CN105727993A - Fct-phase FePtCu ternary alloy nano particle catalyst and synthesis method thereof - Google Patents
Fct-phase FePtCu ternary alloy nano particle catalyst and synthesis method thereof Download PDFInfo
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- 229910002058 ternary alloy Inorganic materials 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title abstract 2
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 7
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims abstract description 7
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 14
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- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 9
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- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 6
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- 230000008901 benefit Effects 0.000 abstract description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 abstract 1
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- 239000010411 electrocatalyst Substances 0.000 abstract 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 abstract 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B22F1/0003—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides an fct-phase FePtCu ternary alloy nano particle catalyst and a synthesis method thereof. A polyalcohol reduction method is adopted, and metal precursors (including anhydrous FeCl2, platinum acetylacetonate and copper acetylacetonate), 1,2-hexadecanediol, oleic acid and oleylamine are heated to react in an organic solvent hexadecylamine, and are stirred in an N2 protection atmosphere; after heating and cooling, n-hexane and ethanol are added, and then the mixture is centrifuged and separated; supernatant is removed and sediment is dried to obtain a nano particle product; the structure, magnetism and catalytic activity of the nano particle product are determined; and the diameter of fct-phase FePtCu ternary alloy nano particles is 9-15 nanometers, the coercive force reaches 900Oe-4800Oe, an HER (Hydrogen Evolution Reaction) electro-catalytic property is characterized under the condition of 10mA/cm<2> and the over-potential eta=34-44mV Tafel slope b is equal to 23.6mV/dec-28.2mV/dec, and the ORR (Oxygen Reduction Reaction) electro-catalytic performance is excellent. The invention further synthesizes the fct-phase FePtCu ternary alloy nano particle catalyst with excellent performance. The fct-phase FePtCu ternary alloy nano particle catalyst does not need to be subjected to high-temperature annealing treatment, has the advantages of simplicity in preparation, low cost, high catalytic activity and good catalyst stability, and has very great application potential by being used as the HER and OOR electro-catalyst.
Description
[technical field]
The invention belongs to nanotechnology and catalytic field.More specifically, the present invention relates to a kind of face-centered tetragonal structure FePtCu ternary alloy nano beaded catalyst and synthetic method thereof, its liberation of hydrogen evolution reaction (HER) and redox reactions (ORR) performance are the most superior, it is adaptable to use on water electrolysis hydrogen production and fuel cell.
[background technology]
The energy is a grand strategy development field of world, finds a challenge and opportunity that high efficient energy sources are the current facings of scientific and technological circle.The unsustainable property of Fossil fuel, and combustion of fossil fuels release harmful gas cause environmental pollution, a large amount of CO2The serious global problems such as the greenhouse effect produced order about the mankind's continuous exploration to new forms of energy.Hydrogen energy source is that one has high fuel value, cleaning and the free of contamination energy [1].Hydrogen energy source is as sustainable, clean energy resource, it is thus achieved that the extensive concern of countries in the world researcher.The production of Hydrogen Energy the most mainly relies on coal at present, the reformation of natural gas obtains, and this will necessarily aggravate the consumption of non-regeneration energy and bring problem of environmental pollution.Therefore, utilizing water decomposition hydrogen manufacturing is then fundamentally one of desirable route solving the energy and problem of environmental pollution.
Industrial electrolysis water has been one hundred years of history, and hydrogen prepared by electrolysis water is considered as optimal energy carrier [2].It can make the renewable sources of energy reach balance with the final utilization of the energy, and the catalyst efficiency yet with water electrolysis hydrogen production is low and energy consumption is high, greatly limit it and produces on a large scale.In recent years, the catalysis that the research of water electrolysis hydrogen production concentrates on raising electrode material is active, thus the overpotential under equal cathode reaction electric current during reducing evolving hydrogen reaction.At present, platinum group noble metal is the eelctro-catalyst that electrolysis Aquatic product hydrogen efficiency is the highest, but platinum metal is rare precious metal, is used for making electrolysis water catalyst and cost can be caused to raise, and platinum (Pt) is that noble metal is easily poisoned [3] by sulfur.In acidic electrolysis bath, Pt is as the highest eelctro-catalyst of HER efficiency, its limitation used makes research worker be devoted to find the cathod catalyst that can match in excellence or beauty with it always, and this hydrogen evolution electrode material not only to have preferable stability, more to decrease on cost.As prepared platino metal alloy, utilize a large amount of base metal synthesis no-Pt catalysts existed on the earth, such as sulfide, phosphide, carbide etc..Hydrogen is its fuel as fuel cell as the reason of clean energy resource, (HOR) is reacted at anode generation oxidation of hydrogen, at negative electrode generation oxygen reduction reaction (ORR) reaction release electric energy, product only has water not produce harmful substance simultaneously.Key currently, with respect to the research of fuel cell concentrates on the performance improving negative electrode ORR catalyst and the loading reducing Pt.The ORR catalyst of business is Pt/C nano-particle.Research shows, uses Fe, alloying Pt such as Co, Ni, Cu can improve catalysis activity and the electrochemical stability of Pt, and has the performance [4] being better than business Pt/C nano-particle.
