CN103111308A - Method for directly synthesizing Pt-Co bimetallic nanoparticles utilizing water phase and application - Google Patents
Method for directly synthesizing Pt-Co bimetallic nanoparticles utilizing water phase and application Download PDFInfo
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- CN103111308A CN103111308A CN2013100685907A CN201310068590A CN103111308A CN 103111308 A CN103111308 A CN 103111308A CN 2013100685907 A CN2013100685907 A CN 2013100685907A CN 201310068590 A CN201310068590 A CN 201310068590A CN 103111308 A CN103111308 A CN 103111308A
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Abstract
The invention discloses a method for directly synthesizing Pt-Co bimetallic nanoparticles utilizing a water phase and application thereof. The method comprises the following steps of: dissolving a platinum precursor salt and cobalt (II) acetylacetonate hydrate in water, and simultaneously adding polyvinylpyrrolidone to mix; and then placing a mixture in a sealed container, filling 1-3 MPa hydrogen, heating to 60-100 DEG C, and carrying out reduction reaction for 4-8 hours to obtain the Pt-Co bimetallic nanoparticles. The Pt-Co bimetallic nanoparticles are isolated through a magnetic field action so as to be used as a good catalyst for low-temperature water-phase Fischer-Tropsch synthesis, and the catalytic activity of the catalyst is greatly superior to that of the traditionally synthesized alloyed Pt-Co nanoparticles and the Pt-Co nanoparticles of a core-shell structure.
Description
Technical field
The present invention relates to directly synthetic preparation method with Pt-Co bimetal nano particles of the synthetic performance of good low temperature water Fischer-Tropsch of a kind of water, belong to catalytic field.
Background technology
Fischer-Tropsch is synthetic can be converted into valuable fuels and chemicals with coal, natural gas equal energy source, have consequence more strict today in petroleum resources worsening shortages, Oil products refining, Fischer-Tropsch oil can replenish existing product oil well because of its high-purity high-quality.Its main catalyst metals is Ru, Fe or Co, Co because of its cheap price and high heavy hydrocarbon selectively be widely used in industrial Fischer-Tropsch synthetic in.The tradition Fischer-Tropsch synthetic often need to more than 200 ℃ to reach good activity and selectivity, use 1.0%Re-15%Co-Al as people such as Davis
2O
3For catalyst reacts at 220 ℃, activity is 3.4mol
COMol
Co -1H
-1(Fuel2003,82,805-815).
Because Fischer-Tropsch is synthetic is exothermic process, is feasible so find a new efficient cryogenic process, we have realized that the water Fischer-Tropsch is synthetic thus: the Ru catalyst is made several nanometers and put into water and react, active significantly raising under the low temperature of 150 ℃.The editor of Britain imperial family chemistry meeting speaks highly of this work, is called " cleaning and green ".So we more need at Fe or Co be this realize that the water Fischer-Tropsch is synthetic on can the catalyst of actual industrial.In view of Fe active mutually can not be in water stable existence, Co base water Fischer-Tropsch is synthetic is a problem that is significant.
Rarely have at present the synthetic report of liquid phase Co Fischer-Tropsch, as people such as Dupont, the Co nano particle is scattered in ionic liquid, react at 210 ℃, activity only has 0.04mol
COMol
Co -1H
-1(ChemSusChem2008,1,291-294).As for reacting in water, the synthetic Co nano particle of all methods all exists the activity of low-temp reaction extremely low at present, methane selectively crosses the shortcoming such as high and can't finely use.Consider that Pt is the synthetic auxiliary agent of Co base Fischer-Tropsch, add Pt to be worth attempting in system.And that existing Pt-Co synthesis methods for nanoparticles mostly is oil phase is synthetic, and employing oleic acid/oleyl amine is protective agent, has hindered the metal site and has made it to lose catalytic performance.So the synthetic stable Pt-Co nano particle of water is to realize the synthetic key point of high-performance Co base low temperature water Fischer-Tropsch.
