CN105727993B - A kind of fct phase FePtCu ternary alloy nano beaded catalyst and its synthetic method - Google Patents
A kind of fct phase FePtCu ternary alloy nano beaded catalyst and its synthetic method Download PDFInfo
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- CN105727993B CN105727993B CN201610037612.7A CN201610037612A CN105727993B CN 105727993 B CN105727993 B CN 105727993B CN 201610037612 A CN201610037612 A CN 201610037612A CN 105727993 B CN105727993 B CN 105727993B
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- 229910002058 ternary alloy Inorganic materials 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 229920005862 polyol Polymers 0.000 claims abstract description 3
- 150000003077 polyols Chemical class 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 65
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 12
- 239000006228 supernatant Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 6
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 abstract description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005642 Oleic acid Substances 0.000 abstract description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 6
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 abstract description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 239000010949 copper Substances 0.000 description 9
- 229910005335 FePt Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- -1 it be 30~50% Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000003252 repetitive effect Effects 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009529 body temperature measurement Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 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
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
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- 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
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- 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 proposes a kind of fct phase FePtCu ternary alloy nano beaded catalyst and its synthetic methods.Using polyol reduction method, in N2In protective atmosphere, by metal precursor (anhydrous FeCl2, acetylacetone,2,4-pentanedione platinum, acetylacetone copper), 1,2- hexadecane diol, oleic acid and oleyl amine heat in organic solvent cetylamine and react and be stirred.By heating, it is cooling, add n-hexane, ethyl alcohol, centrifuge separation, removes supernatant, obtains nano-particle product after drying precipitate, and measure its structure, magnetism, catalytic activity, the diameter of fct-FePtCu ternary alloy nano particle is 9~15 nanometers, and coercivity is characterized in 10mA/cm up to 900~4800Oe, HER electrocatalysis characteristic2Under the conditions of overpotentialTower phenanthrene slope b=23.6~28.2mV/dec, ORR electrocatalysis characteristic is excellent.One-step synthesis of the present invention has gone out the fct phase FePtCu ternary alloy nano beaded catalyst of superior performance.It is not required to the high temperature anneal, preparation is simple, and at low cost, catalytic activity is high, and catalyst stability is good.There are very big potentiality in the application as HER, ORR elctro-catalyst.
Description
【Technical field】
The invention belongs to nanotechnologies and catalytic field.More particularly it relates to a kind of face-centered tetragonal structure
FePtCu ternary alloy nano beaded catalyst and its synthetic method, liberation of hydrogen, which develops, reacts (HER) and redox reactions
(ORR) performance is very superior, suitable for using on water electrolysis hydrogen production and fuel cell.
【Background technique】
The energy is a grand strategy development field of countries in the world today, and finding high efficient energy sources is that scientific and technological circle are common at present
The challenge faced and opportunity.The unsustainable property of fossil fuel, and the pernicious gas of combustion of fossil fuels release cause
Environmental pollution, a large amount of CO2The serious global problem such as the greenhouse effects of generation drives continuous spy of the mankind to new energy
Rope.Hydrogen energy source is a kind of with high fuel value, cleaning and the free of contamination energy [1].Hydrogen energy source is as sustainable, cleaning energy
Source obtains the extensive concern of countries in the world researcher.The production of Hydrogen Energy at present also mainly comes by the reformation of coal, natural gas
It obtains, this will necessarily aggravate the consumption of non-regeneration energy and bring problem of environmental pollution.Therefore, then using water decomposition hydrogen manufacturing
It is fundamentally to solve one of the energy and the desirable route of problem of environmental pollution.