Within 2000, IBM Washington research center professor Sun Shouheng successfully synthesizes self-assembled nanometer magnetic Fe Pt bianry alloy array by high temperature organic process method, the FePt array of this method synthesis is face-centered cubic (fcc) phase, needing to make FePt be face-centered tetragonal (fct) phase by fcc phase in version through high annealing, its performance could improve.But the method nano-particle in high-temperature annealing process can be reunited.In order to solve this problem, many research groups take the method for doping, such as by the metal-doped reduction system phase transition temperature such as Au, Ag, Sb, thus improve particle agglomeration [5] to a certain extent.
How to find new alloy nanoparticle so that it is there is higher evolving hydrogen reaction (HER) and the performance of oxygen reduction reaction (ORR), be the middle problem demanding prompt solution that currently taps a new source of energy.The present inventor studies through lot of experiments on the basis of this research method, and by introducing Cu element, one-step synthesis has gone out fct phase high HER performance FePtCu ternary alloy nano beaded catalyst, and it also has good potentiality in the application of fuel cell.
[list of references]
[1]Lewis N S,Nocera D G.Proceedings of the National Academy of Sciences,2006,103(43):15729-15735.
[2]Wang M,Wang Z,Gong X,et al,Renewable and Sustainable Energy Reviews,2014,29:573-588.
[3]Gudmundsdóttir S,Skúlason E,Weststrate K J,et al,Physical Chemistry Chemical Physics,2013,15(17):6323-6332.
[4]Li Q,Wu L,Wu G,et al,Nano Letter,2015,15:2468-2473.
[5]Wang H,Shang P,Zhang J,et al,Chemistry of Materials,2013,25(12):2450-2454.
Summary of the invention
It is an object of the invention to propose the FePtCu ternary alloy nano beaded catalyst of a kind of fct phase.It has evolving hydrogen reaction (HER) and the superior function of oxygen reduction reaction (ORR).
Another object of the present invention is the synthetic method of the FePtCu ternary alloy nano beaded catalyst proposing a kind of fct phase.The method can directly generate the FePtCu ternary alloy nano beaded catalyst of fct phase.
The present invention is realized in.The FePtCu ternary alloy nano beaded catalyst of a kind of fct phase is elementary composition by Fe, Pt, Cu tri-kinds, that prepare with polyol reduction method, there is the FePtCu ternary alloy nano beaded catalyst of fct phase, wherein Fe element is 30～50%, Pt element is 30～50%, and Cu element is 20%～40%.
Three kinds of element percentage that the FePtCu ternary alloy nano beaded catalyst technique effect of described fct phase is optimal are: Fe element is 50 ± 2%, and Pt element is 30 ± 2%, and Cu element is 20 ± 2%.
The synthetic method of the FePtCu ternary alloy nano beaded catalyst of the present invention a kind of fct phase.The steps include:
First, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu (acac)2) as metal precursor, the 1 of 1.5mmol, 2-hexadecane diol pours in four mouthfuls of round-bottomed flasks of 100ml as reducing agent mixing, adds high boiling organic solvent cetylamine as reaction dissolvent, at the N of flowing2Atmosphere is carried out heat and mechanical agitation, when whole mixed solution temperature is raised to 110 DEG C, adding coating material oleic acid and oleyl amine after insulation 10min be respectively 1ml, treats that solution is heated to about 320 DEG C, carries out heating condensing reflux at this temperature and keeps mechanic whirl-nett reaction 2.5～3.5 hours.
