CN104707601A - Preparation method of electrocatalyst of proton exchange membrane fuel cell - Google Patents

Preparation method of electrocatalyst of proton exchange membrane fuel cell Download PDF

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CN104707601A
CN104707601A CN201310694946.8A CN201310694946A CN104707601A CN 104707601 A CN104707601 A CN 104707601A CN 201310694946 A CN201310694946 A CN 201310694946A CN 104707601 A CN104707601 A CN 104707601A
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catalyst
preparation
transition metal
solution
ptau
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CN104707601B (en
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邱艳玲
张华民
许壮
钟和香
毛景霞
邓呈维
柳丝丝
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Dalian Institute of Chemical Physics of CAS
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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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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation method of an electrocatalyst of a proton exchange membrane fuel cell, a core-shell-like structural PtxAuyMz nano seed colloid solution is prepared, PtxAuyMz is supported on the carbon carrier surface, and the catalyst is obtained by centrifugal filtration, washing and drying, distribution of x, y and z of PtxAuyMz nanoparticles is that: x:y:z =1:0.001-0.01:5-30, and the Pt loading amount is 10-40%; the catalyst surface atomic rearrangement is performed by the final heat treatment process; compared with the prior art, the catalyst nanoparticles prepared by the method are well dispersed, and have obvious Pt and Au enrichment characteristics, Pt surface enrichment helps to improve utilization ratio of Pt atoms so as to improve the precious metal mass ratio activity of the catalyst, and Au surface enrichment is conducive to the realization of surface modification and improvement of the electrochemical stability of the nanoparticles.

Description

A kind of preparation method of Electro Catalysts for PEMFC
Technical field
The present invention relates to fuel cell, particularly a kind of Electro Catalysts for PEMFC preparation method.
Background technology
Fuel cell is the energy conversion device that a kind of chemical energy by fuel and oxidant is converted into electric energy.Wherein, Proton Exchange Membrane Fuel Cells (Proton Exchange MembraneFuel Cell, PEMFC) be with pure hydrogen or purification reformed gas for fuel, perfluoro sulfonic acid membrane is electrolyte, having can room temperature starts fast, specific power is except having fuel and specific energy high, have broad application prospects in fields such as fixed power station, electric automobile and portable power supplies, be considered to a types of fuel cells of current most practicality, be subject to the great attention of countries in the world government and scientific research institution.
At present, can be applicable to cathodic oxygen reduction (ORR) catalyst of PEMFC, no matter consider from active or the angle in service life, Pt is catalyst based remains optimal eelctro-catalyst.But the cost of Pt is high, active high, and stability is low, still can not meet the demand of large-scale commercial application.Therefore, main catalytic activity and stability around improving platinum based catalyst conducts a research both at home and abroad at present, thus reaches the use amount reducing noble metal, the target improving catalyst stability.In the configuration aspects that Pt is catalyst based, researcher by the catalyst of the special nanostructured of design and synthesis, expose more advantage crystal face, or carry out finishing, improve the characterization of adsorption of Pt to O, to improve ORR catalytic activity and the electrochemical stability of Pt; Or Pt and base metal are prepared alloy catalyst, on the one hand Some substitute Pt, reduce the consumption of Pt, on the other hand by the electronic structure of metallic bond modulation Pt, thus improve the ORR catalytic activity of Pt; The third aspect is nucleocapsid structure (the M@Pt) catalyst that base metal is core, Pt is shell by designing, substitute the Pt atom not participating in catalytic reaction, not only significantly improve the utilization rate of Pt atom, reduce the consumption of Pt, and by the interaction between core-shell structure copolymer, regulate and control the electronic structure of surperficial Pt atom, obtain high ORR catalytic activity.For the platinum based catalyst of nucleocapsid structure, conventional and effective method is the core first preparing the first metal in non-aqueous system, then make Pt or Pt by underpotential deposition technology and between the second metallic atom and first metallic atom on surface, displacement reaction occur, thus obtaining the Pt shell only having several atomic thickness.If Kotaro Sasaki etc. is at document Core-Protected PlatinumMonolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes, Angew.Chem.Int.Ed.2010,49, report in 8602 – 8607, under acetamide and tert-butylamine borine exist, first reduce palladium acetylacetonate.Then, we are respectively the Pd@FePt nano particle of 4.9 ± 0.8nm and 0.9 ± 0.1nm with FePt these Pd nano particles coated, the average thickness obtaining core and shell.This in non-aqueous system cladding process not only to raw material and preparation environmental requirement strict, and post processor is loaded down with trivial details, and there is potential problem of environmental pollution.Adzic etc. are at document Platinum monolayer electrocatalysts:tunable activity, stability, and self-healing properties [J] .Electrocatalysis2012; 3:163-9. reports the M@Pt/C catalyst that the preparation of a kind of electrochemical deposition method is shell with Pt monoatomic layer.First base metal-precious metal alloys nano particle is prepared, through high temperature induction noble metal after surface segregation, underpotential deposition one deck Cu, then adopt Pt to replace, namely obtain M@Pt/C catalyst.The catalyst that this legal system is standby, the utilization rate of Pt atom significantly improves, and the mass ratio activity of noble metal can reach more than 4 times of Pt/C catalyst.But to preparation technology, this electrochemical deposition method requires that strictly preparation process is loaded down with trivial details, be difficult to realize scale.
