CN107900374B - Preparation method of cubic platinum nano material with good uniformity - Google Patents
Preparation method of cubic platinum nano material with good uniformity Download PDFInfo
- Publication number
- CN107900374B CN107900374B CN201711108148.7A CN201711108148A CN107900374B CN 107900374 B CN107900374 B CN 107900374B CN 201711108148 A CN201711108148 A CN 201711108148A CN 107900374 B CN107900374 B CN 107900374B
- Authority
- CN
- China
- Prior art keywords
- cuprous oxide
- reaction
- nano material
- cubic
- noble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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 a preparation method of a cubic platinum nano material, which is characterized in that cuprous oxide with a cubic structure is uniformly dispersed in low molecular alcohol, and low molecular alcohol soluble of noble metal salt is added under the stirring conditionLiquid, ultrasonic stirring and mixing; the cuprous oxide with the cubic structure is prepared by the following method: adding CuCl into the mixture under stirring at 50-60 deg.C2Adding excessive NaOH solution into the solution to react for 0.5-1h, then slowly dropwise adding ascorbic acid solution, reacting for 3-4h, centrifuging, respectively washing with water and ethanol, and finally vacuum drying to obtain cuprous oxide with a cubic structure. Dropwise adding the mixed solution obtained in the step into water for reaction; and removing the cuprous oxide core after the reaction is finished to obtain the hollow noble metal nano material. The invention adopts the method of firstly ultrasonically stirring and mixing cuprous oxide and noble metal salt in low molecular alcohol and then dropwise adding the mixture into water for reaction, overcomes the defect of uneven reaction of the conventional method, and prepares the hollow noble metal nano material which accurately replicates the appearance of the cuprous oxide template.
Description
The application is a divisional application of the invention with the application number of 2015109948517 and the name of 'a method for preparing hollow noble metal nano material by using cuprous oxide as a template'.
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a cubic platinum nano material.
Background
The noble metal nano material with the hollow structure integrates the advantages of the hollow structure and the noble metal nano particles, has the properties of low density, large specific surface area, high stability, surface permeability and the like, has more catalytic active sites, greatly improves the electrocatalytic activity, and has special application prospect in the fields of biochemistry, catalytic chemistry, material science and the like. And because the noble metal is expensive, the hollow structure can not only greatly improve the electrocatalytic activity, but also save the cost. The method for preparing the hollow noble metal nano material by using cuprous oxide as a template comprises the following steps: firstly, Cu is added2O is dispersed in water by ultrasonic wave, and then noble metal salt solution is added into Cu under the condition of stirring2In O suspension, reacting to obtain Cu coated with noble metal2Nuclear of O, and finally Cu removal2O template to obtain Cu-based2O-shaped noble metal hollow structure. Such methods add noble metal salts in solution to Cu2In O suspension, Cu which is first contacted with a noble metal salt may be caused by non-uniformity of reactants in the system2O is excessively coated to cause the reactionThe unevenness, which results in the unevenness of the final hollow noble metal nanomaterial, is manifested by the inability to accurately replicate the template morphology, increased surface roughness, and a large number of local fractures.
Disclosure of Invention
The invention aims to provide a preparation method of a cubic platinum nano material with good uniformity.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a cubic platinum nano material comprises the following steps:
(1) uniformly dispersing cuprous oxide with a cubic structure in low molecular alcohol, adding a low molecular alcohol solution of noble metal salt under stirring, and ultrasonically stirring and mixing; the cuprous oxide with the cubic structure is prepared by the following method: adding CuCl into the mixture under stirring at 50-60 deg.C2Adding excessive NaOH solution into the solution to react for 0.5-1h, then slowly dropwise adding ascorbic acid solution, reacting for about 3-4h, centrifuging, respectively washing with water and ethanol, and finally vacuum drying to obtain cuprous oxide with a cubic structure.
(2) Dropwise adding the mixed solution obtained in the step (1) into water for reaction;
(3) and removing the cuprous oxide core after the reaction is finished to obtain the hollow noble metal nano material.
