CN107745134B - A kind of polygonal pattern PtCoFe alloy nanoparticle and preparation method thereof - Google Patents
A kind of polygonal pattern PtCoFe alloy nanoparticle and preparation method thereof Download PDFInfo
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- CN107745134B CN107745134B CN201710990624.6A CN201710990624A CN107745134B CN 107745134 B CN107745134 B CN 107745134B CN 201710990624 A CN201710990624 A CN 201710990624A CN 107745134 B CN107745134 B CN 107745134B
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Abstract
The present invention relates to a kind of polygonal PtCoFe alloy nanoparticles and preparation method thereof.The present invention is with chloroplatinic acid; cobalt chloride and ferric trichloride are that using PVP as reducing agent and protective agent the CTAB and NaBr of certain content is added in raw material; the higher polygonal pattern PtCoFe alloy nano particle of selectivity, the cleaning of preparation method green are prepared under hydrogen reducing atmosphere.The polygonal PtCoFe alloy nano particle step atom obtained is more, and active site density is high, is with a wide range of applications.
Description
Technical field
The invention belongs to function nano alloy fields.Specifically, the present invention is that prepare one kind more using hydrothermal synthesis method
Angular looks PtCoFe alloy nano particle.
Background technique
Precious metals pt nano-structured calalyst is widely used in industry due to its excellent catalytic performance and thermal stability
Catalysis, bionic, the fields such as electro-catalysis.But due to some restraining factors in practical applications, such as easily poisoning, the service life it is short with
And it is at high price, so that this excellent nanocatalyst can not further genralrlization and application.Research worker is in order to solve this
A little problems substitute Pt frequently with by cheap 3d transition metal element part at present, form Pt base binary/multicomponent alloy and urge
Agent, and controlled by condition, probe into its pattern, the relationship of composition and stable in catalytic performance.
In numerous transition metal elements, Co and Fe respectively as one of transition metal element more abundant on the earth,
It is that Pt base bianry alloy preferably selects.The report for preparing PtCoFe alloy nanoparticle submethod at present is less, and these methods
It is all organic solvent macromolecular as solvent, most of PtCoFe alloy nano particle being synthesized is wrapped up by organic matter, living
Property position cannot expose, and can not be in contact with reactant.Therefore it designs and exploitation aqueous solution preparation PtCoFe alloy nano particle has
There is important meaning.A kind of method for preparing polygonal PtCoFe alloy nano particle that the present invention develops, substantially increases Pt's
Step atomicity increases the active site density of PtCoFe alloy.
Fuel cell is considered as the important power device of traditional internal combustion engine alternative in the near future.Proton exchange
Another important feature of membrane cell is that it both can be using clean energy resource such as hydrogen etc. as fuel, also can be with reproducible small
Molecular organic such as formic acid, ethyl alcohol, methanol etc. is fuel.According to before studies have shown that Pt catalyst is proton exchange membrane combustion
Expect the best catalyst of catalytic performance in battery, but the high cost and utilization rate of Pt catalyst limits to a certain extent
The application prospect of fuel cell, therefore prepare to be used to improve the catalyst for improving electrocatalysis characteristic and have become and be currently urgently badly in need of solving
Certainly the problem of.
Summary of the invention
In view of the above technical problems, the present invention solves current Pt nano-structured calalyst and there is easily poisoning, the service life it is short with
And the technical problems such as at high price, a kind of polygonal pattern PtCoFe alloy nano particle of high density active position is prepared, Pt is improved
The performance of nano-structured calalyst.
To achieve the above object, the present invention is achieved by the following technical solutions:
A kind of experimental procedure of polygonal PtCoFe alloy nano particle preparation method is as follows:
It measures 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration is the cobalt chloride and 3.0mL concentration of 1.66mmol/L
For 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into PVP K30 and hexadecane
Base trimethylammonium bromide CTAB and NaBr, are stirred dissolution with magnetic stirring apparatus, then with empty in hydrogen discharge reaction kettle
After gas, 0.8MPa hydrogen is passed through into reaction kettle, then heating is reacted, after reaction by ethyl alcohol centrifuge washing, cold
The processing steps such as dry are lyophilized, obtain polygonal PtCoFe alloy nano particle.