Summary of the invention
The invention provides the preparation method of simple and easy, the controlled Electro Catalysts for PEMFC of a kind of preparation process, platinum based catalyst prepared by the method has the outstanding advantages of active high, good stability.In the current potential scan round test of simulation PEMFC Practical Condition, this catalyst is spontaneous carries out surface reconstruction, and ORR catalytic activity improves gradually, shows excellent active hold facility.
The composition of catalyst and concrete preparation method, comprise the following steps:
A kind of loaded, high activity, high stability platinum based catalyst and preparation method thereof, first prepare the ternary metal nano particle Pt of class nucleocapsid structure xau ym z, then it is evenly supported in the high-area carbon surface through purified treatment, eventually passes the atomic rearrangement that Technology for Heating Processing carries out catalyst surface, thus obtain the catalyst structure of surface enrichment element Pt.
Pt xau ym zthe x of nano particle, y, z are distributed as: x:y:z=1:0.001 ~ 0.01:5 ~ 30; After Overheating Treatment, nearly surface atom consists of x:y:z=85 ~ 50:5 ~ 10:10 ~ 40.In supported catalyst, the mass content of Pt is 10 ~ 40%
High-area carbon is Vulcan XC-72, KB300, KB600, BP2000 isoreactivity charcoal.
So-called purification process technique goes deimpurity process for using non-oxidizable aqueous acid to high-area carbon, and treatment temperature is 60 ~ 80 DEG C, and the processing time is 2 ~ 8h.The optimization process time is 3 ~ 5h.Non-oxidizing acid is hydrochloric acid, dust technology.
So-called Technology for Heating Processing is heat treatment in reducing atmosphere, and temperature ranges is 120 ~ 300 DEG C, and optimum treatmenting temperature is 150 ~ 250 DEG C; Processing time is 0.5 ~ 5h, and the optimization process time is 2 ~ 4h; Reducing atmosphere is H 2with mixing of inert gas, H 2be 1:1 ~ 1:10 with the flow-rate ratio of inert gas, optimum flow ratio is 1:3 ~ 1:6.Inert gas is high-purity Ar, high-purity N 2.One in high-purity He.
The method of described fuel cell electro-catalyst comprises the steps:
1) dissolving of transition metal precursor
Under room temperature condition, by transition metal precursor uniform dissolution in higher boiling, water miscible alcoholic solvent; The concentration of transition metal ions in alcoholic solution is 10mM ~ 100mM, and optium concentration is 30 ~ 70mM.
So-called transition metal is the one in Mn, Fe, Co, Ni, Cu, Zn, and presoma is halide, nitrate, acetate.
So-called high-boiling point alcohol solvent is ethylene glycol, propane diols, the one in glycerine.
2) protection of transition metal ions
Under room temperature condition, in the alcoholic solution of consoluet transition metal precursor, add protective agent.Here protective agent is can form the reagent of complex with transition metal; comprise trisodium citrate (SC); disodium ethylene diamine tetraacetate (EDETATE SODIUM); or for the salt of protectiveness micella can be formed with transition metal; comprise hexadecyltrimethylammonium chloride (CTAC), softex kw (CTAB), neopelex (SDBS).
The mol ratio of protective agent and transition metal ions is 0.5:1 ~ 5:1, and optimum mole ratio is 1:1 ~ 3:1.
3) reduction reaction
Under an inert atmosphere, add the aqueous solution that concentration is 0.1M ~ 0.5M reducing agent, adding speed is 0.05ml s -1~ 0.5ml s -1, it is 0.1 ~ 0.3ml s that the best adds speed -1, reducing agent is determined according to the metering ratio of chemical reaction with the mol ratio of transition metal ions.Reaction time is 1 ~ 5h.Obtain the transition metal nanometer seed of stable existence in colloidal form.
So-called reducing agent is boron hydride or formaldehyde.
Inert atmosphere for pass into high-purity Ar in reaction system continuously, high-purity N 2or the one in the inert gas such as high-purity He, inert gas flow velocity is 10 ~ 100ml min -1, optimum flow rate is 30 ~ 80ml min -1.
4) coordination of noble metal precursor body regulates
Complexant is added in the mixing precursor water solution of Pt presoma and Au.The atomic ratio of transition metal and Pt is 5:1 ~ 30:1, and best atomic ratio is 10:1 ~ 25:1; The mol ratio of element Pt and Au is 500:1 ~ 50:1, and best atomic ratio is 150:1 ~ 70:1; The molar ratio of complexant and element Pt and Au sum is 0:1 ~ 20:1, and optimum mole ratio is 3:1 ~ 10:1.
Pt presoma is H 2ptCl 6, PtCl 4, K 2ptCl 6, Na 2ptCl 6, K 2ptCl 4in one.In its aqueous solution, element Pt concentration is 5mM ~ 50mM, and optimum concentration range is 10mM ~ 30mM.
