CN105945298A - Preparation method for hollow palladium nanospheres - Google Patents
Preparation method for hollow palladium nanospheres Download PDFInfo
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- CN105945298A CN105945298A CN201610261081.XA CN201610261081A CN105945298A CN 105945298 A CN105945298 A CN 105945298A CN 201610261081 A CN201610261081 A CN 201610261081A CN 105945298 A CN105945298 A CN 105945298A
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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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- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0549—Hollow particles, including tubes and shells
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
- B22F1/0655—Hollow particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a preparation method for hollow palladium nanospheres. The preparation method comprises the steps that polyethyleneimine serves as a stabilizer, and ascorbic acid serves as a reducing agent; cuprous oxide nanospheres are synthesized at first; and then, the cuprous oxide nanospheres are used as a mold plate, hydrazine hydrate is used as a reducing agent, and potassium tetrachloropalladate or palladium chloride is reduced into the hollow palladium nanospheres which are regular in shape, uniform in size and good in dispersibility and stability through a hydrothermal reduction method. The preparation method for the hollow palladium nanospheres is simple and economical, and the prepared hollow palladium nanospheres show excellent electro-catalysis activity and stability to a formic acid catalytic reaction, have potential application prospects in the direct formic acid fuel cell field and are suitable for industrial large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of Pd nano particle, particularly relate to the preparation of a kind of hollow palladium nanosphere
Method, this Pd nano particle shows higher catalysis activity and stability as catalyst to formic acid.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) with hydrogen as fuel owing to price is high, without suitable hydrogen source and
The problems such as less than 0 DEG C Nafion membrane icing, also fail to commercialization so far.DMFC (DMFC)
Have fuel handling and easy to use, volume is little and specific energy advantages of higher, but methanol is poisonous, volatile, high
Inflammable, and easily cause battery performance to decline through Nafion membrane.Research in recent years finds, formic acid is a kind of
Preferably methanol alternative fuel, direct methanoic acid fuel cell (DFAFC) has lot of advantages, as nontoxic in formic acid,
Nonflammable etc..Owing to Nafion membrane having between sulfonic acid group and formate anion repulsive interaction, therefore, formic acid
Much lower to the permeability ratio methanol of Nafion membrane, DFAFC receives more and more attention.
In DFAFC, formic acid oxidation on palladium catalyst is mainly carried out by direct way, and therefore palladium is urged
Agent is more much better than platinum catalyst to the electro catalytic activity of formic acid oxidation.Therefore palladium catalyst increasingly comes into one's own.
But, owing to palladium reserves are rare, how under the activity and selectivity premise improving palladium-based catalyst, to reduce palladium
Consumption is still the study hotspot in this field.
Show according to previously research: owing to the performance of palladium catalyst is had relatively by particle diameter, pattern and the crystal face of palladium particle
Big impact, therefore, the palladium nanostructured of design pattern and size tunable seems most important.Such as: by { 100}
The small size Pd nano particle that crystal face is constituted to the catalytic performance of formic acid ratio by { 110} and { 111} crystal face is constituted
Pd nano particle is much better.At present, the palladium nanostructured of different-shape, as octahedra in nanometer tetrahedron, nanometer,
Nanosphere, nano wire, nano-hollow ball and nanocube, (include template by different synthetic methods
Method, crystal seed method, chemical reduction method, sol-gel process and thermal decomposition method etc.) prepare.
Summary of the invention
The technical problem to be solved is to provide the preparation of a kind of simple and effective hydrothermal reduction method to have
Uniformly and the method for the controlled hollow palladium nanosphere of pattern, size and composition.
Solve the technical scheme that above-mentioned technical problem used to be made up of following step:
1, Nano balls of cuprous oxide is prepared
It is that 1:1～3:1～1.5 adds steaming in molar ratio by copper chloride or copper sulfate, polymine, ascorbic acid
In distilled water, mix homogeneously, with the pH value of sodium hydrate aqueous solution regulation gained mixed liquor to 10～13, room temperature
Stir 20～30 minutes, obtain Nano balls of cuprous oxide solution.
