CN106450359A - Preparation method of oxide@ precious metal core-shell nanowire catalyst - Google Patents

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

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CN106450359A
CN106450359A CN201611136275.3A CN201611136275A CN106450359A CN 106450359 A CN106450359 A CN 106450359A CN 201611136275 A CN201611136275 A CN 201611136275A CN 106450359 A CN106450359 A CN 106450359A
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preparation
oxide
catalyst
noble metal
metal core
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CN106450359B (en
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初园园
张宁
司源
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • 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

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  • 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

The invention discloses a preparation method of an oxide@ precious metal core-shell nanowire direct methanol fuel catalyst and relates to a preparation method of direct alcohol fuel cell catalysts. According to the preparation method disclosed by the invention, the problems that nanosized catalyst Pt particles are poisoned, the transmission of alcohol fuels is hindered and the preparation cost of the catalyst is high existing in a performance degradation mechanism of an existing direct alcohol fuel cell catalyst are solved. The method comprises the following steps: taking thiol undecanoic acid as a passivator for protecting precious metal nanoparticles; self-assembling a transition metal precursor on protected nanoparticles; adding a surfactant and hydrolyzing to obtain a dispersed oxide@ precious metal nanoparticle catalyst. The catalyst prepared by the method disclosed by the invention facilitates the transmission of the alcohol fuels, and has the advantages of low cost, as well as high poison resistance, high activity and high stability of a product. The product disclosed by the invention is mainly used for a catalyst of a methanol fuel cell.

Description

The preparation method of oxide@noble metal core-shell nano line catalyst
Technical field
The present invention relates to the preparation method of direct alcohol fuel cell catalyst.
Background technology
Energy density is high, structure is simple, the low advantage of running temperature because it has for direct alcohol fuel cell (DAFC) And increasingly cause the interest of scientist all over the world.But the decay of existing direct alcohol fuel cell catalyst performance The poisoning of active component Pt particle present in mechanism, Aalcohols fuel transmission are obstructed, the problems such as carrier is unstable perishable；With methanol As a example fuel, methanol oxidation, first from the beginning of methanol dehydrogenation, produces CH2The series of intermediate products such as OH, further oxidation produces Formic acid and the CO of absorptionadsDeng species, these poison species and will occupy the active sites (making it be poisoned) of Pt, hinder the absorption of methanol Oxidation.
Content of the invention
The purpose of the present invention in order to solve existing direct alcohol fuel cell catalyst performance decline fall mechanism present in Nano level active component Pt particle is poisoned, Aalcohols fuel transmission is obstructed and the problem of catalyst preparation high cost, and provides oxygen The preparation method of compound@noble metal core-shell nano line catalyst
In the present invention, the preparation method of oxide@noble metal core-shell nano line catalyst is to realize according to following steps：First, Using consisting of phase-transferring agent, the anion of precious metal salt is transferred in dichloromethane, remove aqueous phase, add acetone, sequentially add MUA passivator and reducing agent, are precipitated and wash, and are dissolved in recovery granule in the organic solvent of acidifying.Described is organic molten Agent includes oxolane, ether, acetonitrile, acetone, methanol, and described reducing agent includes sodium borohydride, lithium aluminium hydride reduction.2nd, by cerium Salt dissolves in methyl alcohol, adds decanol, is added dropwise over methoxide solution, obtains gas and glassy yellow and white precipitate, will mix Thing mechanical agitation, evaporation product are dissolved in dichloromethane, are stirred for, evaporate repeatedly, final compound is dissolved in dichloromethane Alkane, white precipitate is filtered away, re-evaporation.Mixing time 0.5h～1.5h.3rd, the product that step one obtains is added to step In the middle of rapid two products, add surfactant and be hydrolyzed, hydrolysis time 3h～5h.Obtain the core of oxide noble metal Shell nano thread structure, it is nucleocapsid structure that the method prepares catalyst, and surface pore is enriched, specific surface area is higher.
In the present invention, the preparation method of oxide@noble metal core-shell nano line can also be realized according to the following steps：First, we To prepare the noble metal nano particles of lauryl amine protection using two-phase Brust-Schriffrin method.Using consisting of phase-transferring agent The anion of precious metal salt is transferred to organic solvent (CH2Cl2) in, it is separated, removes aqueous phase, be dried, add 12 equivalents afterwards Lauryl amine.Next, adding excessive LiBEt in solution3H, is stirred vigorously, and forms opaque dark solution, continues Continuous stirring 10～20min, washing, ultrasonic, centrifugation three times to four times.2nd, ligand exchange.By by lauryl amine-Pt nanometer Granule and 11 Mercaptoundecanoic acid are codissolved in 3: 1 CH2Cl2Lauryl amine 11- mercapto-undecanoic is completed in/THF solution The replacement of acid.Solution is stirred at room temperature 18h.Solvent removed in vacuo, gained black solid is suspended in CH2Cl2In, ultrasonic Process and be centrifuged three times to remove excessive lauryl amine.Then black solid is re-dissolved in THF and filters.3rd, to In organic solvent containing metal precursor Deca step 2 product, be stirred vigorously, the water of metal precursor simultaneously The water by Deca 0.5～1.0ml for the solution, dissolving is in organic solvent.Metal precursor includes Ti (OBu)4、Zr(OBu)4、Ce (OBu)4.
Brief description
Fig. 1 is Pt@CeO2Transmission electron microscope picture.
Specific embodiment
For being best understood from the present invention, with reference to embodiment, the present invention is done and further describe in detail, but the present invention Claimed scope is not limited to the scope represented by embodiment.
Specific embodiment one：In present embodiment the preparation method of oxide@noble metal core-shell nano line be according to Lower step is realized：First, metal nanoparticle that 11- Mercaptoundecanoic acid (MUA) as passivator thiol synthesis salt protect is used； Using consisting of phase-transferring agent, the anion of precious metal salt is transferred in dichloromethane, remove aqueous phase, add acetone, sequentially add MUA passivator and reducing agent, are precipitated and wash, and are dissolved in recovery granule in the organic solvent of acidifying, described is organic molten Agent includes oxolane, ether, acetonitrile, acetone, methanol, described reducing agent include sodium borohydride, lithium aluminium hydride reduction two, by transition Dissolving metal salts in methyl alcohol, add decanol, are added dropwise over methoxide solution, obtain gas and glassy yellow and white precipitate, will Mixture stirring, evaporation product are dissolved in dichloromethane, are stirred for, evaporate repeatedly, final compound is dissolved in dichloromethane Alkane, white precipitate is filtered away, re-evaporation.Mixing time 0.5h～1.5h.3rd, the product that step one obtains is added to step In the middle of rapid two products, add surfactant and be hydrolyzed, hydrolysis time 3h～5h hour.Obtain oxide noble metal Core-shell nano line structure, the method prepare catalyst be nucleocapsid structure, surface pore enrich, specific surface area higher.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Precious metal salt described in step one For K2PdCl4、K2RhCl4、K2IrCl4、K2PtCl4.Other steps are identical with specific embodiment one with parameter.
Specific embodiment three：Present embodiment from unlike specific embodiment one or two：Described in step one two Chloromethanes: acetone=1: 1.Other steps are identical with specific embodiment one or two with parameter.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Add in step 2 The methoxide solution mass fraction entering is 20wt%～40wt%.One of other steps and parameter and specific embodiment one to three Identical.
Specific embodiment five：Described surfactant has stearic acid, Oleic acid, lauric acid, sodium lauryl sulphate, the moon Lauryl sulfate, dodecylbenzene sodium sulfonate or glycocholic acid.Other steps and parameter and one of specific embodiment one to four phase With.Specific embodiment six：The preparation method of present embodiment oxide@noble metal core-shell nano line can also be according to the following steps Realize：First, we to prepare the noble metal nano particles of lauryl amine protection using two-phase Brust-Schriffrin method. Using consisting of phase-transferring agent, the anion of precious metal salt is transferred to organic solvent (CH2Cl2) in, it is separated, removes aqueous phase, be dried, afterwards Add the lauryl amine of 12 equivalents.Next, adding excessive LiBEt in solution3H, is stirred vigorously, and is formed opaque Dark solution, continue stirring 10～20min, washing, ultrasonic, centrifugation three times to four times.Described organic solvent includes dichloromethane Alkane, dichloroethanes, methylene bromide, trichloro ethylene.2nd, ligand exchange.By by lauryl amine-Pt nano-particle and 11 sulfydryls Hendecanoic acid is codissolved in 3: 1CH2Cl2The replacement of lauryl amine 11- Mercaptoundecanoic acid is completed in/THF solution.Will be molten Liquid is stirred at room temperature.Solvent removed in vacuo, gained black solid is suspended in organic solvent, and supersound process is simultaneously centrifuged three times To remove excessive lauryl amine.Then black solid is re-dissolved in THF and filters.3rd, to containing metal precursor Organic solvent in Deca step 2 product, be stirred vigorously simultaneously, the hydrolysis of metal precursor pass through Deca 0.5～ The water of 1.0mL, dissolving is in organic solvent.Metal precursor includes Ti (OBu)4、Zr(OBu)4、Ce(OBu)4.
Specific embodiment seven：Present embodiment from unlike specific embodiment six：Precious metal salt described in step one For K2PdCl4、K2RhCl4、K2IrCl4、K2PtCl4.Other steps are identical with specific embodiment six with parameter.
Specific embodiment eight：Present embodiment from unlike specific embodiment six to seven：Step one centrifugation Speed is 10000 revs/min.Other steps are identical with specific embodiment six to seven with parameter.
Specific embodiment nine：Present embodiment from unlike specific embodiment seven to eight：Step 2 is at room temperature Stirring 16～20h, other steps are identical with specific embodiment seven to eight with parameter.