Au presoma is AuCl 3, Au (O 2cCH 3) 3, HAuCl 4, NaAuCl 4, KAuCl 4in one.In its aqueous solution, elements A u concentration is 2mM ~ 20mM, and optimum concentration range is 5mM ~ 10mM.
So-called complexant is for providing Br -reagent, as the one of sodium bromide (NaBr), KBr (KBr), softex kw (CTAB).
5) Pt of class nucleocapsid structure xau ym znanometer Spawn preparation
Under an inert atmosphere, be added in the colloidal solution of transition metal nanometer seed by the mixing precursor water solution of Pt and Au regulated through complexant, the reaction time is 1 ~ 10h, and optimum reacting time is 1.5 ~ 3h.Obtain the Pt of class nucleocapsid structure xau ym zthe colloidal solution of nanometer seed.
6) the supporting and sedimentation of platinum based catalyst nano particle
High-area carbon through purified treatment is dispersed in higher boiling, water miscible alcoholic solvent by A, is then added to Pt xau ym zin the colloidal solution of nanometer seed, by Pt under stirring xau ym znano particle evenly supports in high-area carbon surface.Mixing time is 4 ~ 12h.
The high-area carbon of so-called purified treatment goes deimpurity process for using non-oxidizable aqueous acid to high-area carbon, and treatment temperature is 60 ~ 80 DEG C, and the processing time is 2 ~ 8h.The optimization process time is 3 ~ 5h.
So-called non-oxidizing acid is that concentration is not higher than hydrochloric acid or the nitric acid of 2M.
Here high-area carbon is Vulcan XC-72, KB300, KB600, BP2000 isoreactivity charcoal.
At loaded Pt xau ym zin/C, the mass content of Pt is 10 ~ 40%.
B is to 1) in add dilute acid solution, regulate PH to 1, carry out the loaded Pt of charcoal xau ym zthe sedimentation of catalyst.
7) post processing of loaded platinum based catalyst nano particle
A is centrifugal or filter, deionized water is washed, drying, obtains loaded platinum based catalyst nano particle;
B heat treatment is by Pt xau ym z/ C catalyst is heat treatment in reducing atmosphere, and the atom on promoting catalyst surface rearranges, and increases the ratio of surperficial Pt.
Beneficial effect of the present invention
Compared with prior art, catalyst nano-particles good dispersion prepared by the present invention, there is obvious Pt, Au enrichment characteristics, the surface enrichment of Pt is conducive to the utilization rate improving Pt atom, thus the noble metal mass ratio improving catalyst is active, and the surface enrichment of Au is conducive to realizing finishing, improve the electrochemical stability of nano particle.
In Kaolinite Preparation of Catalyst process, use complexant to carry out coordination adjustment to noble metal precursor body, reduce reduction potential, thus control reaction speed, promote particle uniformity;
The Pt of preparation class nucleocapsid structure xau ym znanometer seed, farthest can become noble metal by surperficial base metal atomic substitutions;
Carry out the atomic rearrangement of catalyst surface through Technology for Heating Processing, utilize the high-affinity between platinum and hydrogen, promote that platinum element is to catalyst particle surface aggregation.
Utilize non-oxidizable acid treatment carbon carrier, effectively can remove the metal impurities that carrier itself contains, at utmost can also keep the hydrophilic and hydrophobic of carrier.
Eelctro-catalyst preparation method provided by the invention is simple, controllability good, and aqueous phase reactions system, room temperature preparation condition and lower heat treatment temperature make the method both save the energy, reduce manufacturing cost again, easily realize large-scale commercial Application.
Platinum based catalyst prepared by the present invention can directly apply to the negative electrode of Proton Exchange Membrane Fuel Cells, also can be used as the cathod catalyst of other fuel cells.
Accompanying drawing explanation
Fig. 1 is the PtAu that embodiment 1 synthesizes preparation 0.01cu 18the X-ray diffraction spectrogram of/XC-72 catalyst;
Fig. 2 is the PtAu that embodiment 1 synthesizes preparation 0.01cu 18/ XC-72 catalyst HR-TEM collection of illustrative plates before heat treatment;
Fig. 3 is the PtAu that embodiment 1 synthesizes preparation 0.01cu 18/ XC-72 catalyst HR-TEM collection of illustrative plates after heat treatment;
Fig. 4 is the PtAu that embodiment 1 synthesizes preparation 0.01cu 18cyclic voltammetry curve before and after the heat treatment of/XC-72 catalyst compares;
Fig. 5 is the PtAu that embodiment 1 synthesizes preparation 0.01cu 18linear scan (ORR) curve before and after the heat treatment of/XC-72 catalyst compares;
Fig. 6 is the PtAu that embodiment 1 synthesizes preparation 0.01cu 18linear scan (ORR) curve before and after/XC-72 catalyst high potential (0.6 ~ 1.2V vs RHE) scan round 2000 circle compares;
Fig. 7 is the PtAu that embodiment 6 synthesizes preparation 0.004zn 15the cyclic voltammetry curve of/KB300 catalyst.
