CN105945298B - A kind of preparation method of hollow palladium nanosphere - Google Patents

A kind of preparation method of hollow palladium nanosphere Download PDF

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Publication number
CN105945298B
CN105945298B CN201610261081.XA CN201610261081A CN105945298B CN 105945298 B CN105945298 B CN 105945298B CN 201610261081 A CN201610261081 A CN 201610261081A CN 105945298 B CN105945298 B CN 105945298B
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palladium
hollow
nanosphere
preparation
cuprous oxide
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CN105945298A (en
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陈煜�
汉术和
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Shaanxi Normal University
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Shaanxi Normal University
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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
    • 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
    • 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
    • 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
    • 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 kind of preparation method of hollow palladium nanosphere, this method is reducing agent by stabilizer, ascorbic acid of polyethyleneimine, first synthesizing Nano balls of cuprous oxide, it is again reducing agent by template, hydrazine hydrate of Nano balls of cuprous oxide, potassium chloropalladite or palladium bichloride is reduced into by regular shape, size uniformity, dispersiveness and the hollow palladium nanosphere having good stability using hydrothermal reduction method.Preparation method of the present invention is simple, economical, and obtained hollow palladium nanosphere shows excellent electro catalytic activity and stability to Catalyzed by Formic Acid reaction, has potential application prospect in direct methanoic acid fuel cell field, is adapted to industrialization large-scale production.

Description

A kind of preparation method of hollow palladium nanosphere
Technical field
The present invention relates to a kind of preparation method of Pd nano particle, more particularly to a kind of preparation side of hollow palladium nanosphere Method, the Pd nano particle show higher catalytic activity and stability as catalyst to formic acid.
Background technology
Using hydrogen as fuel Proton Exchange Membrane Fuel Cells (PEMFC) due to price is high, without suitable hydrogen source and below 0 DEG C The problems such as Nafion membrane freezes, also fail to be commercialized (Design of active Pt on TiO2 based so far nanofibrous cathode for superior PEMFC performance and durability at high temperature.Applied Catalysis B:Environmental,2017；204:421-429).Direct methanol fuel Battery (DMFC) has the advantages that fuel handling and easy to use, small volume and higher than energy, but methanol is poisonous, volatile, high It is inflammable, and easily cause battery performance to decline through Nafion membrane.Research in recent years finds that formic acid is a kind of preferable methanol Alternative fuel, direct methanoic acid fuel cell (DFAFC) have a lot of advantages, and such as formic acid is nontoxic, nonflammable (Influence of solution pH on Pt anode catalyst in direct formic acid fuel cells.ACS Catalysis,2015；5:6848-6851).Due to having repulsive interaction between sulfonic acid group and formate anion in Nafion membrane, Therefore, formic acid is much lower to the permeability ratio methanol of Nafion membrane, and DFAFC has received more and more attention (Carbon supported Pd-based bimetallic and trimetallic catalyst for formic acid electrochemical oxidation.Applied Catalysis B:Environnebtal,2016；180:758- 765)。
In DFAFC, oxidation of the formic acid on palladium catalyst is mainly carried out by direct way, therefore palladium catalyst is to first The electro catalytic activity of acid oxidase is more much better than platinum catalyst.(the Pd-Cu alloy with therefore palladium catalyst is increasingly taken seriously hierarchical network structure as enhanced electrocatalysts for formic acid oxidation.International Journal of Hydrogen Energy,2016；41:6773-6780).However, by Rare in palladium reserves, it is still the field that the dosage of palladium how is reduced under the premise of the activity and selectivity of palladium-based catalyst is improved Study hotspot.
Shown according to previous research：Due to the particle diameter, pattern and crystal face of palladium particle have to the performance of palladium catalyst it is larger Influence, therefore, the palladium nanostructured for designing pattern and size tunable seems most important.Such as：It is made up of { 100 } crystal face small Size Pd nano particle is more much better than the Pd nano particle being made up of { 110 } and { 111 } crystal face to the catalytic performance of formic acid (Multi-Generation Overgrowth Induced Synthesis of Three-Dimensional Highly Branched Palladium Tetrapods and Their Electrocatalytic Activity for Formic Acid Oxidation.Nanoscale,2014,6,2776-2781).At present, the palladium nanostructured of different-shape, such as nanometer four Face body, nanometer octahedron, nanosphere, nano wire, nano-hollow ball and nanocube, with different synthetic method (bags Include template, crystal seed method, chemical reduction method, sol-gel process and thermal decomposition method etc.) (Arginine-Assisted is prepared Synthesis and Catalytic Properties of Single Crystalline Palladium Tetrapods.ACS Applied Materials Interfaces,2014,6,22790-22795)。
The content of the invention
The technical problems to be solved by the invention are to provide a kind of simple and effective hydrothermal reduction method and prepare have The method of even and pattern, size and the controllable hollow palladium nanosphere of composition.
Technical scheme is made up of following step used by solving above-mentioned technical problem：
1st, Nano balls of cuprous oxide is prepared
It is 1 in molar ratio by copper chloride or copper sulphate, polyethyleneimine, ascorbic acid:1~3:1~1.5 adds distilled water In, it is well mixed, the pH value for adjusting gained mixed liquor with sodium hydrate aqueous solution is stirred at room temperature 20~30 minutes to 10~13, Obtain Nano balls of cuprous oxide solution.
2nd, hollow palladium nanosphere is prepared
The aqueous solution of potassium chloropalladite or palladium bichloride is adjusted into pH value to 10~13 with 0.5mol/L sodium hydrate aqueous solutions Afterwards, it is added in Nano balls of cuprous oxide solution, and adds hydrazine hydrate, wherein potassium chloropalladite or palladium bichloride, hydrazine hydrate, oxidation Cuprous mol ratio is 1:7~20:1.5~2, reduction reaction 20~40 minutes at 50~80 DEG C, then it is stirred at room temperature 16~ 24 hours, centrifugation, washing, dry, obtain hollow palladium nanosphere.
In above-mentioned steps 1, preferably copper chloride or copper sulphate, polyethyleneimine, the mol ratio of ascorbic acid is 1:2:1.2 The number-average molecular weight of wherein described polyethyleneimine is 300~1200.
In above-mentioned steps 2, preferably potassium chloropalladite or palladium bichloride, hydrazine hydrate, the mol ratio of cuprous oxide is 1:10: 1.85。
In above-mentioned steps 2, reduction reaction 30 minutes further preferably at 60 DEG C.
Beneficial effects of the present invention are as follows：
1st, the present invention uses a small amount of polyethyleneimine (PEI) preparing cuprous nano for stabilizer and guiding agent During ball, stabilizers of the PEI as copper chloride, the N therein and Cu in copper chloride2+Complexing, makes copper chloride and Vitamin C The speed that reduction reaction occurs for acid is gentleer, so as to obtain the Nano balls of cuprous oxide of size and morphology controllable, excessive PEI Molecular Adsorption is on the surface of Nano balls of cuprous oxide；During hollow palladium nanosphere is prepared, adsorb in cuprous nano The PEI of ball surface in the guiding agent of cuprous oxide superficial growth, makes palladium be easier to be grown in Nano balls of cuprous oxide table as palladium Face, while the PEI adsorbed on Nano balls of cuprous oxide surface is used as Cu again2+Stabilizer, cuprous oxide is easy to by air In dioxygen oxidation.
2nd, the present invention is using Nano balls of cuprous oxide as template, using sodium chloropalladite as palladium presoma, Pd2+It is being adsorbed in oxidation Under the PEI of cuprous nanometer ball surface guiding then oriented growth is aoxidized in the presence of PEI on Nano balls of cuprous oxide surface The cuprous dioxygen oxidation by air turns into Cu2+Ion, Cu2+Ion can be removed by washing, finally give pattern, size Homogeneous hollow palladium nanosphere.
3rd, the present invention does not need high temperature, it is not necessary to the longer reaction time, it is not necessary to complicated pH regulation processes, operation letter Single, product yield is high and homogeneity is good, is adapted to large-scale production.
4th, hollow palladium nanosphere prepared by the present invention is shown excellent compared with being commercialized palladium black to Catalyzed by Formic Acid reaction Electro catalytic activity and stability, there is potential application prospect in direct methanoic acid fuel cell field.
Brief description of the drawings
Fig. 1 is the SEM figures of hollow palladium nanosphere prepared by embodiment 1.
Fig. 2 is the TEM figures of hollow palladium nanosphere prepared by embodiment 1.
Fig. 3 is the TEM figures of hollow palladium nanosphere prepared by embodiment 2.
Fig. 4 is the TEM figures of hollow palladium nanosphere prepared by embodiment 3.
Fig. 5 is the TEM figures of hollow palladium nanosphere prepared by embodiment 4.
Fig. 6 is the TEM figures of hollow palladium nanosphere prepared by embodiment 5.
Fig. 7 is the TEM figures of hollow palladium nanosphere prepared by embodiment 6.
Fig. 8 is the TEM figures of hollow palladium nanosphere prepared by embodiment 7.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to These embodiments.
Embodiment 1
1st, Nano balls of cuprous oxide is prepared
Take 1mL 0.05mol/L CuCl2The aqueous solution, the polyethyleneimine that 0.2mL 0.5mol/L number-average molecular weights are 600 Amine aqueous solution, 0.6mL 0.1mol/L aqueous ascorbic acid add 10mL distilled water, after being stirred 3 minutes, use The pH value of 0.5mol/L sodium hydrate aqueous solution regulation gained mixed liquor is stirred at room temperature 20 minutes to 11.5, it is sub- to obtain oxidation Copper nanosphere solution.
2nd, hollow palladium nanosphere is prepared
The 0.45mL 0.06mol/L potassium chloropalladite aqueous solution is adjusted into pH value with 0.5mol/L sodium hydrate aqueous solutions To after 11.5, it is added in the Nano balls of cuprous oxide solution that step 1 obtains, and adds the water that 15.5 μ L mass fractions are 80% The hydrazine aqueous solution is closed, heating water bath constant temperature reduction reaction 30 minutes, is then stirred at room temperature 24 hours to 60 DEG C, centrifuged with distilled water, Washing, 60 DEG C of dryings, obtain hollow palladium nanosphere (see Fig. 1 and 2).
Embodiment 2
In embodiment 1, copper chloride used is replaced with equimolar copper sulphate, the equimolar chlorination of potassium chloropalladite Palladium is replaced, and other steps are same as Example 1, obtain hollow palladium nanosphere (see Fig. 3).
Embodiment 3
In embodiment 1,0.2mL 0.5mol/L number-average molecular weights are 600 aq. polyethyleneimine 0.1mL The aq. polyethyleneimine that 0.5mol/L number-average molecular weights are 600 is replaced, and other steps are same as Example 1, obtain hollow Palladium nanosphere (see Fig. 4).
Embodiment 4
In embodiment 1,0.2mL 0.5mol/L number-average molecular weights are 600 aq. polyethyleneimine 0.3mL The aq. polyethyleneimine that 0.5mol/L number-average molecular weights are 600 is replaced, and other steps are same as Example 1, obtain hollow Palladium nanosphere (see Fig. 5).
Embodiment 5
In embodiment 1, the hydrazine hydrate aqueous solution that 15.5 μ L mass fractions are 80% is 80% with 30 μ L mass fractions Hydrazine hydrate aqueous solution is replaced, and other steps are same as Example 1, obtain hollow palladium nanosphere (see Fig. 6).
Embodiment 6
In the step 1 of embodiment 1 and 2, pH value is adjusted to 13 with 0.5mol/L sodium hydrate aqueous solutions, other steps with Embodiment 1 is identical, obtains hollow palladium nanosphere (see Fig. 7).
Embodiment 7
In the step 2 of embodiment 1, heating water bath is to 80 DEG C, constant temperature reduction reaction 20 minutes, other steps and embodiment 1 is identical, obtains hollow palladium nanosphere (see Fig. 8).

Claims (5)

1. a kind of preparation method of 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 1 in molar ratio by copper chloride or copper sulphate, polyethyleneimine, ascorbic acid:1~3:1~1.5 adds in distilled water, Well mixed, the pH value for adjusting gained mixed liquor with sodium hydrate aqueous solution is stirred at room temperature 20~30 minutes, obtained to 10~13 Nano balls of cuprous oxide solution；
(2) hollow palladium nanosphere is prepared
By the aqueous solution of potassium chloropalladite or palladium bichloride with after 0.5mol/L sodium hydrate aqueous solutions regulation pH value to 10~13, add Enter into Nano balls of cuprous oxide solution, and add hydrazine hydrate, wherein potassium chloropalladite or palladium bichloride, hydrazine hydrate, cuprous oxide Mol ratio be 1:7~20:1.5~2, reduction reaction 20~40 minutes at 50~80 DEG C, it is small to be then stirred at room temperature 16~24 When, centrifugation, washing, dry, obtain hollow palladium nanosphere.
2. the preparation method of hollow palladium nanosphere according to claim 1, it is characterised in that：In step (1), the chlorine It is 1 to change copper or copper sulphate, polyethyleneimine, the mol ratio of ascorbic acid:2:1.2.
3. the preparation method of hollow palladium nanosphere according to claim 1 or 2, it is characterised in that：Described polyethyleneimine The number-average molecular weight of amine is 300~1200.
4. the preparation method of hollow palladium nanosphere according to claim 1, it is characterised in that：In step (2), the chlorine Sub- palladium acid potassium or palladium bichloride, hydrazine hydrate, the mol ratio of cuprous oxide are 1:10:1.85.
5. the preparation method of the hollow palladium nanosphere according to claim 1 or 4, it is characterised in that：In the step (2), Reduction reaction 30 minutes at 60 DEG C.
CN201610261081.XA 2016-04-25 2016-04-25 A kind of preparation method of hollow palladium nanosphere Expired - Fee Related CN105945298B (en)

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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
CN107520462A (en) * 2017-08-01 2017-12-29 江苏理工学院 A kind of preparation method of tetrahedral CuCl/Au alloys
CN107470649B (en) * 2017-08-01 2019-09-10 江苏理工学院 A kind of preparation method of tetrahedral CuCl/Pt alloy
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
CN110676473B (en) * 2019-10-10 2022-04-15 陕西师范大学 Preparation method of multi-stage porous Rh nanosheet
CN110976906B (en) * 2019-12-04 2021-07-27 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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CN104722775B (en) * 2015-03-11 2016-09-07 浙江大学 A kind of two dimension hollow palladium nano-crystal and preparation method thereof
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