Further, in the step (1), the noble metal salt is H2PtCl6Or/and Na2PdCl4(ii) a In the step (1), the low molecular alcohol is one or more of methanol, ethanol and glycol. In the step (1), the molar ratio of the added noble metal salt to the cuprous oxide is about 1.4-2.3: 1. In the step (1), ultrasonic stirring and mixing are carried out for 60-90min at the temperature of 20-25 ℃. In the step (2), the mixed solution is dripped into water with the volume of 10-15 times of that of the mixed solution at the dripping speed of 12-20ml/min for reaction for 30-60 min.
Further, in the step (3), after the reaction is finished, the product is centrifuged for 2-5min under the condition of 4000-10000 rpm, 18-25% of ammonia water is added for complexation to remove cuprous oxide nuclei, and then 0.1-0.5mol/L of nitric acid is added for reaction at 10-25 ℃ to remove copper generated by disproportionation reaction, so as to obtain the hollow noble metal nano material.
Most preferably, the preparation method of the cubic platinum nano material with good uniformity comprises the following steps:
(1) adding 100 ml of CuCl with the concentration of 0.01mol/L under the stirring condition at the temperature of 55 DEG C2Adding 10mL of 2mol/L NaOH solution into the solution, reacting for 0.5h, slowly dropwise adding 10mL of 0.6mol/L ascorbic acid solution, reacting for 3h, centrifuging, respectively washing with water and ethanol, and finally vacuum drying at 40 ℃ for 12 h to obtain cuprous oxide with a cubic structure;
(2) 10mg of cuprous oxide with cubic structure is evenly dispersed in 10ml of ethanol, and 20mM of H is added under the stirring condition2PtCl6Ethanol solution of H2PtCl6The mol ratio of the raw materials to cuprous oxide is 1.4:1, and the raw materials are stirred and mixed for 60min by ultrasonic at 25 ℃;
(3) dropwise adding the mixed solution obtained in the step (2) into water with the volume 15 times that of the mixed solution at the dropwise adding speed of 20ml/min to react for 30 min;
(4) and after the reaction is finished, centrifuging the product for 5min under the condition of 5000 revolutions, adding 20% ammonia water for complexation to remove cuprous oxide cores, and then adding 0.1mol/L nitric acid for reaction at 25 ℃ to remove copper generated by disproportionation reaction, thereby obtaining the cubic hollow Pt nano material.
The invention has the following beneficial effects:
the invention adopts the method of firstly ultrasonically stirring and mixing cuprous oxide and noble metal salt in low molecular alcohol and then dropwise adding the mixture into water for reaction, overcomes the defect of uneven reaction of the conventional method, and prepares the hollow noble metal nano material which accurately replicates the appearance of the cuprous oxide template.
Drawings
Fig. 1 is a scanning electron micrograph of the cubic hollow Pt nanomaterial prepared in example 1.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
According to the diversity of the shape and the size of the cuprous oxide, hollow noble metal nano materials with different structures can be designed and synthesized, and the following examples and comparative examples take the cuprous oxide with a cubic structure as an example.
The cubic cuprous oxide used in the following examples and comparative examples was prepared by the following method:
adding 100 ml of CuCl with the concentration of 0.01mol/L under the stirring condition at the temperature of 55 DEG C2Adding 10mL of 2mol/L NaOH solution into the solution, reacting for 0.5h, slowly dropwise adding 10mL of 0.6mol/L ascorbic acid solution, reacting for 3h, centrifuging, respectively washing with water and ethanol, and finally vacuum drying at 40 ℃ for 12 h to obtain cuprous oxide with a cubic structure.