Detailed description of the invention:
Catalyst electrochemical property test condition:
Working electrode: the glass-carbon electrode of coating PtxAuyMz/C film
To electrode: platinum filament
Reference electrode: saturated calomel electrode (SCE)
Electrolyte: freshly prepared 0.5M HClO 4the aqueous solution
Before the test of CV curve, electrolyte leads to more than high-purity Ar 30min to saturated.
Sweep limits: 0 ~ 1.2V vs RHE
Sweep speed: 20mV s -1
Before linear scan (ORR) test, electrolyte leads to O 2, more than 30min to saturated, current potential is scanned up to 1.0V from 0V, sweeps fast 10mV s-1, electrode rotating speed 1600rpm.
Embodiment 1
1) under stirring at room temperature condition, by 223mg Cu (NO 3) 23H 2o (M:241.6) uniform dissolution is in 23ml propane diols;
2) under stirring at room temperature condition, to 1) in add the propylene glycol solution of 7.5ml trisodium citrate (SC), this solution concentration is 0.04gSC/ml;
3) in 2, pass into more than high-purity Ar 30min, Ar flow velocity is 60ml min -1;
4) 31.5mg sodium borohydride is dissolved in 3ml deionized water;
5) under room temperature, high argon atmospher, by 4) in the aqueous solution slowly drop to 3) in, rate of addition controls as 0.15ml s -1, reduction reaction starts immediately, and after 2h is carried out in reaction, obtain the Cu nanometer seed of stable existence in colloidal form, its concentration is 27.5mM;
6) 5) in reaction carry out period, prepare 15mM be H 2ptCl 6the aqueous solution and 10mM HAuCl 4the aqueous solution.
That draw 3.3ml15mM is H 2ptCl 6the aqueous solution and 63 μ L10mM HAuCl 4the aqueous solution, fully after mixing, adds 42mg NaBr powder, leaves standstill to mixture color and no longer change after mixing.
7) under an inert atmosphere, by 6) in mixed solution is disposable is added to 5 fast) in the colloidal solution of Cu nanometer seed that obtains, carry out the displacement reaction between Pt and Au and transiting metal surface atom, the reaction time is 3h, obtains the PtAu of class nucleocapsid structure 0.01cu 18the colloidal solution of nanometer seed.
8) the supporting and sedimentation of platinum based catalyst nano particle
A by through 0.5M HCl, 60 DEG C, the 40mg Vulcan XC-72 of 3h purified treatment is dispersed in propane diols, is then added to 7) in the PtAu that obtains 0.01cu 18in the colloidal solution of nanometer seed, stirring at room temperature 6h, by PtAu 0.01cu 18nano particle evenly supports in high-area carbon surface.
B is to 1) in add 2MHNO 3the aqueous solution, regulates PH to 1, carries out the loaded PtAu of charcoal 0.01cu 18the sedimentation of catalyst.
9) post processing of loaded platinum based catalyst nano particle
A treats PtAu 0.01cu 18after obvious sedimentation occurs/XC-72 catalyst, it is filtered, deionized water is washed, vacuum drying;
B heat treatment is by PtAu 0.01cu 18/ XC-72C catalyst is at H 2/ N 2200 DEG C of heat treatment 4h in the reducing atmosphere of=1/5, obtain the ternary platinum based catalyst of high activity, high stability.
XRD bulk structure and XPS surface composition sign, electro-chemical activity and stability test are carried out to the catalyst prepared.
Fig. 1 is the PtAu of preparation 0.01cu 18/ XC-72C catalyst compares spectrogram with the XRD of commercialization 20 (wt.) %Pt/C (Johnson matthey company produces) catalyst.The diffraction maximum position of obtained catalyst occurs obviously to move to right, this illustrates that the Cu that there is higher proportion in Pt-Au-Cu nano particle participates in alloying.In conjunction with Bragg formula and Vegard law, by the change of Pt (111) diffraction maximum position, calculate and learn PtAu 0.01cu 18the alloy phase of/XC-72C catalyst consists of Pt 58cu 42.
Characterized by XPS and learn, PtAu 0.01cu 18the nearly surface composition of/XC-72C catalyst is Pt 79au 5cu 16, have obvious Pt, Au enrichment characteristics, the surface enrichment of Pt is conducive to the utilization rate improving Pt atom, thus the noble metal mass ratio improving catalyst is active, and the surface enrichment of Au is conducive to realizing finishing, improves the electrochemical stability of nano particle.
Fig. 2 is PtAu 0.01cu 18the STEM photo of/XC-72C catalyst.As can be seen from STEM photo, Pt-Au-Cu nano particle is dispersed on high-area carbon very uniformly.The average grain diameter of Pt-Au-Cu nano particle at about 3nm, but is not very perfect.
Fig. 3 is the PtAu after heat treatment 0.01cu 18the STEM photo of/XC-72C catalyst.After heat treatment, nano grain surface there occurs reconstruct, and pattern changes to almost spherical.Because treatment temperature is relatively low, only occurred a small amount of aggregate, and the particle diameter of nano particle does not occur obviously to grow up.