Industrial electrolysis water has been one hundred years of history, and the hydrogen of electrolysis water preparation is considered as that the optimal energy carries
Body [2].It can make the final use of the renewable sources of energy and the energy reach balance, however due to the catalyst of water electrolysis hydrogen production
Low efficiency and energy consumption height greatly limit its large-scale production.In recent years, the research of water electrolysis hydrogen production, which concentrates on, improves electrode
The catalytic activity of material, thus the overpotential during reducing evolving hydrogen reaction under same cathode reaction electric current.Currently, the expensive gold of platinum group
Category is the highest elctro-catalyst of electrolysis water hydrogen generation efficiency, however platinum metal is rare precious metal, for doing electrolysis water catalysis
Agent will lead to cost raising, and platinum (Pt) is that noble metal is easy to poison [3] by sulphur.In acidic electrolysis bath, Pt is imitated as HER
The highest elctro-catalyst of rate, the limitation used make researchers have been devoted to find the cathode that can match in excellence or beauty with it and urge
Agent, this hydrogen evolution electrode material will not only have preferable stability, more to decrease in cost.Such as prepare platinum base metal
Alloy synthesizes no-Pt catalyst, such as sulfide, phosphide, carbide etc. using existing base metals a large amount of on the earth.Hydrogen
It is its fuel as fuel cell as the reason of clean energy resource, oxidation of hydrogen reaction (HOR) occurs in anode, is sent out in cathode
Raw oxygen reduction reaction (ORR) reaction release electric energy, while product only has water without generating harmful substance.Currently, about fuel
The key of the research of battery concentrates on the performance for improving cathode ORR catalyst and reduces the loading of Pt.The ORR catalysis of business
Agent is Pt/C nano particle.Studies have shown that the catalytic activity and electrification of Pt can be improved in Co, Ni, the alloyings such as Cu Pt using Fe
Stability is learned, and there is the performance [4] better than business Pt/C nano particle.
The Washington IBM research center professor Sun Shouheng in 2000 successfully synthesizes self-assembled nanometer with high temperature organic process method
The FePt array of magnetic Fe Pt bianry alloy array, this method synthesis is face-centered cubic (fcc) phase, needs to make through high annealing
FePt is face-centered tetragonal (fct) phase by fcc phase transition, and performance could improve.But this method is received in high-temperature annealing process
Rice grain can reunite.In order to solve this problem, the method that many research groups take doping, such as with gold such as Au, Ag, Sb
Belong to doping reduction system phase transition temperature, to improve particle agglomeration [5] to a certain extent.
New alloy nanoparticle how is found, higher evolving hydrogen reaction (HER) and oxygen reduction reaction (ORR) are made it have
Performance, be the middle urgent problem to be solved that currently taps a new source of energy.The present inventor is on the basis of this research method by a large amount of
Experimental study, by introducing Cu element, one-step synthesis has gone out the high HER performance FePtCu ternary alloy nano particulate catalytic of fct phase
Agent also has good potentiality in the application of fuel cell.
【Bibliography】
[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 a kind of FePtCu ternary alloy nano beaded catalyst of fct phase.It has
The superior function of evolving hydrogen reaction (HER) and oxygen reduction reaction (ORR).
Another object of the present invention is to propose a kind of synthesis of the FePtCu ternary alloy nano beaded catalyst of fct phase
Method.This method can directly generate the FePtCu ternary alloy nano beaded catalyst of fct phase.
The invention is realized in this way.A kind of FePtCu ternary alloy nano beaded catalyst of fct phase be by Fe, Pt,
Tri- kinds of element compositions of Cu, FePtCu ternary alloy nano particulate catalytic prepared with polyol reduction method, with fct phase
Agent, it be 30~50%, Cu element is 20%~40% that wherein Fe element, which is 30~50%, Pt element,.
The optimal three kinds of element percentages of FePtCu ternary alloy nano beaded catalyst technical effect of the fct phase
For：It is 30 ± 2%, Cu element is 20 ± 2% that Fe element, which is 50 ± 2%, Pt element,.
A kind of synthetic method of the FePtCu ternary alloy nano beaded catalyst of fct phase of the present invention.Its step is：
Firstly, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu
(acac)2) it is used as metal precursor, 1, the 2- hexadecane diol of 1.5mmol pours into four mouthfuls of circles of 100ml as reducing agent mixing
In the flask of bottom, high boiling organic solvent cetylamine is added as reaction dissolvent, in the N of flowing2Heating and machine are carried out in atmosphere
Tool stirring when entire mixed solution temperature is raised to 110 DEG C, is added coating material oleic acid after keeping the temperature 10min and oleyl amine is respectively
1ml, is heated to 320 DEG C or so to solution, carry out at this temperature heating condensing reflux and keep mechanic whirl-nett reaction 2.5~
3.5 hour.