Example 1
The method for preparing the hollow noble metal nano material by using the cuprous oxide as the template in the embodiment 1 comprises the following steps:
(1) 10mg of cuprous oxide of cubic structure are homogeneously dispersed in about 10ml of ethanol, and 20mM of H are added with stirring2PtCl6Ethanol solution of H2PtCl6The molar ratio of the cuprous oxide to the cuprous oxide is about 1.4:1, and the mixture is stirred and mixed by ultrasonic for 60min at the temperature of 25 ℃;
(2) dropwise adding the mixed solution obtained in the step (1) into water with the volume 15 times that of the mixed solution at the dropping acceleration of about 20ml/min for reacting for 30 min;
(3) and after the reaction is finished, centrifuging the product for 5min under the condition of 5000 revolutions, adding 20% ammonia water for complexation to remove cuprous oxide cores, and then adding 0.1mol/L nitric acid for reaction at 25 ℃ to remove copper generated by disproportionation reaction, thereby obtaining the cubic hollow Pt nano material.
Example 2
The method for preparing the hollow noble metal nano material by using the cuprous oxide as the template in the embodiment 2 comprises the following steps:
(1) 10mg of cuprous oxide with cubic structure is uniformly dispersed in 10ml of methanol, and 30mM of Na is added under stirring2PdCl4Methanol solution to make Na2PdCl4The mol ratio of the raw materials to cuprous oxide is 2.0:1, and the raw materials are stirred and mixed for 70min by ultrasonic at 25 ℃;
(2) dropwise adding the mixed solution obtained in the step (1) into water with the volume being 12 times of that of the mixed solution at the dropwise adding speed of 15ml/min to react for 50 min;
(3) and after the reaction is finished, centrifuging the product for 5min under the condition of 8000 revolutions, adding 20% ammonia water for complexation to remove cuprous oxide nuclei, and then adding 0.2mol/L nitric acid for reaction at 20 ℃ to remove copper generated by disproportionation reaction, thereby obtaining the cubic hollow Pd nano material.
Example 3
The method for preparing the hollow noble metal nano material by using the cuprous oxide as the template in the embodiment 3 comprises the following steps:
(1) 10mg of cuprous oxide with cubic structure is uniformly dispersed in 10ml of ethylene glycol, and 20mM of H is added under stirring2PtCl6Ethylene glycol solution and 30mM Na2PdCl4Ethylene glycol solution of H2PtCl6And Na2PdCl4The molar ratio of the sum to cuprous oxide is 2.3:1, and the mixture is stirred and mixed for 90min by ultrasonic at 20 ℃;
(2) dropwise adding the mixed solution obtained in the step (1) into water with the volume of 10 times of that of the mixed solution at the dropwise adding speed of 12ml/min to react for 60 min;
(3) and after the reaction is finished, centrifuging the product for 2min under the condition of 10000 revolutions, adding 18% ammonia water for complexation to remove cuprous oxide cores, and then adding 0.5mol/L nitric acid for reaction at 10 ℃ to remove copper generated by disproportionation reaction to obtain the cubic hollow PtPd nano material.
Comparative example 1
The method for preparing the hollow noble metal nano material by using the cuprous oxide as the template in the comparative example 1 comprises the following steps of:
(1) 10mg of cuprous oxide with cubic structure is uniformly dispersed in 10ml of water, and 20mM of H is added under stirring2PtCl6Aqueous solution of H2PtCl6The mol ratio of the cuprous oxide to the cuprous oxide is 1.4:1, and the mixture is stirred and reacts for 60min at the temperature of 25 ℃;
(2) and after the reaction is finished, centrifuging the product for 5min under the condition of 5000 revolutions, adding 20% ammonia water for complexation to remove cuprous oxide cores, and then adding 0.1mol/L nitric acid for reaction at 25 ℃ to remove copper generated by disproportionation reaction, thereby obtaining the cubic hollow Pt nano material.
The roughness of the cubic hollow Pt nanomaterial prepared in example 1 was 10-20nm, and the roughness of the cubic hollow Pt nanomaterial prepared in comparative example 1 was 20-50 nm.