Fig. 4 is PtAu before and after heat treatment 0.01cu 18the CV curve of/XC-72C catalyst compares.Heat treatment rear catalyst declines at the response current of hydrogen desorption zoneofoxidation.But in the oxidation/reduction district of Pt, the reduction peak current potential can observing surperficial Pt-Ox species is shuffled about 30mV.The change of this surface characteristics, is conducive to the raising of ORR catalytic activity.
Fig. 5 is PtAu before and after heat treatment 0.01cu 18the ORR catalytic activity test result of/XC-72C catalyst.After heat treatment, after the reconstruct of Pt-Au-Cu nano grain surface, catalytic activity significantly improves, and ORR half wave potential is shuffled about 15mV.Known by Levich-Koutecky formulae discovery, the mass ratio activity of heat treatment rear catalyst is 300mA mg -1pt.
Fig. 6 is the PtAu after heat treatment 0.01cu 18the comparison of the ORR active testing result of/XC-72C catalyst before and after 2000 overall height current potential scan rounds.After the scan round of experience 2000 circle current potential, PtAu 0.01cu 18there is not any decline in the ORR catalytic activity of/XC-72C catalyst, significantly improves on the contrary.Calculate known, PtAu after electric potential scanning 0.01cu 18the noble metal mass ratio activity of/XC-72C catalyst is 543mA mg-1, reaches more than 6 times of Pt/C catalyst.As can be seen here, PtAu 0.01cu 18/ XC-72C catalyst, under simulation PEMFC service condition, has excellent active hold facility.
Embodiment 2
1) under stirring at room temperature condition, by 230mg Co (CH 3cOO) 24H 2o(M:249.1) uniform dissolution is in 92ml ethylene glycol;
2) under stirring at room temperature condition, to 1) in add the ethylene glycol solution of 8.6ml EDETATE SODIUM (M:372.2), this solution concentration is 0.02g EDETATE SODIUM/ml.
3) in 2, high-purity N is passed into 2more than 40min, N 2flow velocity is 100ml min -1.
4) 100mg potassium borohydride is dissolved in 3ml deionized water;
5) at room temperature, high N 2under atmosphere, by 4) in the aqueous solution slowly drop to 3) in, rate of addition controls as 0.3ml s -1, reduction reaction starts immediately, and after 3h is carried out in reaction, obtain the Co nanometer seed of stable existence in colloidal form, its concentration is 8.4mM.
6) 5) in reaction carry out period, prepare 5mM be K 2ptCl 4the aqueous solution and 2mM KAuCl 4the aqueous solution.
That draw 7.0ml, 5mM is K 2ptCl 4the aqueous solution and 50 μ L, 2mM KAuCl 4the aqueous solution, fully after mixing, adds 12.5mg KBr powder, leaves standstill to mixture color and no longer change after mixing.
7) under an inert atmosphere, by 6) in mixed solution is disposable is added to 5 fast) in the colloidal solution of Co nanometer seed that obtains, carry out the displacement reaction between Pt and Au and Co surface atom, the reaction time is 2h, obtains the PtAu of class nucleocapsid structure 0.001co 30the colloidal solution of nanometer seed.
8) the supporting and sedimentation of platinum based catalyst nano particle
A will through 0.5M HNO 3, 80 DEG C, the 53mg KB300 of 5h purified treatment is dispersed in ethylene glycol, is then added to 7) in the PtAu that obtains 0.001co 30in the colloidal solution of nanometer seed, stirring at room temperature 8h, by PtAu 0.001co 30nano particle evenly supports in high-area carbon surface.B is to 1) in add 2MHNO 3the aqueous solution, regulates PH to 1, carries out the loaded PtAu of charcoal 0.001co 30the sedimentation of catalyst.
9) post processing of loaded platinum based catalyst nano particle
A treats PtAu 0.001co 30after obvious sedimentation occurs/KB300 catalyst, it is filtered, deionized water is washed, vacuum drying;
B heat treatment is by PtAu 0.001co 30/ KB300 catalyst is at H 2150 DEG C of heat treatment 2h in the reducing atmosphere of/Ar=1/3, obtain the ternary platinum based catalyst of high activity, high stability.
Embodiment 3
1) under stirring at room temperature condition, by 0.328g NiCl 26H 2o(M:327.5,1mmol) uniform dissolution (70mM) in 14.3ml glycerine;
2) under stirring at room temperature condition, to 1) in add the glycerin solution of 60ml CTAC (M:320), this solution concentration is 50mM.
3) be 10ml min to passing into high-purity more than He40min, He flow velocity in 2 -1.
4) under room temperature, high He atmosphere, to 3) in slowly drip 22 μ L, 37% formalin, rate of addition controls as 0.01ml s -1, reduction reaction starts immediately, and after 5h is carried out in reaction, obtain the Ni nanometer seed of stable existence in colloidal form, its concentration is 13.4mM.
5) 4) in reaction carry out period, prepare 30mM be PtCl 4the aqueous solution and 5mMAuCl 3the aqueous solution.
6) that draw 6.7ml, 30mM is PtCl 4the aqueous solution and 268 μ L, 5mMKAuCl 4the aqueous solution, fully after mixing, adds 5.1ml, 20mM CTAB aqueous solution powder, leaves standstill to mixture color and no longer change after mixing.