Summary of the invention
The object of the invention is to prepare a kind of directly synthetic at water, can be in water the platinum-cobalt composite nanometer particle of stable existence, make it have the synthetic performance of good Fischer-Tropsch.
Pt-Co bimetal nano particles provided by the present invention is directly synthetic at aqueous phase, and the preparation method comprises the following steps:
1) with platinum precursor salt and hydration acetylacetone cobalt (II) (Co (C
5H
7O
2)
22H
2O, CAS:14024-48-7) be dissolved in the water, add simultaneously polyvinylpyrrolidone (PVP) to mix;
2) with step 1) the gained mixture is placed in airtight container, is filled with 1～3MPa hydrogen, is warming up to 60～100 ℃ of reduction reactions 4～8 hours, obtains the Pt-Co bimetal nano particles.
Above-mentioned steps 1) in, described platinum precursor salt is generally water miscible platinum salt, such as being selected from one or more in following compounds: platinous chloride, platinic sodium chloride, potassium chloroplatinate, chlorine Abel acid sodium, potassium chloroplatinite etc.Hydration acetylacetone cobalt (II) is cobalt precursors salt.Wherein, the amount ratio of platinum precursor salt and cobalt precursors salt is counted by the amount of substance of platinum and cobalt: platinum: cobalt=3～20: 100, be preferably 5～10: 100.
Step 1) PVP that adds in makes platinum-cobalt nanometer particle stable existence in water as protective agent.The consumption of PVP is pressed monomer whose molecular weight (～111gmol
-1) conversion, for the amount of substance of metal (platinum and cobalt) 5～20 times are preferably 8～10 times.
The inventive method adopts hydration diacetyl acetone cobalt (II) as cobalt precursors salt, it can be slightly soluble in water, and acetylacetone,2,4-pentanedione can generate pentanediol by hydrogenation under the catalytic action of platinum, thereby no longer cobalt is carried out chelating, and then cobalt is restored from precursor salt, obtain at last platinum-cobalt nanometer particle.
Step 2) the Pt-Co bimetal nano particles that obtains has good magnetic, easily carries out Magnetic Isolation, and under magnetic fields, supernatant liquid is clear liquid, does not have platinum residual.
In the Pt-Co bimetal nano particles of the inventive method preparation, platinum: the ratio of the amount of substance of cobalt is 3～20: 100, is preferably 5～10: 100.The particle diameter of particle is at 2.0～5.5nm.
The Pt-Co bimetal nano particles of the present invention's preparation can be used as the synthetic good catalyst of low temperature (130～180 ℃) water Fischer-Tropsch.For example: in example of the present invention, synthesized the 10at%Pt-Co nano particle according to described method, average grain diameter is 3.4 ± 0.5nm, then utilizes this nano particle as catalyst, in closed system, with CO: H
2=1: 2 (mol ratios) are synthesis gas, and initial pressure is 3MPa, react under 160 ℃ to pressure drop be 2.0MPa, recording the CO activity of conversion is 1.1mol
COMol
Co -1H
-1, C
5+Selective is 70wt%, and methane selectively is 10wt%, CO
2Seldom.At C
2+In product, alkene account for all products near half.And this catalyst circulation is functional, and the activity of 5 secondary responses does not obviously descend,
After reaction, the average grain diameter of 10at%Pt-Co nano particle is 3.5 ± 0.5nm.
The building-up process of Pt-Co bimetal nano particles of the present invention as shown in Figure 1, platinum is synchronizeed reduction under hydrogen atmosphere with cobalt, therefore nano particle has unique " the cobalt individual layer of growing on platinum particles " and reach " cobalt nanometer particle that monatomic platinum is inlayed " structure (referring to Fig. 3), makes its catalytic activity greatly be better than alloying Pt-Co nano particle that tradition synthesizes and the Pt-Co nano particle of nucleocapsid structure.
Technical advantage of the present invention is:
1, designed with the thinking of another kind of metal as catalyst base metal reduction preparation nano particle, made cobalt precursors to obtain platinum-cobalt nanometer particle with hydrogen reducing under the low temperature of 60 ℃.This particle has the structures such as " the cobalt individual layer of growing on platinum particles ", " the Co nano particle that monatomic Pt inlays ".
2, developed the synthetic good catalyst of a kind of water Fischer-Tropsch, its under 160 ℃ of conditions active with support active comparable under 200-220 ℃ of Co catalyst; Heavy hydrocarbon is selectively fine simultaneously, C
5+Alkene alkane occupy more than 70% of product, alkene accounts for half of product.
So the present invention is with a wide range of applications from the synthetic angle of nano particle or catalyst angle.
Description of drawings
Fig. 1 is the synthetic schematic diagram of Pt-Co nano particle of the present invention.
Fig. 2 is electromicroscopic photograph and the particle diameter distribution map of the synthetic 10at%Pt-Co nano particle of embodiment 2, measure with high-resolution-ration transmission electric-lens Tecnai F-30 field emission microscope, a) being wherein the nano particle of observing under low contrast, is b) nano particle of observing under high-contrast.
Fig. 3 has shown the concrete structure of the 10at%Pt-Co nano particle that embodiment 2 is synthetic, measures with NionUltra STEM-100 scanning transmission electron microscope, and high square ring is swept dark field mode.Wherein: a) show the Co nano particle that monatomic Pt inlays (the small circle indication be monatomic Pt, larger circle indication be the Co nano particle); B) show the Co individual layer of growing on the Pt nano particle (in great circle than the small circle indication be the Pt nano particle, outer field great circle indication be the Co individual layer).
The specific embodiment
The present invention is described further below by embodiment, but the scope that does not limit the present invention in any way.
Synthesizing of embodiment 15%Pt-Co nano particle
With platinum precursor salt potassium chloroplatinite 0.042g and cobalt precursors salt hydration acetylacetone cobalt (II) 0.586g, be dissolved in 40mL water, add simultaneously 2.2g PVP.Mixture is transferred in stainless steel cauldron excellent sealing.Then be filled with 2MPa hydrogen in reactor, stir rapidly afterwards and be warming up to 60 ℃, reduced 4 hours.Obtain the Pt-Co bimetal nano particles by Magnetic Isolation.
Synthesizing of embodiment 210%Pt-Co nano particle
With platinum precursor salt potassium chloroplatinite 0.084g and cobalt precursors salt hydration acetylacetone cobalt (II) 0.586g, be dissolved in 40mL water, add simultaneously 2.2g PVP.Mixture is transferred in stainless steel cauldron excellent sealing.Then be filled with 2MPa hydrogen in reactor, stir rapidly afterwards and be warming up to 60 ℃, reduced 4 hours.Obtain the Pt-Co bimetal nano particles by Magnetic Isolation.
The particle diameter of the 10%Pt-Co nano particle that is synthesized distributes as shown in Figure 2, and average grain diameter is 3.4 ± 0.5nm.There is " the cobalt individual layer of growing on platinum particles " and " the Co nano particle that monatomic Pt inlays " structure in the concrete structure of this 10%Pt-Co nano particle as shown in Figure 3.
Synthesizing of Comparative Examples 1Co-NaBH4 nano particle
The synthetic method of Co-NaBH4 nano particle in contrast is as follows: with hydration cobalt acetate (II) (Co (OAc)
24H
2O) 0.50g and PVP2.2g mixed dissolution in water 40mL, add sodium borohydride (NaBH4) solid 0.40g, and follow abundant stirring.Synthetic nano particle is separated, washes twice by a permanent magnet.Subsequently, nano particle is transferred to and is used for carrying out the water Fischer-Tropsch synthesis in the water 40mL that contains PVP2.2g.