Preferably, the amount ranges of PVP K30 are 190-230mg, more preferably 210mg.
Preferably, the amount ranges of cetyl trimethylammonium bromide are 60mg.
Wherein: the dosage of NaBr and the dosage of cetyl trimethylammonium bromide are identical, the study found that Na+Ion and Br-
The ratio of the ion guiding role marginal to PtCoFe crystal topology, only when the additional amount of CTAB and NaBr are equal
In the case where for 60mg, polygonal PtCoFe alloy nano particle of the invention can be just obtained, unexpected technical effect is reached.
Preferably, the temperature range for heating reaction is 180-220 DEG C.
Further, it should be noted that the hydrogen atmosphere of 0.8MPa is also the polygonal PtCoFe of the synthesis present invention under primary condition
The essential factor of alloy nano particle, since hydrogen has reproducibility, it is bis- that the present invention constitutes vapor phase hydrogen-liquid phase P VP
Phase reduction system is used to synthesize PtCoFe alloy for the first time, constitutes a mutually matched entirety with other experiment parameters, collaboration exists
Polygonal PtCoFe alloy of the invention can be just obtained together.
Beneficial effects of the present invention: the present invention is with chloroplatinic acid, and cobalt chloride and ferric trichloride are raw material, using PVP as reducing agent
And protective agent is prepared the higher polygonal pattern PtCoFe alloy of selectivity and is received using specific CTAB and NaBr additional amount
Rice corpuscles, the cleaning of method green.The polygonal PtCoFe alloy nano particle step atom obtained is more, and active site density is high, display
Outstanding methanol and formic acid electro-chemical activity, is with a wide range of applications.
Detailed description of the invention
Fig. 1 is the XRD spectrum for the polygonal PtCoFe alloy nano particle that embodiment 1 is prepared；
Fig. 2 is the TEM map for the polygonal PtCoFe alloy nano particle that embodiment 1 is prepared；
Fig. 3 is the polygonal PtCoFe alloy nano particle that embodiment 1 is prepared and business Pt/C as methanol electro-oxidizing
The cyclic voltammetry curve comparison diagram of catalyst；
Fig. 4 is the polygonal PtCoFe alloy nano particle that embodiment 1 is prepared and business Pt/C as formic acid electroxidation
The cyclic voltammetry curve comparison diagram of catalyst；
Fig. 5 is the TEM map for the PtCoFe alloy nano particle that comparative example 1 is prepared；
Fig. 6 is the TEM map for the PtCoFe alloy nano particle that comparative example 2 is prepared.
Specific embodiment
Below by way of the implementation and possessed beneficial effect of specific embodiment the present invention will be described in detail technical solution, but not
It can regard as any restriction to enforceable range of the invention.
Embodiment 1
It measures 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration is the cobalt chloride and 3.0mL concentration of 1.66mmol/L
For 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into PVP K30 and hexadecane
Base trimethylammonium bromide CTAB and NaBr, are stirred dissolution with magnetic stirring apparatus, then with empty in hydrogen discharge reaction kettle
After gas, 0.8MPa hydrogen is passed through into reaction kettle, then heats and is reacted at 200 DEG C, after reaction by ethyl alcohol from
The processing steps such as heart washing, freeze-drying, obtain polygonal PtCoFe alloy nano particle (as shown in Figure 2), wherein polyethylene pyrrole
The amount ranges of pyrrolidone K30 are 210mg, and the amount ranges of cetyl trimethylammonium bromide are 60mg, the dosage of NaBr with
The dosage of cetyl trimethylammonium bromide is identical.