Stop heating, mixed solution system naturally cools to 80 DEG C at normal temperature, and 60ml body is then added into four-hole bottle
Product is than being 1：The packing of solution equalization is transferred in centrifuge tube by 1 n-hexane and the mixed solution of dehydrated alcohol, and with revolving speed
3000~5000 revs/min are centrifuged, and remove the resulting yellowish-brown supernatant of centrifugation, then equalization is added to centrifuge tube respectively
Ethanol solution is cleaned and is centrifugated to residue, in the same way repetitive operation 3~4 times, until supernatant is colourless
It is transparent, clean black residual product can be obtained.
The centrifuge separation is the centrifuge separation carried out using the centrifuge that existing market is sold, such as Yancheng City Kate
The centrifuge of laboratory apparatus Co., Ltd production.
Finally, clean black residue is dried for 70 DEG C in drying box, then use X-ray diffraction analysis
(XRD) structure for measuring its nanoparticle obtains the face-centered tetragonal structure FePtCu ternary alloy nano granular product.
X-ray diffraction analysis (XRD) is respectively adopted in the high HER performance fct-FePtCu ternary alloy nano particle again
The structure and magnetism of its nanoparticle are measured with comprehensive physical property measuring system (PPMS), confirmation obtains FePtCu nano particle.
The present invention uses the factory of XRD instrument：Japanese Shimadzu Corporation.
XRD determining condition：Indoor temperature measurement, the angle of diffraction are 15~90 degree, and other conditions are normal condition.It is prepared by the present invention
Sample is the FePtCu powder of nanometric particles after drying.
XRD interpretation of result shows that FePtCu nanoparticle sample crystallinity prepared by the present invention is obvious, has face-centered tetragonal
The crystal characteristic of phase；FePtCu nano particle is calculated according to Scherrer formula D=K λ/β cos θ and fct phase (111) half-peak breadth
The partial size of sample, particle size are 9~15 nanometers.
The present invention uses the factory of PPMS instrument：Quantum Design company of the U.S..
PPMS determination condition：Indoor temperature measurement, test magnetic field strength are 4 teslas, and other conditions are normal condition.The present invention
The sample of preparation is the FePtCu nano particle after drying.
PPMS interpretation of result shows that the present invention prepares sample and has the characteristics that magnetic strong, high coercitive, and coercivity can
Up to 900~4700Oe.
The present invention in the course of the study, further relates to the electrochemical workstation using the production of Shanghai Chen Hua company
(CHI760E) test of the HER electro-catalysis characterization performance of the FePtCu ternary alloy nano particle of this high HER performance is carried out.
Electrochemical workstation (CHI760E) test condition：Indoor temperature measurement, platinized platinum are used as to electrode, Ag/AgCl electrode conduct
Reference electrode, electrolyte 0.5MH2SO4, sweep speed 5mV/s, scanning voltage is -0.4~1.5V.
Electrochemical results analysis shows, sample prepared by the present invention has preferable stablize in acidic electrolysis bath
Property, in 10mA/cm2Under the conditions of overpotential η=34~44mV, tower phenanthrene slope b=23.6~28.2mV/dec,
In terms of test data, HER electrocatalysis characteristic of the invention is substantially better than FePt bianry alloy and business Pt/C.
(referring to attached drawing)
The beneficial effects of the invention are as follows：
The present invention has gone out the high HER performance FePtCu ternary alloy nano particle of fct phase by introducing Cu element, one-step synthesis
Catalyst.This method does not need the high temperature anneal in any manner, need to only can be obtained through low temperature drying and stablize, is resistance to
The FePtCu ternary alloy nano particle of the fct phase of acid, and there is the HER electrocatalysis better than fcc phase FePt and business Pt
Energy.
Present invention obtains homogeneous fct and coercivity reaches 4700Oe, avoids in the prior art because annealing under high temperature
It handles and bring nanoparticle agglomerates problem.Catalyst preparation of the invention is simple, at low cost, is prepared into electrode,
Stability and catalytic activity are all more excellent in acidic electrolysis bath.
There is good advantage in electrolysis aquatic products hydrogen catalyst as HER elctro-catalyst, in the application of ORR catalyst
Also there are very big potentiality.