7) under an inert atmosphere, by 6) in mixed solution is disposable is added to 5 fast) in the colloidal solution of Co nanometer seed that obtains, carry out the displacement reaction between Pt and Au and Ni surface atom, the reaction time is 1h, obtains the PtAu of class nucleocapsid structure 0.006ni 5the colloidal solution of nanometer seed.
8) the supporting and sedimentation of platinum based catalyst nano particle
A by through 0.5M HCl, 60 DEG C, the 353mg BP2000 of 8h purified treatment is dispersed in glycerine, is then added to 7) in the PtAu that obtains 0.006ni 5in the colloidal solution of nanometer seed, stirring at room temperature 10h, by PtAu 0.006ni 5nano particle evenly supports in high-area carbon surface.
B is to 1) in add 2MHNO 3the aqueous solution, regulates PH to 1, carries out the loaded PtAu of charcoal 0.006ni 5the sedimentation of catalyst.
9) post processing of loaded platinum based catalyst nano particle
A treats PtAu 0.006ni 5after obvious sedimentation occurs/BP2000 catalyst, it is filtered, deionized water is washed, vacuum drying;
B heat treatment is by PtAu 0.006ni 5/ BP2000 catalyst is at H 2300 DEG C, heat treatment 5h in the reducing atmosphere of/Ar=1/10, obtain the ternary platinum based catalyst of high activity, high stability.
Embodiment 4
1) under stirring at room temperature condition, by 180mg Fe (NO 3) 2(anhydrous, M:179.9) uniform dissolution is in 33ml ethylene glycol;
2) under stirring at room temperature condition, to 1) in add the ethylene glycol solution of 20ml CTAB, this solution concentration is 50mM.
3) in 2, high-purity N is passed into 2more than 40min, N 2flow velocity is 30ml min -1.
4) 38mg sodium borohydride is dissolved in 3ml deionized water;
5) at room temperature, high N 2under atmosphere, by 4) in the aqueous solution slowly drop to 3) in, rate of addition controls as 0.5ml s -1, reduction reaction starts immediately, and after reaction carries out 1.5, obtain the Co nanometer seed of stable existence in colloidal form, its concentration is 17.9mM.
6) 5) in reaction carry out period, prepare 50mM be K 2ptCl 6the aqueous solution and 20mM Au (O 2cCH 3) 3the aqueous solution.
That draw 1.3ml, 50mM is K 2ptCl 4the aqueous solution and 13 μ L, 20mMKAuCl 4the aqueous solution, fully after mixing, adds 101mg KBr powder, leaves standstill to mixture color and no longer change after mixing.
7) under an inert atmosphere, by 6) in mixed solution is disposable is added to 5 fast) in the colloidal solution of Co nanometer seed that obtains, carry out the displacement reaction between Pt and Au and Fe surface atom, the reaction time is 2h, obtains the PtAu of class nucleocapsid structure 0.004fe 15the colloidal solution of nanometer seed.
8) the supporting and sedimentation of platinum based catalyst nano particle
A by through 0.5M HCl, 60 DEG C, the 20mg KB600 of 3h purified treatment is dispersed in ethylene glycol, is then added to 7) in the PtAu that obtains 0.004fe 15in the colloidal solution of nanometer seed, stirring at room temperature 8h, by PtAu 0.004fe 15nano particle evenly supports in high-area carbon surface.
B is to 1) in add 2MHNO 3the aqueous solution, regulates PH to 1, carries out the loaded PtAu of charcoal 0.004fe 15the sedimentation of catalyst.
9) post processing of loaded platinum based catalyst nano particle
A treats PtAu 0.004fe 15after obvious sedimentation occurs/KB600 catalyst, it is filtered, deionized water is washed, vacuum drying;
B heat treatment is by PtAu 0.001co 30/ KB300 catalyst is at H 2heat treatment 3h in the reducing atmosphere of/Ar=1/1, obtains the ternary platinum based catalyst of high activity, high stability.
Embodiment 5
1) under stirring at room temperature condition, by 137mg Zn (NO 3) 2(anhydrous, M:136.29) uniform dissolution is in 10ml propane diols;
2) under stirring at room temperature condition, to 1) in add the propylene glycol solution of 8.8ml SC, this solution concentration is 0.04gSC/ml.
3) in 2, more than high-purity Ar 40min is passed into, N 2flow velocity is 50ml min -1.
4) 54mg potassium borohydride is dissolved in 3ml deionized water;
5) under room temperature, high Ar atmosphere, by 4) in the aqueous solution slowly drop to 3) in, rate of addition controls as 0.2ml s -1, reduction reaction starts immediately, and after 4h is carried out in reaction, obtain the Zn nanometer seed of stable existence in colloidal form, its concentration is 46mM.
6) 5) in reaction carry out period, prepare 10mM be Na 2ptCl 4the aqueous solution and 2mM NaAuCl 4the aqueous solution.
That draw 5.4ml, 10mM is Na 2ptCl 4the aqueous solution and 0.345ml, 2mMNaAuCl 4the aqueous solution, fully after mixing, adds 56mg NaBr powder, leaves standstill to mixture color and no longer change after mixing.