The test of methanol (formic acid) electroxidation: anodic oxidation performance test is using conventional three-electrode system, in CHI650D
It is carried out on type electrochemical workstation.It is a platinum filament to electrode with saturated calomel electrode (SCE) for reference electrode, and the electricity that works
Extremely diameter be 3mm glass-carbon electrode (GC).A certain amount of catalyst suspension (holding metal quality is 4 μ g) is taken to drip to GC electrode
Surface on it is dry under infrared lamp, then having one end of sample against UV ozone lamp working electrode drop, (launch wavelength is
185nm and 254nm, power 10W) it is separated by 5mm irradiation 12h to remove the organic molecule (such as PVP) of sample surfaces.Then exist
Drip the 0.5wt%Nafion solution (ethyl alcohol dilution) of upper 1.5 μ L in the surface of working electrode.The test of catalyst electrochemical activation area
With 0.5M H2SO4Solution first leads to the high-purity N of 30min as electrolyte before experiment2To electrolyte deoxygenation, then with 50mV/s speed
Rate carries out cyclic voltammetric (CV) scanning, and the scanning range of setting is -0.24~1.0V.It is N that superjacent is kept in experimentation2
Atmosphere.The test of methanol (formic acid) electroxidation is in 0.5M H2SO4+2M CH3OH(0.5M H2SO4+ 0.25M HCOOH) electrolyte
Middle progress leads to high-purity N before CV test2Purging 30min is used to remove dissolved oxygen in electrolyte, the scanning range set as-
0.2~1.0V determines that scanning speed is 50mV/s.Current density is with unit catalyst electrochemical activation area on working electrode
(cm2) on electric current indicate.It is bent that each working electrode encloses obtained stable CV with the rate loop scan process 50 of 50mV/s
Line.Prepared by polygonal PtCoFe nanoparticle for embodiment 1, its electricity just sweeping peak and being normalized on electrochemical surface area ECSA
Current density represents the size of the latent active of catalyst, from figs. 3 and 4 it can be seen that polygonal PtCoFe nanoparticle is in first
Highest current density in alcohol electroxidation is 3.52mA cm-2Highest current density in the experiment of formic acid electroxidation is 1.02mA
cm-2, the methanol highest current density much higher than commercial Pt/C is 0.47mA cm-2, formic acid highest current density is 0.24mA cm-2。
Comparative example 1
It measures 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration is the cobalt chloride and 3.0mL concentration of 1.66mmol/L
For 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into PVP K30 and hexadecane
Base trimethylammonium bromide CTAB and NaBr, are stirred dissolution with magnetic stirring apparatus, then with empty in hydrogen discharge reaction kettle
After gas, 0.8MPa hydrogen is passed through into reaction kettle, then heats and is reacted at 200 DEG C, after reaction by ethyl alcohol from
The processing steps such as heart washing, freeze-drying, wherein the amount ranges of PVP K30 are 210mg, cetyl three
The amount ranges of methyl bromide ammonium are 60mg, and the dosage of NaBr is 70mg, obtain PtCoFe alloy nano particle (such as Fig. 5 institute
Show), and test condition same as Example 1 is used, obtaining its highest current density in methanol electro-oxidizing is 1.86mA
cm-2, the highest current density in the experiment of formic acid electroxidation is 0.38mA cm-2。
Comparative example 2
It measures 1.0mL chloroplatinic acid (19.3mmol/L), 4.0mL concentration is the cobalt chloride and 3.0mL concentration of 1.66mmol/L
For 1.66mmol/L ferric chloride aqueous solutions in 30ml reaction kettle, be subsequently added into PVP K30 and hexadecane
Base trimethylammonium bromide CTAB and NaBr, are stirred dissolution with magnetic stirring apparatus, 0.8MPa are then passed through into reaction kettle
Then air is heated at 200 DEG C and is reacted, pass through the processing steps such as ethyl alcohol centrifuge washing, freeze-drying after reaction,
Wherein, the amount ranges of PVP K30 are 210mg, and the amount ranges of cetyl trimethylammonium bromide are 60mg,
The dosage of NaBr is 70mg, is obtained PtCoFe alloy nano particle (as shown in Figure 6), and uses test same as Example 1
Condition, obtaining its highest current density in methanol electro-oxidizing is 1.41mA cm-2, formic acid electroxidation experiment in highest
Current density is 0.32mA cm-2。
Moreover, it relates to arrive multiple groups comparative example, it will not enumerate in view of length, be respectively relative to embodiment 1
Change one or more parametric variables, cannot get this hair in the case where changing one or more variable as the result is shown
Bright polygonal pattern PtCoFe alloy nano particle, showing has collaboration between each technical characteristic of the technical solution of the application
Effect, and methanol electro-oxidizing-catalyzing activity is respectively less than 2.0mA cm-2, formic acid electro-oxidizing-catalyzing activity is respectively less than 0.5mA cm-2,
Far below the catalytic activity of the embodiment of the present invention 1, show the technical solution of the application no matter from alloy pattern or catalytic activity
For reached unexpected technical effect.