2, hollow palladium nanosphere is prepared
By the aqueous solution of potassium chloropalladite or Palladous chloride. with 0.5mol/L sodium hydrate aqueous solution regulation pH value extremely
After 10～13, join in Nano balls of cuprous oxide solution, and add hydrazine hydrate, wherein potassium chloropalladite or chlorine
Change palladium, hydrazine hydrate, the mol ratio of Red copper oxide are 1:7～20:1.5～2, at 50～80 DEG C reduction reaction 20～
40 minutes, then it is stirred at room temperature 16～24 hours, is centrifuged, washs, is dried, obtain hollow palladium nanosphere.
In above-mentioned steps 1, preferably copper chloride or copper sulfate, polymine, the mol ratio of ascorbic acid is
1:2:1.2, the number-average molecular weight of wherein said polymine is 300～1200.
In above-mentioned steps 2, preferably potassium chloropalladite or Palladous chloride., hydrazine hydrate, the mol ratio of Red copper oxide is
1:10:1.85。
In above-mentioned steps 2, further preferably reduction reaction 30 minutes at 60 DEG C.
Beneficial effects of the present invention is as follows:
1, the present invention uses a small amount of polymine (PEI) to be stabilizer and guiding agent, in preparation oxidation Asia
During copper nanosphere, PEI is as the stabilizer of copper chloride, the N therein and Cu in copper chloride2+Complexation,
Make copper chloride gentleer with the speed of ascorbic acid generation reduction reaction, thus obtain size and morphology controllable
Nano balls of cuprous oxide, the PEI Molecular Adsorption of excess is on the surface of Nano balls of cuprous oxide；Preparing hollow palladium
During nanosphere, adsorb the PEI on Nano balls of cuprous oxide surface as palladium in Red copper oxide superficial growth
Guiding agent, make palladium be easier to be grown in Nano balls of cuprous oxide surface, adsorb at Nano balls of cuprous oxide simultaneously
The PEI on surface is again as Cu2+Stabilizer, make Red copper oxide be easy to by the dioxygen oxidation in air.
2, the present invention is with Nano balls of cuprous oxide as template, with sodium chloropalladite for palladium presoma, Pd2+In absorption
Under the guiding of the PEI on Nano balls of cuprous oxide surface, oriented growth is on Nano balls of cuprous oxide surface, then exists
The lower Red copper oxide of the effect of PEI is become Cu by the dioxygen oxidation in air2+Ion, Cu2+Ion is by washing i.e.
Can remove, finally give the hollow palladium nanosphere of pattern, size uniformity.
3, the present invention need not high temperature, it is not necessary to the longer response time, it is not necessary to complicated pH regulation process,
Simple to operate, product yield is high and homogeneity is good, is suitable for large-scale production.
4, hollow palladium nanosphere prepared by the present invention is compared with commercialization palladium black, shows excellent to Catalyzed by Formic Acid reaction
Different electro catalytic activity and stability, have potential application prospect in direct methanoic acid fuel cell field.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the hollow palladium nanosphere of embodiment 1 preparation.
Fig. 2 is the TEM figure of the hollow palladium nanosphere of embodiment 1 preparation.
Fig. 3 is the TEM figure of the hollow palladium nanosphere of embodiment 2 preparation.
Fig. 4 is the TEM figure of the hollow palladium nanosphere of embodiment 3 preparation.
Fig. 5 is the TEM figure of the hollow palladium nanosphere of embodiment 4 preparation.
Fig. 6 is the TEM figure of the hollow palladium nanosphere of embodiment 5 preparation.
Fig. 7 is the TEM figure of the hollow palladium nanosphere of embodiment 6 preparation.
Fig. 8 is the TEM figure of the hollow palladium nanosphere of embodiment 7 preparation.
Detailed description of the invention
The present invention is described in more detail with embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is not only
It is limited to these embodiments.
Embodiment 1
1, Nano balls of cuprous oxide is prepared
Take the CuCl of 1mL 0.05mol/L2Aqueous solution, 0.2mL 0.5mol/L number-average molecular weight are the poly-second of 600
Alkene imines aqueous solution, the aqueous ascorbic acid of 0.6mL 0.1mol/L add 10mL distilled water, stir mixing 3
After minute, with the pH value of the sodium hydrate aqueous solution regulation gained mixed liquor of 0.5mol/L to 11.5, room temperature is stirred
Mix 20 minutes, obtain Nano balls of cuprous oxide solution.