Comparative example 1 reaction is not uniform, resulting in the obtained cubic hollow Pt nanomaterial being non-uniform, the template morphology cannot be accurately replicated, a large amount of local crushing and surface roughness increase occur; and the embodiment 1 overcomes the defect of uneven reaction, and the obtained cubic hollow Pt nano material can reproduce the appearance of the template uniformly and accurately.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (1)
1. A preparation method of a cubic platinum nano material with good uniformity is characterized by comprising the following steps: the method comprises the following steps:
(1) adding 100 ml of CuCl with the concentration of 0.01mol/L under the stirring condition at the temperature of 55 DEG C2Adding 10mL of 2mol/L NaOH solution into the solution, reacting for 0.5h, slowly dropwise adding 10mL of 0.6mol/L ascorbic acid solution, reacting for 3h, centrifuging, respectively washing with water and ethanol, and finally vacuum drying at 40 ℃ for 12 h to obtain cuprous oxide with a cubic structure;
(2) 10mg of cuprous oxide of cubic structure are homogeneously dispersed in about 10ml of ethanol, and 20mM of H are added with stirring2PtCl6Ethanol solution of H2PtCl6The molar ratio of the cuprous oxide to the cuprous oxide is about 1.4:1, and the mixture is stirred and mixed by ultrasonic for 60min at the temperature of 25 ℃;
(3) dropwise adding the mixed solution obtained in the step (2) into water with the volume 15 times that of the mixed solution at the dropping acceleration of about 20ml/min for reacting for 30 min;
(4) and after the reaction is finished, centrifuging the product for 5min under the condition of 5000 revolutions, adding 20% ammonia water for complexation to remove cuprous oxide cores, and then adding 0.1mol/L nitric acid for reaction at 25 ℃ to remove copper generated by disproportionation reaction, thereby obtaining the cubic hollow Pt nano material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711108148.7A CN107900374B (en) | 2015-12-28 | 2015-12-28 | Preparation method of cubic platinum nano material with good uniformity |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510994851.7A CN105537614B (en) | 2015-12-28 | 2015-12-28 | A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template |
| CN201711108148.7A CN107900374B (en) | 2015-12-28 | 2015-12-28 | Preparation method of cubic platinum nano material with good uniformity |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510994851.7A Division CN105537614B (en) | 2015-12-28 | 2015-12-28 | A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107900374A CN107900374A (en) | 2018-04-13 |
| CN107900374B true CN107900374B (en) | 2020-06-23 |
Family
ID=55817427
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510994851.7A Active CN105537614B (en) | 2015-12-28 | 2015-12-28 | A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template |
| CN201711108148.7A Active CN107900374B (en) | 2015-12-28 | 2015-12-28 | Preparation method of cubic platinum nano material with good uniformity |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510994851.7A Active CN105537614B (en) | 2015-12-28 | 2015-12-28 | A kind of method that hollow noble metal nanometer material is prepared using cuprous oxide as template |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN105537614B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109055961B (en) * | 2018-08-29 | 2020-08-28 | 深圳先进技术研究院 | Noble metal supported nano-frame catalyst and preparation method and application thereof |
| CN109759135B (en) * | 2019-02-02 | 2020-02-21 | 哈尔滨工业大学 | Preparation method of composite material for removing heavy metal/hydrophobic ppcps in reclaimed water |
| CN112028109B (en) * | 2020-08-24 | 2022-11-08 | 广东省医疗器械研究所 | Composite nano material and preparation method and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0251666B2 (en) * | 1980-03-24 | 1990-11-08 | Iyutokemisuka Inst | |
| JPS56136904A (en) * | 1980-03-31 | 1981-10-26 | Toshiba Corp | Production of platinum group particle |