7) under an inert atmosphere, by 6) in mixed solution is disposable is added to 5 fast) in the colloidal solution of Co nanometer seed that obtains, carry out the displacement reaction between Pt and Au and Zn surface atom, the reaction time is 10h, obtains the PtAu of class nucleocapsid structure 0.01zn 18the colloidal solution of nanometer seed.
8) the supporting and sedimentation of platinum based catalyst nano particle
A by through 0.5M HCl, 60 DEG C, the 53mg XC72C of 2h purified treatment is dispersed in propane diols, is then added to 7) in the PtAu that obtains 0.01zn 18in the colloidal solution of nanometer seed, stirring at room temperature 10h, by PtAu 0.01zn 18nano particle evenly supports in high-area carbon surface.
B is to 1) in add 2MHNO 3the aqueous solution, regulates PH to 1, carries out the loaded PtAu of charcoal 0.01zn 18the sedimentation of catalyst.
9) post processing of loaded platinum based catalyst nano particle
A treats PtAu 0.01zn 18after obvious sedimentation occurs/XC-72 catalyst, it is filtered, deionized water is washed, vacuum drying;
B heat treatment is by PtAu 0.01zn 18/ XC-72 catalyst is at H 2180 DEG C of heat treatment 4h in the reducing atmosphere of/Ar=1/5, obtain the ternary platinum based catalyst of high activity, high stability.
Embodiment 6
1) under stirring at room temperature condition, by 126mgMnCl 2(anhydrous, M:125.91) uniform dissolution is in 20ml ethylene glycol;
2) under stirring at room temperature condition, to 1) in add the ethylene glycol solution of 50ml SDBS, this solution concentration is 100mM.
3) in 2, high-purity N is passed into 2more than 40min, N 2flow velocity is 60ml min -1.
4) 31.5mg sodium borohydride is dissolved in 3ml deionized water;
5) at room temperature, high N 2under atmosphere, by 4) in the aqueous solution slowly drop to 3) in, rate of addition controls as 0.3ml s -1, reduction reaction starts immediately, and after 3h is carried out in reaction, obtain the Co nanometer seed of stable existence in colloidal form, its concentration is 8.4mM.
6) 5) in reaction carry out period, prepare 10mM be Na 2ptCl 6the aqueous solution and 2mM NaAuCl 4the aqueous solution.
That draw 6.7ml, 10mM is Na 2ptCl 6the aqueous solution and 0.146mL, 2mMNaAuCl 4the aqueous solution, fully after mixing, adds 35mg NaBr powder, leaves standstill to mixture color and no longer change after mixing.
7) under an inert atmosphere, by 6) in mixed solution is disposable is added to 5 fast) in the colloidal solution of Mn nanometer seed that obtains, carry out the displacement reaction between Pt and Au and Mn surface atom, the reaction time is 3h, obtains the PtAu of class nucleocapsid structure 0.004mn 15the colloidal solution of nanometer seed.
8) the supporting and sedimentation of platinum based catalyst nano particle
A by through 0.5M HCl, 60 DEG C, the 31mg KB300 of 4h purified treatment is dispersed in ethylene glycol, is then added to 7) in the PtAu that obtains 0.004mn 15in the colloidal solution of nanometer seed, stirring at room temperature 8h, by PtAu 0.004zn 15nano particle evenly supports in high-area carbon surface.
B is to 1) in add 2MHNO 3the aqueous solution, regulates PH to 1, carries out the loaded PtAu of charcoal 0.004mn 15the sedimentation of catalyst.
9) post processing of loaded platinum based catalyst nano particle
A treats PtAu 0.004mn 15after obvious sedimentation occurs/KB300 catalyst, it is filtered, deionized water is washed, vacuum drying;
B heat treatment is by PtAu 0.004mn 15/ KB300 catalyst is at H 2180 DEG C of heat treatment 3h in the reducing atmosphere of/Ar=1/5, obtain the ternary platinum based catalyst of high activity, high stability.

Claims (6)

1. a preparation method for Electro Catalysts for PEMFC, is characterized in that:
Preparation has the Pt of class nucleocapsid structure xau ym zthe colloidal solution of nanometer seed, by Pt xau ym zsupport in high-area carbon surface, after centrifugal filtration, washing drying, obtain catalyst, Pt xau ym zthe x of nano particle, y, z are distributed as x:y:z=1:0.001 ~ 0.01:5 ~ 30, and the loading of Pt is 10 ~ 40%; Eventually pass Technology for Heating Processing and atomic rearrangement is carried out to catalyst surface;
The wherein Pt of class nucleocapsid structure xau ym zthe preparation process of the colloidal solution of nanometer seed comprises: do not add in the precursor water solution of Pt and Au or add complexant, under an inert atmosphere, by regulate without complexant or be added in the colloidal solution of transition metal M nanometer seed through the precursor water solution of Pt and Au that complexant regulates, reaction 1 ~ 10h is prepared from;
Technology for Heating Processing is heat treatment in reducing atmosphere, and temperature ranges is 120 ~ 300 DEG C, and the processing time is 0.5 ~ 5h; After Technology for Heating Processing, surface atom consists of x:y:z=85 ~ 50:5 ~ 10:10 ~ 40.