Stop heating, mixed solution system naturally cools to 80 DEG C at normal temperatures, then in four-hole bottle, add normal hexane and the mixed solution of dehydrated alcohol that 60ml volume ratio is 1:1, solution equalization subpackage is transferred in centrifuge tube, and be centrifuged separating with rotating speed 3000～5000 revs/min, remove the yellowish-brown supernatant of centrifugal gained, add impartial ethanol solution to centrifuge tube the most respectively residue is carried out and centrifugation, repetitive operation 3～4 times in the same fashion, until supernatant is water white transparency, the black residual product cleaned i.e. can be obtained.
Described centrifugation is the centrifuge that the centrifugation that the centrifuge using existing market to sell is carried out, such as Yancheng City Kate experimental apparatus company limited produce.
Finally, by clean black residue in drying baker 70 DEG C be dried, then use X-ray diffraction analysis (XRD) to measure the structure of its nanoparticle, obtain described face-centered tetragonal structure FePtCu ternary alloy nano granular product.
Described high HER performance fct-FePtCu ternary alloy nano granule is respectively adopted X-ray diffraction analysis (XRD) again and comprehensive physical measurement system (PPMS) measures structure and the magnetic of its nanoparticle, confirms to obtain FePtCu nano-particle.
The present invention uses the factory of XRD instrument: Shimadzu Corporation of Japan.
XRD determining condition: indoor temperature measurement, the angle of diffraction is 15～90 degree, and other condition is normal condition.Sample prepared by the present invention is dried FePtCu powder of nanometric particles.
XRD interpretation of result shows, FePtCu nanoparticle sample crystallinity prepared by the present invention is obvious, has the crystal characteristic of face-centered tetragonal phase；Calculate the particle diameter of FePtCu nanoparticle sample according to Scherrer formula D=K λ/β cos θ and fct phase (111) half-peak breadth, its grain size is 9～15 nanometers.
The present invention uses the factory of PPMS instrument: Quantum Design company of the U.S..
PPMS condition determination: indoor temperature measurement, test magnetic field intensity is 4 teslas, and other condition is normal condition.Sample prepared by the present invention is dried FePtCu nano-particle.
PPMS interpretation of result shows, the present invention prepares sample and has the coercitive feature that magnetic is strong, high, and its coercivity is up to 900～4700Oe.
The present invention, during research, further relates to the test of the HER electro-catalysis sign performance of the FePtCu ternary alloy nano granule using the electrochemical workstation (CHI760E) of Shanghai Chen Hua company production to carry out this high HER performance.
Electrochemical workstation (CHI760E) test condition: indoor temperature measurement, platinized platinum is as to electrode, and Ag/AgCl electrode is as reference electrode, and electrolyte is 0.5MH2SO4, sweep speed is 5mV/s, and scanning voltage is-0.4～1.5V.
Electrochemical results analysis shows, sample prepared by the present invention has preferable stability in acidic electrolysis bath, at 10mA/cm2Under the conditions of overpotential η=34～44mV, tower phenanthrene slope b=23.6～28.2mV/dec,
In terms of test data, the HER electrocatalysis characteristic of the present invention is substantially better than FePt bianry alloy and business Pt/C.(referring to accompanying drawing)
The invention has the beneficial effects as follows:
The present invention is by introducing Cu element, and one-step synthesis has gone out fct phase high HER performance FePtCu ternary alloy nano beaded catalyst.This method need not the high temperature anneal adopted in any way, only i.e. can need to be stablized through cold drying, the FePtCu ternary alloy nano granule of acidproof fct phase, and has the HER electrocatalysis characteristic being better than fcc phase FePt and business Pt.
Present invention obtains homogeneous fct and coercivity reaches 4700Oe, it is to avoid because of annealing and the nanoparticle agglomerates problem brought under high temperature in prior art.The catalyst preparation of the present invention is simple, and low cost is prepared into electrode, and in acidic electrolysis bath, stability and catalysis activity are the most excellent.
In electrolysis Aquatic product hydrogen catalyst, have good advantage as HER eelctro-catalyst, the application of ORR catalyst also has the biggest potentiality.