【Detailed description of the invention】
Fig. 1 shows catalyst of the present invention and the X ray diffracting spectrums of binary fcc-FePt
Fig. 2 indicates fct-Fe of the present invention50Pt30Cu20The Curve of Magnetic Hysteresis Loop figure of ternary alloy nano beaded catalyst
Fig. 3 indicates business Pt, fcc-FePt and fct-Fe50Pt30Cu20HER polarization curve
Fig. 4 indicates business Pt, fcc-FePt and fct-Fe50Pt30Cu20Tower phenanthrene curve graph
Fig. 5 indicates business Pt, fcc-FePt and fct-Fe50Pt30Cu20Cyclical stability curve graph
Fig. 6 indicates fct-Fe50Pt30Cu20ORR polarization curve
【Specific embodiment】
Below by embodiment it will be better understood that meaning of the present invention.
Embodiment 1：Prepare fct-Fe of the invention50Pt30Cu20Ternary alloy nano beaded catalyst, percentage Fe
It is 30 ± 2%, Cu element is 20 ± 2% that element, which is 50 ± 2%, Pt element,.
Firstly, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu
(acac)2) it is used as metal precursor, 1.5mmol 1,2- hexadecane diol pours into four mouthfuls of circles of 100ml as reducing agent mixing
In the flask of bottom, 20~25g high boiling organic solvent cetylamine is as reaction dissolvent, in the N of flowing2That is heated in atmosphere is same
When entire mixed solution temperature is raised to 110 DEG C, coating material oleic acid and oil is added after keeping the temperature 10min in Shi Jinhang mechanical stirring
Each 1mL of amine, is heated to 320 DEG C or so to solution, carries out heating condensing reflux at this temperature and keeps mechanic whirl-nett reaction 2.5
~3.5 hours.
Stop heating, so that entire mixed solution system is naturally cooled to 80 DEG C at normal temperature after removing heating device, so
It is 1 that 60ml volume ratio is added in backward four-hole bottle：1 n-hexane and the mixed solution of dehydrated alcohol, by the equal equal part of black particle
Dress is transferred in centrifuge tube, and is centrifuged with 3000~5000 revs/min of revolving speed, is removed in the resulting yellowish-brown of centrifugation
Clear liquid, then impartial ethanol solution is added to centrifuge tube respectively and is centrifuged, repetitive operation 3~4 times in the same way, until
Supernatant be it is colorless and transparent, clean black residue can be obtained.
Clean black residue is dried in vacuum, 60~70 DEG C of conditions finally, obtains fct-Fe50Pt30Cu20
Ternary alloy nano particle.
It measures to obtain using method described in this specification：
Fe50Pt30Cu20Ternary alloy nano particle is face-centered tetragonal phase, and partial size is 11nm or so；
Fe50Pt30Cu20The magnetic property of ternary alloy nano particle is that coercivity reaches 3600Oe；
It is electrolysed Fe in the reaction of aquatic products hydrogen50Pt30Cu20Ternary alloy nano particle is in 10mA/cm2Under the conditions of overpotential η=
34mV, tower phenanthrene slope b=23.6mV/dec；
Embodiment 2：Prepare fct-Fe of the invention30Pt50Cu20Ternary alloy nano beaded catalyst, percentage Fe
It is 50 ± 2%, Cu element is 20 ± 2% that element, which is 30 ± 2%, Pt element,.
Firstly, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu
(acac)2) it is used as metal precursor, 1, the 2- hexadecane diol of 1.5mmol pours into four mouthfuls of circles of 100ml as reducing agent mixing
In the flask of bottom, 20~25g high boiling organic solvent cetylamine is as reaction dissolvent, in the N of flowing2That is heated in atmosphere is same
When entire mixed solution temperature is raised to 110 DEG C, coating material oleic acid and oil is added after keeping the temperature 10min in Shi Jinhang mechanical stirring
Each 1mL of amine, is heated to 320 DEG C or so to solution, carries out heating condensing reflux at this temperature and keeps mechanic whirl-nett reaction 2.5
~3.5 hours.
Stop heating, entire mixed solution system is made to naturally cool to 80 DEG C of left sides at normal temperature after removing heating device
The right side, it is 1 that 60ml volume ratio is then added into four-hole bottle：1 n-hexane and the mixed solution of dehydrated alcohol, black particle is equal
Equal packing are transferred in centrifuge tube, and are centrifuged with 3000~5000 revs/min of revolving speed, and it is resulting yellowish-brown to remove centrifugation
Color supernatant, then impartial ethanol solution is added to centrifuge tube respectively and is centrifuged, repetitive operation 3~4 times in the same way,
Until supernatant be it is colorless and transparent, clean black residue can be obtained.
Clean black residue is dried in vacuum, 60~70 DEG C of conditions finally, obtains Fe30Pt50Cu20Ternary
Alloy nanoparticle.
It measures to obtain using method described in this specification：
Fe30Pt50Cu20Ternary alloy nano particle is face-centered tetragonal phase, and partial size is 10nm or so；
Fe30Pt50Cu20The magnetic property of ternary alloy nano particle is that coercivity reaches 900Oe；
It is electrolysed Fe in the reaction of aquatic products hydrogen30Pt50Cu20Ternary alloy nano particle is in 10mA/cm2Under the conditions of overpotential η=
44mV, tower phenanthrene slope b=27mV/dec；
Embodiment 3：Prepare fct-Fe of the invention35Pt45Cu20Ternary alloy nano beaded catalyst, percentage Fe
It is 45 ± 2%, Cu element is 20 ± 2% that element, which is 35 ± 2%, Pt element,.
Firstly, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu
(acac)2) it is used as metal precursor, 1.5mmol 1,2- hexadecane diol pours into four mouthfuls of circles of 100ml as reducing agent mixing
In the flask of bottom, 20~25g high boiling organic solvent cetylamine is as reaction dissolvent, in the N of flowing2That is heated in atmosphere is same
When entire mixed solution temperature is raised to 110 DEG C, coating material oleic acid and oil is added after keeping the temperature 10min in Shi Jinhang mechanical stirring
Each 1mL of amine, is heated to 320 DEG C or so to solution, carries out heating condensing reflux at this temperature and keeps mechanic whirl-nett reaction 2.5
~3.5 hours.
Stop heating, entire mixed solution system is made to naturally cool to 80 DEG C of left sides at normal temperature after removing heating device
The right side, it is 1 that 60ml volume ratio is then added into four-hole bottle：1 n-hexane and the mixed solution of dehydrated alcohol, black particle is equal
Equal packing are transferred in centrifuge tube, and are centrifuged with 3000~5000 revs/min of revolving speed, and it is resulting yellowish-brown to remove centrifugation
Color supernatant, then impartial ethanol solution is added to centrifuge tube respectively and is centrifuged, repetitive operation 3~4 times in the same way,
Until supernatant be it is colorless and transparent, clean black residual product can be obtained.
Clean black residue is dried in vacuum, 60~70 DEG C of conditions finally, obtains Fe35Pt45Cu20Ternary
Alloy nanoparticle.
It measures to obtain using method described in this specification：
Fe35Pt45Cu20Ternary alloy nano particle is face-centered tetragonal phase, and partial size is 11nm or so；
Fe35Pt45Cu20The magnetic property of ternary alloy nano particle is that coercivity reaches 4800Oe；
It is electrolysed Fe in the reaction of aquatic products hydrogen35Pt45Cu20Ternary alloy nano particle is in 10mA/cm2Under the conditions of overpotential η=
39mV, tower phenanthrene slope b=25mV/dec；
Embodiment 4：Prepare fct-Fe of the invention35Pt45Cu20Ternary alloy nano beaded catalyst, percentage Fe
It is 35 ± 2%, Cu element is 20 ± 2% that element, which is 45 ± 2%, Pt element,.The high HER performance fct-Fe of the present invention45Pt35Cu20Three
The preparation of first alloy nanoparticle catalyst
Firstly, by the anhydrous FeCl of corresponding mol ratio2, acetylacetone,2,4-pentanedione platinum (Pt (acac)2), acetylacetone copper (Cu
(acac)2) it is used as metal precursor, 1, the 2- hexadecane diol of 1.5mmol pours into four mouthfuls of circles of 100ml as reducing agent mixing
In the flask of bottom, 20~25g high boiling organic solvent cetylamine is as reaction dissolvent, in the N of flowing2That is heated in atmosphere is same
When entire mixed solution temperature is raised to 110 DEG C, coating material oleic acid and oil is added after keeping the temperature 10min in Shi Jinhang mechanical stirring
Each 1mL of amine, is heated to 320 DEG C or so to solution, carries out heating condensing reflux at this temperature and keeps mechanic whirl-nett reaction 2.5
~3.5 hours.
Stop heating, entire mixed solution system is made to naturally cool to 80 DEG C of left sides at normal temperature after removing heating device
The right side, it is 1 that 60ml volume ratio is then added into four-hole bottle：1 n-hexane and the mixed solution of dehydrated alcohol, black particle is equal
Equal packing are transferred in centrifuge tube, and are centrifuged with 3000~5000 revs/min of revolving speed, and it is resulting yellowish-brown to remove centrifugation
Color supernatant, then impartial ethanol solution is added to centrifuge tube respectively and is centrifuged, repetitive operation 3~4 times in the same way,
Until supernatant be it is colorless and transparent, clean black residual product can be obtained.
Clean black residue is dried in vacuum, 60~70 DEG C of conditions finally, obtains Fe45Pt35Cu20Ternary
Alloy nanoparticle catalyst.
It measures to obtain using method described in this specification：
Fe45Pt35Cu20Ternary alloy nano particle is face-centered tetragonal phase, and partial size is 13nm or so；
Fe45Pt35Cu20The magnetic property of ternary alloy nano particle is that coercivity reaches 3100Oe；
It is electrolysed Fe in the reaction of aquatic products hydrogen45Pt35Cu20Ternary alloy nano particle is in 10mA/cm2Under the conditions of overpotential η=
42mV, tower phenanthrene slope b=28.2mV/dec.
Claims (2)
1. a kind of fct phase FePtCu ternary alloy nano beaded catalyst is applied to water electrolysis hydrogen production, it is characterised in that the nanometer
Beaded catalyst is made of tri- kinds of elements of Fe, Pt, Cu, it is being prepared with polyol reduction method, have face-centered tetragonal (fct) phase
FePtCu ternary alloy nano beaded catalyst, when three kinds of element percentages are：Fe element is that 30 ± 2%, Pt element is 50
When ± 2%, Cu element are 20 ± 2%, performance is：In 10mA/cm2Under the conditions of, overpotential η=44mV, tower phenanthrene slope b=
27mV/dec；Or Fe element is 50 ± 2%, Pt element when to be 30 ± 2%, Cu element be 20 ± 2%, performance is：?
10mA/cm2Under the conditions of, overpotential η=34mV, tower phenanthrene slope b=23.6mV/dec.
2. a kind of fct phase FePtCu ternary alloy nano beaded catalyst according to claim 1 is applied to electrolysis water system
Hydrogen, it is characterised in that the size of nano particle is 9~11 nanometers.
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| CN109277103A (en) * | 2018-12-03 | 2019-01-29 | 新疆大学 | A kind of high activity platinum bimetallic liberation of hydrogen catalyst and preparation method thereof |
| CN109439953B (en) * | 2018-12-25 | 2020-03-24 | 湖北大学 | Fe43.4Pt52.3Cu4.3Heterostructure phase polyhedral nanoparticles and preparation method and application thereof |
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| CN111617774B (en) * | 2020-06-10 | 2022-11-08 | 贵州大学 | Synthesis and application of quaternary platinum-iron-rhodium-ruthenium nano alloy with hierarchical structure |
| CN112893834B (en) * | 2021-01-20 | 2021-12-21 | 东北大学 | L10-FePt @ PtBi2/Bi core-shell structure nano-particle and one-step synthesis method thereof |
| CN112952120A (en) * | 2021-02-02 | 2021-06-11 | 郑承盛 | Preparation method of Co3O4/NiPdCo alloy/graphene composite material |
| CN113134604B (en) * | 2021-03-31 | 2023-01-17 | 湖北大学 | Pd x Pt (50-x) Bi 50 Ternary alloy nano-particles and preparation method and application thereof |
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