技学院 Preparation method of proton exchange membrane fuel battery catalyst
CN105013475A (en) * 2015-06-03 2015-11-04 东南大学 Mono-dispersed Pd-Pt nano-catalyst and preparation method therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966144A (en) * 2006-09-06 2007-05-23 大连理工大学 Method for preparing loading type nano Pd/C catalyst from colloidal solution
CN103285880A (en) * 2013-05-28 2013-09-11 浙江科技学院 Preparation method of proton exchange membrane fuel battery catalyst
CN105013475A (en) * 2015-06-03 2015-11-04 东南大学 Mono-dispersed Pd-Pt nano-catalyst and preparation method therefor

Also Published As

Publication number Publication date
CN106450359A (en) 2017-02-22

Similar Documents

Publication Publication Date Title
Yang et al. Syntheses and applications of noble-metal-free CeO2-based mixed-oxide nanocatalysts
US10889532B2 (en) Graphene/metal or metalloid core-shell composite and manufacturing method thereof
CN109467493B (en) Preparation method of metal organic framework material modified nano metal particles
CN102277622B (en) Copper-platinum superlattice alloy nano-tube and preparation method thereof
CN103317141A (en) Method for preparing metal nanoparticles
CN111099650A (en) CeO2Molten salt method for synthesizing nano spherical particles
CN106450359B (en) Preparation method of oxide @ noble metal core-shell nanowire catalyst
CN104646025A (en) Preparation method of hollow Pt/Ni alloy and graphene aerogel compound material
CN105923625B (en) A kind of preparation method of graphene-supported uniform single oxide quantum dot
CN102873337A (en) Poly-allylamine oriented platinum nano cube preparation method
CN111302405A (en) Method for preparing single-layer hydrotalcite nanosheet material in large scale
CN108855217B (en) Preparation method and application of copper-based metal organic framework nano sheet
CN112920001A (en) Method for preparing nano aluminum/porous copper oxide nano thermite by self-assembly of P4VP
CN105536877A (en) Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure
CN103396356A (en) Spirofluorene copper pyridine micro-nano particle and preparation method thereof
CN109078642B (en) Flower-shaped nano-gold composite metal oxide catalyst and preparation method and application thereof
CN102139914A (en) Method for preparing calcium titanate nanoparticles
KR101168653B1 (en) Process for Preparing Nanodendrites
CN105709736A (en) Preparation method of embedded Pt@CeO2 nanotube composite catalyst
CN111375411B (en) Monoatomic Cu/TiO 2 Method for preparing nano-wire
CN108358299B (en) Treatment process for catalytic degradation of dye wastewater by ozone
CN102873334B (en) Ultrasonic radiation preparation method for chrysanthemum-like nano-palladium aggregate material
CN104445340A (en) Method for preparing octahedral cerium oxide self-assembled by nano blocks
CN101891157B (en) Preparation method of mesoporous nano-metal composite oxide
CN104030341A (en) Preparation method of copper oxide nanomaterial

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