[accompanying drawing explanation]
Fig. 1 represents the X ray diffracting spectrum of catalyst of the present invention and binary fcc-FePt
Fig. 2 represents fct-Fe of the present invention50Pt30Cu20The Curve of Magnetic Hysteresis Loop figure of ternary alloy nano beaded catalyst
Fig. 3 represents business Pt, fcc-FePt and fct-Fe50Pt30Cu20HER polarization curve
Fig. 4 represents business Pt, fcc-FePt and fct-Fe50Pt30Cu20Tower phenanthrene curve chart
Fig. 5 represents business Pt, fcc-FePt and fct-Fe50Pt30Cu20Cyclical stability curve chart
Fig. 6 represents fct-Fe50Pt30Cu20ORR polarization curve
[detailed description of the invention]
Meaning of the present invention is will be better understood that below by embodiment.
Embodiment 1: the fct-Fe of the preparation present invention50Pt30Cu20Ternary alloy nano beaded catalyst, its percentage ratio be Fe element be 50 ± 2%, Pt element is 30 ± 2%, and Cu element is 20 ± 2%.
First, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu (acac)2) as metal precursor, 1.5mmol 1,2-hexadecane diol is poured in four mouthfuls of round-bottomed flasks of 100ml as reducing agent mixing, and 20～25g high boiling organic solvent cetylamines are as reaction dissolvent, at the N of flowing2Mechanical agitation is carried out while atmosphere heats, when whole mixed solution temperature is raised to 110 DEG C, coating material oleic acid and each 1mL of oleyl amine is added after insulation 10min, treat that solution is heated to about 320 DEG C, carry out at this temperature heating condensing reflux and keeping mechanic whirl-nett reaction 2.5～3.5 hours.
Stop heating, whole mixed solution system is made to naturally cool to 80 DEG C after removing heater at normal temperatures, then in four-hole bottle, add normal hexane and the mixed solution of dehydrated alcohol that 60ml volume ratio is 1:1, black particle equalization subpackage is transferred in centrifuge tube, and be centrifuged separating with rotating speed 3000～5000 revs/min, remove the yellowish-brown supernatant of centrifugal gained, add impartial ethanol solution to centrifuge tube the most respectively to be centrifuged separating, repetitive operation 3～4 times in the same fashion, until supernatant is water white transparency, i.e. can obtain the black residue cleaned.
Finally clean black residue is dried in vacuum, 60～70 DEG C of conditions, obtains fct-Fe50Pt30Cu20Ternary alloy nano granule.
Use the method described in this specification to measure to obtain:
Fe50Pt30Cu20Ternary alloy nano granule is face-centered tetragonal phase, and its particle diameter is about 11nm；
Fe50Pt30Cu20The magnetic property of ternary alloy nano granule is that coercivity reaches 3600Oe；
Fe in electrolysis Aquatic product hydrogen reaction50Pt30Cu20Ternary alloy nano granule is at 10mA/cm2Under the conditions of overpotential η=34mV, tower phenanthrene slope b=23.6mV/dec；
Embodiment 2: the fct-Fe of the preparation present invention30Pt50Cu20Ternary alloy nano beaded catalyst, its percentage ratio be Fe element be 30 ± 2%, Pt element is 50 ± 2%, and Cu element is 20 ± 2%.
First, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu (acac)2) as metal precursor, the 1 of 1.5mmol, 2-hexadecane diol is poured in four mouthfuls of round-bottomed flasks of 100ml as reducing agent mixing, and 20～25g high boiling organic solvent cetylamines are as reaction dissolvent, at the N of flowing2Mechanical agitation is carried out while atmosphere heats, when whole mixed solution temperature is raised to 110 DEG C, coating material oleic acid and each 1mL of oleyl amine is added after insulation 10min, treat that solution is heated to about 320 DEG C, carry out at this temperature heating condensing reflux and keeping mechanic whirl-nett reaction 2.5～3.5 hours.
Stop heating, whole mixed solution system is made to naturally cool to about 80 DEG C after removing heater at normal temperatures, then in four-hole bottle, add normal hexane and the mixed solution of dehydrated alcohol that 60ml volume ratio is 1:1, black particle equalization subpackage is transferred in centrifuge tube, and be centrifuged separating with rotating speed 3000～5000 revs/min, remove the yellowish-brown supernatant of centrifugal gained, add impartial ethanol solution to centrifuge tube the most respectively to be centrifuged separating, repetitive operation 3～4 times in the same fashion, until supernatant is water white transparency, i.e. can obtain the black residue cleaned.