| JP2837910B2 (en) * | 1990-03-01 | 1998-12-16 | チタン工業株式会社 | Method for producing noble metal fine particles using emulsion type liquid film method |
| JPH0657314A (en) * | 1992-08-06 | 1994-03-01 | Sumitomo Metal Mining Co Ltd | Production of fine palladium powder |
| CN1304107C (en) * | 2004-10-22 | 2007-03-14 | 马贞亮 | Preparation process of photocatalyzing active nano TiO2 collosol |
| CN101690977B (en) * | 2009-09-14 | 2011-06-01 | 西安交通大学 | Preparation method of hollow noble metal nanoparticles |
| CN103043703B (en) * | 2013-01-05 | 2014-06-11 | 河北工业大学 | Preparation method of hollow Cu2O cubic box |
| CN103042231B (en) * | 2013-01-11 | 2014-09-03 | 哈尔滨工业大学 | Preparation method of precious metal nano-particles |
| CN103447549B (en) * | 2013-09-13 | 2015-02-25 | 重庆文理学院 | Preparation method of cobalt nanosphere |
| CN104259473B (en) * | 2014-09-23 | 2017-01-11 | 中国科学院化学研究所 | Hollow spherical precious metal nanometer material preparation method |
-
2015
- 2015-12-28 CN CN201510994851.7A patent/CN105537614B/en active Active
- 2015-12-28 CN CN201711108148.7A patent/CN107900374B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105537614B (en) | 2017-11-28 |
| CN105537614A (en) | 2016-05-04 |
| CN107900374A (en) | 2018-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102992306B (en) | Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof | |
| JP2022116130A (en) | Method for manufacturing silver-coated copper nanowire having core-shell structure by using chemical reduction method | |
| CN107900374B (en) | Preparation method of cubic platinum nano material with good uniformity | |
| CN109108303B (en) | Preparation method of high-dispersity Pt-Cu alloy nanoparticles | |
| CN105597742A (en) | Catalyst and method of reaction for preparing butanedioic anhydride from maleic anhydride through liquid phase hydrogenation | |
| CN107573233A (en) | A kind of cobalt-based MOFs materials and its preparation method and application | |
| CN104600327B (en) | A kind of preparation method of carbon-supported nano platinum alloy catalyst | |
| CN107737593B (en) | TiO (titanium dioxide) 2 Preparation method of nano tube supported bimetallic catalyst | |
| CN104307512A (en) | Supported palladium catalyst and preparation method and application thereof | |
| CN103352254A (en) | Method for preparing octahedral platinoid alloy nanocrystals and octahedral platinoid alloy nanocrystal prepared through adopting same | |
| CN108520965B (en) | Preparation method of platinum-precious metal-copper ternary alloy nano hollow cube | |
| CN109621961B (en) | Method for in-situ preparation of metal high-dispersion catalyst by growing two-dimensional nanosheets | |
| CN107694563A (en) | Palladium carbon catalyst and its preparation method and application | |
| CN104625087A (en) | Method for hydrothermally manufacturing silver nanowires | |
| CN102873337A (en) | Poly-allylamine oriented platinum nano cube preparation method | |
| CN109732100A (en) | A kind of preparation method of the dendritic Pt nanoparticle of small size | |
| CN105879881A (en) | Preparation method of PtPd/Fe3O4 (platinum-palladium/ferroferric oxide) nanocatalyst and application thereof in HECK reaction | |
| CN104001525A (en) | Preparation method for PtCu/C catalyst | |
| CN109012693B (en) | Preparation method and application of Pd-Ni porous nanocage catalytic material | |
| CN104959136B (en) | A kind of preparation method for adding hydrogen into resin egg-shell catalyst | |
| CN109599570B (en) | Dendritic PdPt nano-particles for electrocatalytic methanol oxidation and preparation method thereof | |
| CN103638974A (en) | Catalyst taking graphene nano-sheet as framework as well as preparation method and application of catalyst | |
| CN108906064A (en) | A kind of preparation method for the modified nano zinc oxide that photocatalytic degradation is strong | |
| CN108372308B (en) | Gold nanowire with various close-packed structures in mixed random arrangement and preparation method and application thereof | |
| CN108144609A (en) | A kind of hydrogenolysis of glycerin prepares the preparation method of the catalyst of 1,3- propylene glycol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |