CN107900374A - A kind of preparation method of the good cube platinum nano material of uniformity - Google Patents

A kind of preparation method of the good cube platinum nano material of uniformity Download PDF

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Publication number
CN107900374A
CN107900374A CN201711108148.7A CN201711108148A CN107900374A CN 107900374 A CN107900374 A CN 107900374A CN 201711108148 A CN201711108148 A CN 201711108148A CN 107900374 A CN107900374 A CN 107900374A
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cuprous oxide
solution
added dropwise
water
reaction
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CN107900374B (en
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田亮亮
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Chongqing University of Arts and Sciences
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Chongqing University of Arts and Sciences
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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
    • 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 the preparation method of a kind of cube of platinum nano material, is that the cuprous oxide of cubic structure is dispersed in low mass molecule alcohol, adds the low mass molecule alcohol solution of precious metal salt, ultrasonic agitation mixing under agitation；The cuprous oxide of the cubic structure is prepared by following methods：Under 50 60 DEG C of stirring conditions, toward CuCl2Excessive NaOH solution is added in solution and reacts 0.5 1h, ascorbic acid solution is then slowly added dropwise again, is centrifuged after reacting 3 4h, then is cleaned respectively with water and ethanol, is finally dried in vacuo, obtains the cuprous oxide of cubic structure.The mixed liquor that above step is obtained, which is added dropwise in water, to react；Cuprous oxide core is removed after the completion of reaction, obtains hollow noble metal nanometer material.The present invention uses and cuprous oxide and precious metal salt is first stirred by ultrasonic to mixing in low mass molecule alcohol, the method reacted in water is added dropwise to again, the non-uniform shortcoming of reaction of conventional method is overcome, the uniform accurate hollow noble metal nanometer material for replicating cuprous oxide template pattern is prepared.