Its synthetic method is referring to document ZhipengCai, Hang Wang, Chaoxian Xiao, MengqiZhong, Ding Ma, Yuan Kou, J.Mol.Catal.A:Chem.2010,330,94-98.
Synthesizing of Comparative Examples 210%Pt-Co-NaBH4 nano particle
The synthetic method of 10%Pt-Co-NaBH4 nano particle in contrast is as follows: with hydration cobalt acetate (II) (Co (OAc)
24H
2O) 0.50g, potassium chloroplatinite 0.084g and PVP2.2g mixed dissolution in water 40mL, add sodium borohydride (NaBH4) solid 0.40g, and follow abundant stirring.Synthetic nano particle is separated, washes twice by a permanent magnet.Subsequently, nano particle is transferred to and is used for carrying out the water Fischer-Tropsch synthesis in the water 40mL that contains PVP2.2g.
The nano particle of above-mentioned preparation is carried out the water Fischer-Tropsch synthesis as catalyst, and reaction condition is: the closed system reaction, synthesis gas is CO: H
2=1: 2, initial pressure is 3.0MPa, and reaction temperature is 160 ℃, stops reaction during to 2.0MPa until pressure drop.
The reactivity worth of each catalyst is as shown in following table 1.Can find out, the present invention aqueous phase directly synthetic Pt-Co bimetal nano particles (numbering 3 and 4) the catalytic activity under 160 ℃ of conditions can with support 200-220 ℃ of Co catalyst under activity compare, be much higher than the activity of existing catalyst (numbering 5 and 6) under 160 ℃ of conditions; Simultaneously, the heavy hydrocarbon of catalyst of the present invention is selectively fine, and the alkene alkane of C5+ occupies more than 70% of product, C
2+Hydrocarbon product in alkene occupy half.
Synthetic (160 ℃) reactivity worth of the water Fischer-Tropsch of table 1.Pt-Co nano-particle catalyst and other catalyst relatively
Claims (10)
1. one kind is directly synthesized the method for Pt-Co bimetal nano particles at aqueous phase, comprises the following steps:
1) platinum precursor salt and hydration acetylacetone cobalt (II) are dissolved in the water, add simultaneously polyvinylpyrrolidone to mix;
2) with step 1) the gained mixture is placed in airtight container, is filled with 1～3MPa hydrogen, is warming up to 60～100 ℃ of reduction reactions 4～8 hours, obtains the Pt-Co bimetal nano particles.
2. the method for claim 1, is characterized in that, in step 2) reaction separates the Pt-Co bimetal nano particles by magnetic fields after completing.
3. the method for claim 1, is characterized in that step 1) described in the platinum precursor salt be selected from one or more in following compounds: platinous chloride, platinic sodium chloride, potassium chloroplatinate, chlorine Abel acid sodium and potassium chloroplatinite.
4. the method for claim 1, is characterized in that step 1) described in the amount ratio of platinum precursor salt and hydration acetylacetone cobalt (II) count by the amount of substance of platinum and cobalt: platinum: cobalt=3～20: 100.
5. the method for claim 1, is characterized in that step 1) described in the consumption of polyvinylpyrrolidone be 111gmol by the monomer whose molecular weight
-1Conversion is 5～20 times of the amount of substance of platinum and cobalt.
6. a Pt-Co bimetal nano particles, be that according to claim 1～5, arbitrary described method directly synthesizes at aqueous phase the nano particle that obtains.
7. Pt-Co bimetal nano particles as claimed in claim 6, is characterized in that, platinum in described Pt-Co bimetal nano particles: the ratio of the amount of substance of cobalt is 3～20: 100.
8. Pt-Co bimetal nano particles as claimed in claim 6, is characterized in that, the particle diameter of described Pt-Co bimetal nano particles is at 2.0～5.5nm.
9. the described Pt-Co bimetal nano particles of claim 6 is as the purposes of the synthetic catalyst of water Fischer-Tropsch.