Claims (4)
1. a kind of polygonal pattern PtCoFe alloy nanoparticle preparation method, specific steps are as follows:
Measure 1.0mL concentration be 19.3mmol/L chloroplatinic acid aqueous solution, 4.0mL concentration be 1.66mmol/L cobalt chloride and
3.0mL concentration is the ferric chloride aqueous solutions of 1.66mmol/L in 30ml reaction kettle, is subsequently added into 190-230mg polyethylene pyrrole
Pyrrolidone K30 and 60mg cetyl trimethylammonium bromide CTAB and 60mg NaBr, is stirred molten with magnetic stirring apparatus
Solution is passed through 0.8MPa hydrogen into reaction kettle, then heating is reacted, instead then with after air in hydrogen discharge reaction kettle
Pass through ethyl alcohol centrifuge washing, freeze-drying process step after answering, obtains polygonal PtCoFe alloy nanoparticle.
2. a kind of polygonal pattern PtCoFe alloy nanoparticle preparation method according to claim 1, it is characterised in that: poly-
The amount ranges 210mg of vinylpyrrolidone K30.
3. a kind of polygonal pattern PtCoFe alloy nanoparticle preparation method according to claim 1 or 2, feature exist
In: the temperature range that heating is reacted is 180-220 DEG C.
4. a kind of polygonal PtCoFe alloy nanoparticle, it is characterised in that one kind according to any one of claim 1-3
Polygonal pattern PtCoFe alloy nanoparticle preparation method obtains.
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| CN108786845A (en) * | 2018-06-27 | 2018-11-13 | 济南大学 | A kind of preparation method of dendroid Pt-Ni-Cu alloy nanoparticles |
| CN110048133A (en) * | 2019-04-29 | 2019-07-23 | 济南大学 | A kind of preparation method of cross cube Pt-Cu-Mn alloy nanoparticle |
| CN110048132A (en) * | 2019-04-29 | 2019-07-23 | 济南大学 | A kind of three-dimensional preparation method for propping up forked Pt-Cu-Mn alloy nanoparticle |
| CN110364744A (en) * | 2019-07-23 | 2019-10-22 | 济南大学 | A kind of preparation method of the extra small Pt-Ni-Cu alloy nanoparticle with high miller index surface |
| CN110534756A (en) * | 2019-09-09 | 2019-12-03 | 济南大学 | A kind of preparation method optimizing porous complicated and confused shape Pt-Ru-Ni alloy nanoparticle performance |
| CN111230142A (en) * | 2020-03-08 | 2020-06-05 | 张雪原 | Snowflake-shaped Au nano particle and preparation method thereof |
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| US20120264598A1 (en) * | 2011-04-12 | 2012-10-18 | GM Global Technology Operations LLC | Synthesis of platinum-alloy nanoparticles and supported catalysts including the same |
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