Claims (6)

1. the preparation method of oxide@noble metal core-shell nano line catalyst is it is characterised in that oxide@noble metal core-shell nano The preparation method of line catalyst is to realize according to the following steps：First, using consisting of phase-transferring agent, the anion of precious metal salt is transferred to two In chloromethanes, remove aqueous phase, add acetone, sequentially add MUA passivator and reducing agent, be precipitated and wash, be dissolved in Granule is reclaimed in the organic solvent of acidifying.Described organic solvent includes oxolane, ether, acetonitrile, acetone, methanol, described Reducing agent include sodium borohydride, lithium aluminium hydride reduction.2nd, cerium salt is dissolved in methyl alcohol, add decanol, be added dropwise over methoxide molten Liquid, obtains gas and glassy yellow and white precipitate, mixture mechanical agitation, evaporation product is dissolved in dichloromethane, is stirred for, steams Send out repeatedly, final compound is dissolved in dichloromethane, white precipitate is filtered away, re-evaporation.Mixing time 0.5h ～1.5h.3rd, the product that step one obtains is added in the middle of step 2 product, adds dodecylic acid and be hydrolyzed, hydrolysis Time 3h～5h.Obtain the core-shell nano line structure of oxide noble metal, it is nucleocapsid structure that the method prepares catalyst, table Face gap is enriched, specific surface area is higher.
2. the preparation method of oxide@noble metal core-shell nano line catalyst according to claim 1 is it is characterised in that walk Precious metal salt described in rapid one is K2PdCl4、K2RhCl4、K2IrCl4、K2PtCl4.
3. the preparation method of oxide@noble metal core-shell nano line catalyst according to claim 1 and 2, its feature exists Dichloromethane described in step one: acetone=1: 1.
4. the preparation method of the oxide@noble metal core-shell nano line catalyst according to claim 1,2 or 3, its feature It is that the methoxide solution mass fraction adding in step 2 is 20wt%～40wt%.
5. the preparation method of oxide@noble metal core-shell nano line catalyst is it is characterised in that oxide@noble metal core-shell nano The preparation method of line catalyst is to realize according to the following steps：First, we to be prepared using two-phase Brust-Schriffrin method The noble metal nano particles of lauryl amine protection.Using consisting of phase-transferring agent, the anion of precious metal salt is transferred to organic solvent (CH2Cl2) in, it is separated, removes aqueous phase, be dried, add the lauryl amine of 12 equivalents afterwards.Next, adding in solution The LiBEt of amount3H, is stirred vigorously, and forms opaque dark solution, continues stirring 10～20min, washing, ultrasonic, centrifugation three Secondary to four times.Described organic solvent includes dichloromethane, dichloroethanes, methylene bromide, trichloro ethylene.2nd, ligand exchange.Logical Cross and lauryl amine-Pt nano-particle and 11 Mercaptoundecanoic acid are codissolved in 3: 1CH2Cl2Dodecane is completed in/THF solution The base amine replacement of 11- Mercaptoundecanoic acid.Solution is stirred at room temperature.Solvent removed in vacuo, gained black solid is hanged Float in organic solvent, supersound process is simultaneously centrifuged three times to remove excessive lauryl amine.Then by black solid re-dissolved In THF and filter.3rd, to Deca step 2 in the organic solvent containing metal precursor product, carry out acutely simultaneously Stirring, the water of Deca 0.5～1.0mL is passed through in the hydrolysis of metal precursor, and dissolving is in organic solvent.Metal precursor includes Ti (OBu)4、Zr(OBu)4、Ce(OBu)4.
6. the preparation method of oxide@noble metal core-shell nano line catalyst according to claim 5 is it is characterised in that walk Precious metal salt described in rapid one is K2PdCl4、K2RhCl4、K2IrCl4、K2PtCl4.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111146453A (en) * 2019-12-27 2020-05-12 大连理工大学 Carbon-supported noble metal-transition metal oxide composite electrocatalyst and preparation method and application thereof
CN114497603A (en) * 2021-12-17 2022-05-13 深圳航天科技创新研究院 Catalyst for fuel cell, preparation method thereof 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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111146453A (en) * 2019-12-27 2020-05-12 大连理工大学 Carbon-supported noble metal-transition metal oxide composite electrocatalyst and preparation method and application thereof
CN114497603A (en) * 2021-12-17 2022-05-13 深圳航天科技创新研究院 Catalyst for fuel cell, preparation method thereof and fuel cell
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

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