2. the preparation method of catalyst according to claim 1, is characterized in that:
High-area carbon is the high-area carbon through purification process technique, and purification process technique goes deimpurity process for using non-oxidizable aqueous acid to high-area carbon, and treatment temperature is 60 ~ 80 DEG C, and the processing time is 2 ~ 8h; Non-oxidizing acid is hydrochloric acid or the nitric acid of concentration 0.1-2M.
3. the preparation method of catalyst according to claim 1, is characterized in that: the Pt of class nucleocapsid structure xau ym zin the preparation process of the colloidal solution of nanometer seed, the atomic ratio of transition metal M and Pt is 5:1 ~ 30:1, and the mol ratio of element Pt and Au is 500:1 ~ 50:1, and the molar ratio of complexant and element Pt and Au sum is 0:1 ~ 20:1;
Pt presoma is H 2ptCl 6, PtCl 4, K 2ptCl 6, Na 2ptCl 6, K 2ptCl 4in one; In its aqueous solution, element Pt concentration is 5mM ~ 50mM;
Au presoma is AuCl 3, Au (O 2cCH3) 3, HAuCl 4, NaAuCl 4, KAuCl 4in one; In its aqueous solution, elements A u concentration is 2mM ~ 20mM;
Transition metal M is the one in Mn, Fe, Co, Ni, Cu, Zn;
Complexant is the one of sodium bromide, KBr, softex kw.
4. the preparation method of catalyst according to claim 1, is characterized in that: the reducing atmosphere of Technology for Heating Processing is H 2with mixing of inert gas, H 2be 1:1 ~ 1:10 with the volume ratio of inert gas, inert gas is Ar, N 2, one in He; High-area carbon is active carbon Vulcan XC-72, KB300, KB600 or BP2000.
5. the preparation method of catalyst according to claim 1, is characterized in that: the preparation process of the colloidal solution of transition metal nanometer seed is as follows;
Under room temperature condition; by transition metal M presoma uniform dissolution in alcoholic solvent; protective agent is dissolved in the alcoholic solution of transition metal M presoma; under inert gas shielding; add the aqueous solution that concentration is 0.1 ~ 0.5M reducing agent, adding speed is 0.05 ~ 0.5ml s-1, and reducing agent is determined according to the metering ratio of chemical reaction with the mol ratio of transition metal ions; reaction time is 1 ~ 5h, obtains the colloidal solution of transition metal nanometer seed.
6. the preparation method of catalyst according to claim 5, is characterized in that:
Transition metal M presoma is the halide of metal M, nitrate or acetate;
Alcoholic solvent is the one in ethylene glycol, propane diols, glycerine;
Protective agent is chelator acid citrate trisodium or disodium ethylene diamine tetraacetate or surfactant hexadecyltrimethylammonium chloride, softex kw, neopelex;
The concentration of transition metal ions in alcoholic solution is 10mM ~ 100mM;
The mol ratio of protective agent and transition metal ions is 0.5:1 ~ 5:1;
Reducing agent is boron hydride or formaldehyde;
Inert gas is Ar, N 2, one in He, inert gas flow velocity is 10 ~ 100mlmin -1.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108075144A (en) * 2016-11-18 2018-05-25 中国科学院大连化学物理研究所 A kind of fuel cell catalyst with core-casing structure and preparation and application
CN108786845A (en) * 2018-06-27 2018-11-13 济南大学 A kind of preparation method of dendroid Pt-Ni-Cu alloy nanoparticles
CN112864401A (en) * 2019-11-28 2021-05-28 大连大学 Application of noble metal modified paper electrode in preparation of ethylene glycol electrocatalytic oxidation battery
CN112980247A (en) * 2019-12-14 2021-06-18 中国科学院大连化学物理研究所 High-stability ink-jet printing ink for fuel cell and preparation and application thereof

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CN1382234A (en) * 1999-08-25 2002-11-27 金伯利-克拉克环球有限公司 Biodisintegratable nonwovens with fluid management properties and disposable absorbent products containing same
US20040087441A1 (en) * 2002-10-29 2004-05-06 Christina Bock Platinum based nano-size catalysts

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CN1382234A (en) * 1999-08-25 2002-11-27 金伯利-克拉克环球有限公司 Biodisintegratable nonwovens with fluid management properties and disposable absorbent products containing same
US20040087441A1 (en) * 2002-10-29 2004-05-06 Christina Bock Platinum based nano-size catalysts

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108075144A (en) * 2016-11-18 2018-05-25 中国科学院大连化学物理研究所 A kind of fuel cell catalyst with core-casing structure and preparation and application
CN108786845A (en) * 2018-06-27 2018-11-13 济南大学 A kind of preparation method of dendroid Pt-Ni-Cu alloy nanoparticles
CN112864401A (en) * 2019-11-28 2021-05-28 大连大学 Application of noble metal modified paper electrode in preparation of ethylene glycol electrocatalytic oxidation battery
CN112980247A (en) * 2019-12-14 2021-06-18 中国科学院大连化学物理研究所 High-stability ink-jet printing ink for fuel cell and preparation and application thereof

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