10. purposes as claimed in claim 9, is characterized in that, the synthetic reaction temperature of described water Fischer-Tropsch is 130～180 ℃.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013185559A1 (en) * | 2012-06-15 | 2013-12-19 | 武汉凯迪工程技术研究总院有限公司 | Liquid phase co2 methanation catalyst, preparation method and use thereof |
| CN104415753A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for directly synthesizing bimetallic nano-material |
| CN104493193A (en) * | 2014-11-24 | 2015-04-08 | 北京大学 | Hydro-thermal synthetic method and application of Pt-Ru bimetal nanoparticles |
| CN104551000A (en) * | 2014-12-23 | 2015-04-29 | 国家纳米科学中心 | Platinum-cobalt nano-alloy mimic enzyme and preparing method and purpose thereof |
| CN105044185A (en) * | 2014-12-17 | 2015-11-11 | 吉林师范大学 | Method of biomimetically-synthesizing graphene/gold-silver nano hybrid material through ferritin induction and application thereof |
| CN105234427A (en) * | 2015-11-04 | 2016-01-13 | 中国科学院上海高等研究院 | Platinum alloy nano core-shell cube and preparation method thereof |
| CN105618034A (en) * | 2014-11-24 | 2016-06-01 | 北京大学 | Supported ruthenium nanocluster based catalyst as well as preparation and application thereof |
| CN105887196A (en) * | 2016-04-15 | 2016-08-24 | 中国科学技术大学先进技术研究院 | Pt3Co nanocrystal, catalyst, preparation methods of Pt3Co nanocrystal and catalyst as well as application of catalyst |
| CN106732561A (en) * | 2016-12-31 | 2017-05-31 | 武汉理工大学 | A kind of mesoporous platinum palladium bimetal nano particles and preparation method thereof |
| CN106807365A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of preparation method of core shell structure elctro-catalyst |
| CN109128139A (en) * | 2018-09-17 | 2019-01-04 | 温州大学 | A kind of synthesis technology that Pt-Co cubic block is nanocrystalline |
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Non-Patent Citations (1)
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Cited By (11)
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| WO2013185559A1 (en) * | 2012-06-15 | 2013-12-19 | 武汉凯迪工程技术研究总院有限公司 | Liquid phase co2 methanation catalyst, preparation method and use thereof |
| CN104415753A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for directly synthesizing bimetallic nano-material |
| CN104493193A (en) * | 2014-11-24 | 2015-04-08 | 北京大学 | Hydro-thermal synthetic method and application of Pt-Ru bimetal nanoparticles |
| CN105618034A (en) * | 2014-11-24 | 2016-06-01 | 北京大学 | Supported ruthenium nanocluster based catalyst as well as preparation and application thereof |
| CN105044185A (en) * | 2014-12-17 | 2015-11-11 | 吉林师范大学 | Method of biomimetically-synthesizing graphene/gold-silver nano hybrid material through ferritin induction and application thereof |
| CN104551000A (en) * | 2014-12-23 | 2015-04-29 | 国家纳米科学中心 | Platinum-cobalt nano-alloy mimic enzyme and preparing method and purpose thereof |
| CN105234427A (en) * | 2015-11-04 | 2016-01-13 | 中国科学院上海高等研究院 | Platinum alloy nano core-shell cube and preparation method thereof |
| CN106807365A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of preparation method of core shell structure elctro-catalyst |
| CN105887196A (en) * | 2016-04-15 | 2016-08-24 | 中国科学技术大学先进技术研究院 | Pt3Co nanocrystal, catalyst, preparation methods of Pt3Co nanocrystal and catalyst as well as application of catalyst |
| CN106732561A (en) * | 2016-12-31 | 2017-05-31 | 武汉理工大学 | A kind of mesoporous platinum palladium bimetal nano particles and preparation method thereof |
| CN109128139A (en) * | 2018-09-17 | 2019-01-04 | 温州大学 | A kind of synthesis technology that Pt-Co cubic block is nanocrystalline |
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Application publication date: 20130522 |