Finally clean black residue is dried in vacuum, 60～70 DEG C of conditions, obtains Fe30Pt50Cu20Ternary alloy nano granule.
Use the method described in this specification to measure to obtain:
Fe30Pt50Cu20Ternary alloy nano granule is face-centered tetragonal phase, and its particle diameter is about 10nm；
Fe30Pt50Cu20The magnetic property of ternary alloy nano granule is that coercivity reaches 900Oe；
Fe in electrolysis Aquatic product hydrogen reaction30Pt50Cu20Ternary alloy nano granule is at 10mA/cm2Under the conditions of overpotential η=44mV, tower phenanthrene slope b=27mV/dec；
Embodiment 3: the fct-Fe of the preparation present invention35Pt45Cu20Ternary alloy nano beaded catalyst, its percentage ratio be Fe element be 35 ± 2%, Pt element is 45 ± 2%, and Cu element is 20 ± 2%.
First, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu (acac)2) as metal precursor, 1.5mmol 1,2-hexadecane diol is poured in four mouthfuls of round-bottomed flasks of 100ml as reducing agent mixing, and 20～25g high boiling organic solvent cetylamines are as reaction dissolvent, at the N of flowing2Mechanical agitation is carried out while atmosphere heats, when whole mixed solution temperature is raised to 110 DEG C, coating material oleic acid and each 1mL of oleyl amine is added after insulation 10min, treat that solution is heated to about 320 DEG C, carry out at this temperature heating condensing reflux and keeping mechanic whirl-nett reaction 2.5～3.5 hours.
Stop heating, whole mixed solution system is made to naturally cool to about 80 DEG C after removing heater at normal temperatures, then in four-hole bottle, add normal hexane and the mixed solution of dehydrated alcohol that 60ml volume ratio is 1:1, black particle equalization subpackage is transferred in centrifuge tube, and be centrifuged separating with rotating speed 3000～5000 revs/min, remove the yellowish-brown supernatant of centrifugal gained, add impartial ethanol solution to centrifuge tube the most respectively to be centrifuged separating, repetitive operation 3～4 times in the same fashion, until supernatant is water white transparency, i.e. can obtain the black residual product cleaned.
Finally clean black residue is dried in vacuum, 60～70 DEG C of conditions, obtains Fe35Pt45Cu20Ternary alloy nano granule.
Use the method described in this specification to measure to obtain:
Fe35Pt45Cu20Ternary alloy nano granule is face-centered tetragonal phase, and its particle diameter is about 11nm；
Fe35Pt45Cu20The magnetic property of ternary alloy nano granule is that coercivity reaches 4800Oe；
Fe in electrolysis Aquatic product hydrogen reaction35Pt45Cu20Ternary alloy nano granule is at 10mA/cm2Under the conditions of overpotential η=39mV, tower phenanthrene slope b=25mV/dec；
Embodiment 4: the fct-Fe of the preparation present invention35Pt45Cu20Ternary alloy nano beaded catalyst, its percentage ratio be Fe element be 45 ± 2%, Pt element is 35 ± 2%, and Cu element is 20 ± 2%.Height HER performance fct-Fe of the present invention45Pt35Cu20The preparation of ternary alloy nano beaded catalyst
First, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu (acac)2) as metal precursor, the 1 of 1.5mmol, 2-hexadecane diol is poured in four mouthfuls of round-bottomed flasks of 100ml as reducing agent mixing, and 20～25g high boiling organic solvent cetylamines are as reaction dissolvent, at the N of flowing2Mechanical agitation is carried out while atmosphere heats, when whole mixed solution temperature is raised to 110 DEG C, coating material oleic acid and each 1mL of oleyl amine is added after insulation 10min, treat that solution is heated to about 320 DEG C, carry out at this temperature heating condensing reflux and keeping mechanic whirl-nett reaction 2.5～3.5 hours.
Stop heating, whole mixed solution system is made to naturally cool to about 80 DEG C after removing heater at normal temperatures, then in four-hole bottle, add normal hexane and the mixed solution of dehydrated alcohol that 60ml volume ratio is 1:1, black particle equalization subpackage is transferred in centrifuge tube, and be centrifuged separating with rotating speed 3000～5000 revs/min, remove the yellowish-brown supernatant of centrifugal gained, add impartial ethanol solution to centrifuge tube the most respectively to be centrifuged separating, repetitive operation 3～4 times in the same fashion, until supernatant is water white transparency, i.e. can obtain the black residual product cleaned.