2, hollow palladium nanosphere is prepared
The potassium chloropalladite aqueous solution of 0.45mL 0.06mol/L 0.5mol/L sodium hydrate aqueous solution is regulated
PH value, to after 11.5, joins in the Nano balls of cuprous oxide solution that step 1 obtains, and adds 15.5 μ L matter
Amount mark is the hydrazine hydrate aqueous solution of 80%, heating in water bath to 60 DEG C, constant temperature reduction reaction 30 minutes, then
Be stirred at room temperature 24 hours, washing centrifugal with distilled water, 60 DEG C be dried, obtain hollow palladium nanosphere (see Fig. 1
With 2).
Embodiment 2
In embodiment 1, copper chloride used is replaced with equimolar copper sulfate, potassium chloropalladite equimolar
Palladous chloride. replace, other steps are same as in Example 1, obtain hollow palladium nanosphere (see Fig. 3).
Embodiment 3
In embodiment 1,0.2mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine use of 600
0.1mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine replacement of 600, other steps and embodiment 1
Identical, obtain hollow palladium nanosphere (see Fig. 4).
Embodiment 4
In embodiment 1,0.2mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine use of 600
0.3mL 0.5mol/L number-average molecular weight is the aq. polyethyleneimine replacement of 600, other steps and embodiment 1
Identical, obtain hollow palladium nanosphere (see Fig. 5).
Embodiment 5
In embodiment 1,15.5 μ L mass fractions are that the hydrazine hydrate aqueous solution of 80% is with 30 μ L mass fractions
The hydrazine hydrate aqueous solution of 80% is replaced, and other steps are same as in Example 1, obtain hollow palladium nanosphere (see Fig. 6).
Embodiment 6
In the step 1 and 2 of embodiment 1, with 0.5mol/L sodium hydrate aqueous solution regulation pH value to 13,
Other steps are same as in Example 1, obtain hollow palladium nanosphere (see Fig. 7).
Embodiment 7
In the step 2 of embodiment 1, heating in water bath to 80 DEG C, constant temperature reduction reaction 20 minutes, other steps
The most same as in Example 1, obtain hollow palladium nanosphere (see Fig. 8).
Claims (5)
1. the preparation method of a hollow palladium nanosphere, it is characterised in that it is made up of following step:
(1) Nano balls of cuprous oxide is prepared
It is that 1:1～3:1～1.5 adds steaming in molar ratio by copper chloride or copper sulfate, polymine, ascorbic acid
In distilled water, mix homogeneously, with the pH value of sodium hydrate aqueous solution regulation gained mixed liquor to 10～13, room temperature
Stir 20～30 minutes, obtain Nano balls of cuprous oxide solution；
(2) hollow palladium nanosphere is prepared
By the aqueous solution of potassium chloropalladite or Palladous chloride. with 0.5mol/L sodium hydrate aqueous solution regulation pH value extremely
After 10～13, join in Nano balls of cuprous oxide solution, and add hydrazine hydrate, wherein potassium chloropalladite or chlorine
Change palladium, hydrazine hydrate, the mol ratio of Red copper oxide are 1:7～20:1.5～2, at 50～80 DEG C reduction reaction 20～
40 minutes, then it is stirred at room temperature 16～24 hours, is centrifuged, washs, is dried, obtain hollow palladium nanosphere.
The preparation method of hollow palladium nanosphere the most according to claim 1, it is characterised in that: in step (1)
In, described copper chloride or copper sulfate, polymine, the mol ratio of ascorbic acid are 1:2:1.2.
The preparation method of hollow palladium nanosphere the most according to claim 1 and 2, it is characterised in that: described
The number-average molecular weight of polymine be 300～1200.
The preparation method of hollow palladium nanosphere the most according to claim 1, it is characterised in that: in step (2)
In, described potassium chloropalladite or Palladous chloride., hydrazine hydrate, the mol ratio of Red copper oxide are 1:10:1.85.