Description

A kind of preparation method of the good cube platinum nano material of uniformity
The application is for Application No. 2015109948517, entitled " a kind of using cuprous oxide for template preparation The divisional application of the method for hollow noble metal nanometer material ".
Technical field
The present invention relates to technical field of nano material, and in particular to the preparation method of a kind of cube of platinum nano material.
Background technology
The noble metal nanometer material with hollow-core construction combines hollow-core construction and noble metal nano particles, has The properties such as density is low, specific surface area is big, high stability and Surface Permeability, have more active site, and electro-catalysis is lived Property increase substantially, there is special application prospect in biochemistry, catalysis, the field such as material science.And due to noble metal Costly, hollow-core construction can not only increase substantially electro catalytic activity, but also save cost.It is template currently with cuprous oxide The method for preparing hollow noble metal nanometer material is：First by Cu2O ultrasonic disperses in water, then under agitation by your gold Belong to salting liquid and be added to Cu2In O suspension, the Cu of noble metal cladding is obtained by reaction2O cores, finally remove Cu2O templates, obtain To based on Cu2The noble metal hollow structure of O patterns.Such method is added to Cu in precious metal salt solution2When in O suspension, due to The uneven Cu that can cause first to contact precious metal salt of reactant in system2O is excessively coated, and causes the uneven of reaction, from And the inhomogeneities of final hollow noble metal nanometer material is caused, show as accurately replicating template pattern, surface roughness Increase and substantial amounts of local Fragmentation Phenomena.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the good cube platinum nano material of uniformity.
The object of the invention is achieved through the following technical solutions：
The preparation method of a kind of cube of platinum nano material, comprises the following steps：
（1）The cuprous oxide of cubic structure is dispersed in low mass molecule alcohol, adds the low of precious metal salt under agitation Molecule alcoholic solution, ultrasonic agitation mixing；The cuprous oxide of the cubic structure is prepared by following methods：In 50-60 DEG C of stirring bar Under part, toward CuCl2Excessive NaOH solution reaction 0.5-1h is added in solution, ascorbic acid solution is then slowly added dropwise again, instead It should centrifuge after about 3-4h, then be cleaned respectively with water and ethanol, finally be dried in vacuo, obtain the cuprous oxide of cubic structure.
（2）By step（1）Obtained mixed liquor, which is added dropwise in water, to react；
（3）Cuprous oxide core is removed after the completion of reaction, obtains hollow noble metal nanometer material.
Further, the step（1）In, precious metal salt H2PtCl6Or/and Na2PdCl4；The step（1）In, low point Sub- alcohol is the one or more in methanol, ethanol and ethylene glycol.The step（1）In, the precious metal salt and cuprous oxide of addition Molar ratio be 1.4-2.3:1 or so.The step（1）In, the ultrasonic agitation mixing 60-90min at 20-25 DEG C.The step Suddenly（2）In, mixed liquor is added dropwise in the water of 10-15 times of volume with the rate of addition of 12-20ml/min reacts 30-60min.
Further, the step（3）In, product is centrifuged into 2-5min under the conditions of 4000-10000 turns after the completion of reaction, The ammonium hydroxide complexing for adding 18%-25% removes cuprous oxide core, and the nitric acid for then adding 0.1-0.5mol/L reacts at 10-25 DEG C The copper that disproportionated reaction produces is removed, obtains hollow noble metal nanometer material.
Most preferably say, a kind of preparation method of the good cube platinum nano material of uniformity, comprises the following steps：
（1）Under 55 DEG C of stirring conditions, to the CuCl that 100 ml concentration are 0.01mol/L210mL concentration is added in solution is The NaOH solution of 2mol/L, after reacting 0.5h, then is slowly added dropwise the ascorbic acid solution that 10ml concentration is 0.6mol/L, instead After answering 3h, centrifugation, is cleaned with water and ethanol respectively, and 12 h of last 40 DEG C of vacuum drying, obtain the cuprous oxide of cubic structure；
（2）The cuprous oxide of 10mg cubic structures is dispersed in 10ml ethanol, adds 20mM's under agitation H2PtCl6Ethanol solution, makes H2PtCl6Molar ratio with cuprous oxide is 1.4:1, the ultrasonic agitation mixing 60min at 25 DEG C；
（3）By step（2）Obtained mixed liquor is added dropwise in the water of 15 times of volumes with the rate of addition of 20ml/min to react 30min；
（4）Product is centrifuged into 5min under the conditions of 5000 turns after the completion of reaction, the ammonium hydroxide complexing for adding 20% removes cuprous oxide Core, the nitric acid for then adding 0.1mol/L reacts the copper for removing disproportionated reaction generation at 25 DEG C, obtain cube Pt nanometers hollow Material.
The present invention has following beneficial effect：
The present invention uses and cuprous oxide and precious metal salt is first stirred by ultrasonic to mixing in low mass molecule alcohol, then is added dropwise in water and reacts Method, overcome the non-uniform shortcoming of reaction of conventional method, be prepared and uniform accurate replicate cuprous oxide template shape The hollow noble metal nanometer material of looks.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of cube hollow Pt nano materials prepared by embodiment 1.
Embodiment
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.
According to cuprous oxide pattern and the diversity of size, the hollow noble metal nano of different structure can be designed and synthesized Material, following embodiments and comparative example are by taking the cuprous oxide of cubic structure as an example.
The cuprous oxide for the cubic structure that following embodiments and comparative example are used is prepared by following methods：
Under 55 DEG C of stirring conditions, to the CuCl that 100 ml concentration are 0.01mol/L2It is 2mol/L that 10mL concentration is added in solution NaOH solution, react 0.5h after, then be slowly added dropwise 10ml concentration be 0.6mol/L ascorbic acid solution, react 3h Afterwards, centrifuge, cleaned respectively with water and ethanol, 12 h of last 40 DEG C of vacuum drying, obtain the cuprous oxide of cubic structure.
Embodiment 1
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of embodiment 1, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in about 10ml ethanol, adds 20mM's under agitation H2PtCl6Ethanol solution, makes H2PtCl6Molar ratio with cuprous oxide is about 1.4:1, mixing is stirred by ultrasonic at 25 DEG C 60min；
（2）By step（1）Obtained mixed liquor is added dropwise in the water of 15 times of volumes with the rate of addition of 20ml/min or so to react 30min；
（3）Product is centrifuged into 5min under the conditions of 5000 turns after the completion of reaction, the ammonium hydroxide complexing for adding 20% removes cuprous oxide Core, the nitric acid for then adding 0.1mol/L reacts the copper for removing disproportionated reaction generation at 25 DEG C, obtain cube Pt nanometers hollow Material.
Embodiment 2
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of embodiment 2, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in 10ml methanol, adds 30mM's under agitation Na2PdCl4Methanol solution, makes Na2PdCl4Molar ratio with cuprous oxide is 2.0:1, mixing is stirred by ultrasonic at 25 DEG C 70min；
（2）By step（1）Obtained mixed liquor is added dropwise in the water of 12 times of volumes with the rate of addition of 15ml/min to react 50min；
（3）Product is centrifuged into 5min under the conditions of 8000 turns after the completion of reaction, the ammonium hydroxide complexing for adding 20% removes cuprous oxide Core, the nitric acid for then adding 0.2mol/L reacts the copper for removing disproportionated reaction generation at 20 DEG C, obtain cube Pd nanometers hollow Material.
Embodiment 3
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of embodiment 3, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in 10ml ethylene glycol, adds 20mM's under agitation H2PtCl6The Na of ethylene glycol solution and 30mM2PdCl4Ethylene glycol solution, makes H2PtCl6And Na2PdCl4The sum of with cuprous oxide Molar ratio is 2.3:1, the ultrasonic agitation mixing 90min at 20 DEG C；
（2）By step（1）Obtained mixed liquor is added dropwise in the water of 10 times of volumes with the rate of addition of 12ml/min to react 60min；
（3）Product is centrifuged into 2min under the conditions of 10000 turns after the completion of reaction, the ammonium hydroxide complexing for adding 18% removes cuprous oxide Core, the nitric acid for then adding 0.5mol/L react the copper for removing disproportionated reaction generation at 10 DEG C, obtain a cube hollow PtPd and receive Rice material.
Comparative example 1
The method that hollow noble metal nanometer material is prepared using cuprous oxide as template of comparative example 1, comprises the following steps：
（1）The cuprous oxide of 10mg cubic structures is dispersed in 10ml water, adds 20mM's under agitation H2PtCl6Aqueous solution, makes H2PtCl6Molar ratio with cuprous oxide is 1.4:1, the stirring reaction 60min at 25 DEG C；
（2）Product is centrifuged into 5min under the conditions of 5000 turns after the completion of reaction, the ammonium hydroxide complexing for adding 20% removes cuprous oxide Core, the nitric acid for then adding 0.1mol/L reacts the copper for removing disproportionated reaction generation at 25 DEG C, obtain cube Pt nanometers hollow Material.
The roughness of cube hollow Pt nano materials prepared by embodiment 1 be 10-20nm, cube sky of the preparation of comparative example 1 The roughness of heart Pt nano materials is 20-50nm.
Comparative example 1 reacts uneven, and cube hollow Pt nano materials caused are uneven, it is impossible to accurately replicate template , there is substantial amounts of local broken and surface roughness increase in pattern；And embodiment 1 overcomes the non-uniform shortcoming of reaction, obtain Cube hollow Pt nano materials uniformly and accurate replicate template pattern.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical Cross above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (1)

  1. A kind of 1. preparation method of the good cube platinum nano material of uniformity, it is characterised in that：Comprise the following steps：
    （1）Under 55 DEG C of stirring conditions, to the CuCl that 100 ml concentration are 0.01mol/L210mL concentration is added in solution is The NaOH solution of 2mol/L, after reacting 0.5h, then is slowly added dropwise the ascorbic acid solution that 10ml concentration is 0.6mol/L, instead After answering 3h, centrifugation, is cleaned with water and ethanol respectively, and 12 h of last 40 DEG C of vacuum drying, obtain the cuprous oxide of cubic structure；
    （2）The cuprous oxide of 10mg cubic structures is dispersed in about 10ml ethanol, adds 20mM's under agitation H2PtCl6Ethanol solution, makes H2PtCl6Molar ratio with cuprous oxide is about 1.4:1, mixing is stirred by ultrasonic at 25 DEG C 60min；
    （3）By step（2）Obtained mixed liquor is added dropwise in the water of 15 times of volumes with the rate of addition of 20ml/min or so to react 30min；
    （4）Product is centrifuged into 5min under the conditions of 5000 turns after the completion of reaction, the ammonium hydroxide complexing for adding 20% removes cuprous oxide Core, the nitric acid for then adding 0.1mol/L reacts the copper for removing disproportionated reaction generation at 25 DEG C, obtain cube Pt nanometers hollow Material.
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