Finally clean black residue is dried in vacuum, 60～70 DEG C of conditions, obtains Fe45Pt35Cu20Ternary alloy nano beaded catalyst.
Use the method described in this specification to measure to obtain:
Fe45Pt35Cu20Ternary alloy nano granule is face-centered tetragonal phase, and its particle diameter is about 13nm；
Fe45Pt35Cu20The magnetic property of ternary alloy nano granule is that coercivity reaches 3100Oe；
Fe in electrolysis Aquatic product hydrogen reaction45Pt35Cu20Ternary alloy nano granule is at 10mA/cm2Under the conditions of overpotential η=42mV, tower phenanthrene slope b=28.2mV/dec.
Claims (8)
1. a fct phase FePtCu ternary alloy nano beaded catalyst, it is characterised in that this nano-particle is urged
Agent is elementary composition by Fe, Pt, Cu tri-kinds, that prepare with polyol reduction method, have face-centered tetragonal
(fct) the FePtCu ternary alloy nano beaded catalyst of phase, wherein Fe element is 30～50%, Pt unit
Element is 30～50%, and Cu element is 20%～40%.
2. a synthetic method for fct phase FePtCu ternary alloy nano beaded catalyst described in claim 1,
Comprise the following steps:
1) by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper
(Cu(acac)2) as metal precursor, the 1 of 1.5mmol, 2-hexadecane diol is poured into as reducing agent mixing
In four mouthfuls of round-bottomed flasks of 100ml, add high boiling organic solvent cetylamine as solvent, at N2Protection
Atmosphere is carried out heat and mechanical agitation, when mixed solution temperature rises to 110 DEG C, after insulation 10min respectively
Add surfactant oleic acid and oleyl amine 1mL, continue heat temperature raising and maintain the temperature at 320 DEG C, temperature at this
Carry out under degree heating condensing reflux and keeping mechanic whirl-nett reaction 2.5～3.5 hours；
2) stopping heating, mixed solution system naturally cools to 80 DEG C at normal temperatures, then adds in four-hole bottle
Enter normal hexane and the mixed solution of dehydrated alcohol that about 60ml volume ratio is 1:1, solution equalization subpackage is turned
Shifting is poured in centrifuge tube, is centrifuged separating with rotating speed 3000～5000 revs/min, removes the yellowish-brown of centrifugal gained
Color supernatant, then be centrifuged separating, in the same fashion to the impartial ethanol solution of centrifuge tube addition respectively
Repetitive operation 3～4 times, until supernatant is water white transparency, i.e. can obtain the black residual product cleaned；
3) finally clean black residual product is dried under the conditions of 60～70 DEG C, then uses X-ray
Diffraction analysis (XRD) measures the structure of its nanoparticle, confirms that obtaining fct phase FePtCu ternary alloy three-partalloy receives
Rice grain.
A kind of fct phase FePtCu ternary alloy nano beaded catalyst the most according to claim 1, its
It is characterised by that tri-kinds of element percentage of Fe, Pt, Cu are: Fe element is 50 ± 2%, and Pt element is 30 ± 2%,
Cu element is 20 ± 2%.
4. according to a kind of fct phase FePtCu ternary alloy nano granule described in claim 1 or 2 or 3
Catalyst, it is characterised in that the size of nano-particle is 9～15 nanometers.
5. according to a kind of fct phase FePtCu ternary alloy nano granule described in claim 1 or 2 or 3
Catalyst, it is characterised in that its magnetic property is that coercivity reaches 900～4800Oe.
6. according to a kind of fct phase FePtCu ternary alloy nano granule described in claim 1 or 2 or 3
Catalyst, it is characterised in that its HER electro-catalysis characterizes performance, at 10mA/cm2Under the conditions of overpotential
η=34～44mV, tower phenanthrene slope b=23.6～28.2mV/dec.
7. according to a kind of fct phase FePtCu ternary alloy nano granule described in claim 1 or 2 or 3
Catalyst, it is characterised in that can apply to be electrolysed the HER catalyst of Aquatic product hydrogen.
8. according to a kind of fct phase FePtCu ternary alloy nano granule described in claim 1 or 2 or 3
Catalyst, it is characterised in that can apply to the negative electrode ORR catalyst of fuel cell.
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