5. according to the preparation method of the hollow palladium nanosphere described in claim 1 or 4, it is characterised in that: described
In step (2), reduction reaction 30 minutes at 60 DEG C.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824084A (en) * | 2017-03-15 | 2017-06-13 | 天津大学 | The preparation method of the carbon-supported catalyst of a kind of nano cuprous oxide/copper modification and except iodine application |
| CN107470649A (en) * | 2017-08-01 | 2017-12-15 | 江苏理工学院 | A kind of preparation method of tetrahedral CuCl/Pt alloys |
| CN107520462A (en) * | 2017-08-01 | 2017-12-29 | 江苏理工学院 | A kind of preparation method of tetrahedral CuCl/Au alloys |
| CN110676473A (en) * | 2019-10-10 | 2020-01-10 | 陕西师范大学 | Preparation method of multi-stage porous Rh nanosheet |
| CN110976906A (en) * | 2019-12-04 | 2020-04-10 | 山西大学 | Fluorescent palladium nanocluster and synthesis method and application thereof |
| CN111687427A (en) * | 2019-03-15 | 2020-09-22 | 华中农业大学 | Hollow palladium nanotube with two open ends, preparation method and application thereof |
| CN115960367A (en) * | 2022-12-26 | 2023-04-14 | 浙江科曼奇生物科技股份有限公司 | Preparation method and application of quaternized polyethyleneimine zinc oxide or cuprous oxide particles |
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| US20050056118A1 (en) * | 2002-12-09 | 2005-03-17 | Younan Xia | Methods of nanostructure formation and shape selection |
| CN102036773A (en) * | 2008-03-19 | 2011-04-27 | 巴斯夫欧洲公司 | Metallic nanoparticles stabilised with derivatisied polyethylenimines or polyvinylamines |
| CN104722775A (en) * | 2015-03-11 | 2015-06-24 | 浙江大学 | Two-dimensional hollow palladium nanocrystal and preparation method thereof |
| CN105013476A (en) * | 2015-06-26 | 2015-11-04 | 陕西师范大学 | Preparation method of chemically functionalized Pd nano-wires |
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2016
- 2016-04-25 CN CN201610261081.XA patent/CN105945298B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050056118A1 (en) * | 2002-12-09 | 2005-03-17 | Younan Xia | Methods of nanostructure formation and shape selection |
| CN102036773A (en) * | 2008-03-19 | 2011-04-27 | 巴斯夫欧洲公司 | Metallic nanoparticles stabilised with derivatisied polyethylenimines or polyvinylamines |
| CN104722775A (en) * | 2015-03-11 | 2015-06-24 | 浙江大学 | Two-dimensional hollow palladium nanocrystal and preparation method thereof |
| CN105013476A (en) * | 2015-06-26 | 2015-11-04 | 陕西师范大学 | Preparation method of chemically functionalized Pd nano-wires |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824084A (en) * | 2017-03-15 | 2017-06-13 | 天津大学 | The preparation method of the carbon-supported catalyst of a kind of nano cuprous oxide/copper modification and except iodine application |
| CN107470649A (en) * | 2017-08-01 | 2017-12-15 | 江苏理工学院 | A kind of preparation method of tetrahedral CuCl/Pt alloys |
| CN107520462A (en) * | 2017-08-01 | 2017-12-29 | 江苏理工学院 | A kind of preparation method of tetrahedral CuCl/Au alloys |
| CN111687427A (en) * | 2019-03-15 | 2020-09-22 | 华中农业大学 | Hollow palladium nanotube with two open ends, preparation method and application thereof |
| CN110676473A (en) * | 2019-10-10 | 2020-01-10 | 陕西师范大学 | Preparation method of multi-stage porous Rh nanosheet |
| CN110676473B (en) * | 2019-10-10 | 2022-04-15 | 陕西师范大学 | Preparation method of multi-stage porous Rh nanosheet |
| CN110976906A (en) * | 2019-12-04 | 2020-04-10 | 山西大学 | Fluorescent palladium nanocluster and synthesis method and application thereof |
| CN115960367A (en) * | 2022-12-26 | 2023-04-14 | 浙江科曼奇生物科技股份有限公司 | Preparation method and application of quaternized polyethyleneimine zinc oxide or cuprous oxide particles |
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