CN103449538A - Preparation method of nano palladium oxide hollow spheres - Google Patents
Preparation method of nano palladium oxide hollow spheres Download PDFInfo
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- CN103449538A CN103449538A CN2013102750794A CN201310275079A CN103449538A CN 103449538 A CN103449538 A CN 103449538A CN 2013102750794 A CN2013102750794 A CN 2013102750794A CN 201310275079 A CN201310275079 A CN 201310275079A CN 103449538 A CN103449538 A CN 103449538A
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Abstract
The invention provides a preparation method of nano palladium oxide hollow spheres. The preparation method comprises the following steps: preparing a palladium nitrate-glycine mixed aqueous solution; adding a certain amount of a sodium hydroxide aqueous solution into the palladium nitrate-glycine mixed aqueous solution so as to adjust the pH value of the mixed solution to be alkaline; adding iron particles subjected to palladium chloride surface activation treatment into the mixed aqueous solution of palladium nitrate, glycine and sodium hydroxide; heating the mixed aqueous solution to 85-95 DEG C, and carrying out heat preservation on the mixed aqueous solution; dropwise adding a certain amount of an oxidant solution into the mixed aqueous solution at a certain speed under the condition of mechanical stirring so as to prepare spherical particles with an iron core-palladium oxide shell structure; and after the spherical particles with the iron core-palladium oxide shell structure are taken out and cleaned, adding the spherical particles into an acid solution so as to remove iron cores by dissolving, and carrying out mechanical stirring to obtain the nano palladium oxide hollow spheres. According to the preparation method provided by the invention, through preparing the nano palladium oxide hollow spheres, the surface area of palladium oxide is increased, and then the distribution rate and service efficiency of palladium are improved, thus the purpose of fully using and improving the catalytic activity of palladium oxides is achieved.
Description
Technical field
The invention belongs to field of nano material preparation, relate in particular to a kind of preparation method of palladous oxide hollow ball.
Background technology
The way that generates the palladous oxide particle with katalysis in the orthodox car three-way catalyst is that a certain amount of palladium salt is made an addition in the slurry of catalyst coat powder and weakly acidic aqueous solution mixed preparing and is coated on the support of the catalyst surface, and the carrier that then will be coated with catalyzer is heated to more than 500 ℃ carry out sintering.In sintering process, the palladium salt in slurry is the palladous oxide particle that is attached to the support of the catalyst surface and has katalysis through oxidation transformation.This palladous oxide particle is formed under the high temperature in sintering process, palladous oxide particle dia in the support of the catalyst coating prepared with the method is larger, be about hundreds of nanometers to tens micron, and may form larger alloy body with other precious metal elements (such as rhodium) sintering, the precious metal alloys catalytic activity formed so relatively a little less than, this alloy and metal oxide containing precious metals are because particle is larger simultaneously, the surface-area less, will cause the precious metal of particle inner core part directly to contact with exhaust gas component, reduce effectively taking full advantage of of precious metal, the waste that causes precious metal to use.
The palladous oxide preparation method who exists at present is by palladium salt, as Palladous nitrate, under alkaline environment, is hydrolyzed, and hydrolysate is at high temperature decomposed, and forms palladous oxide.Another kind method is to using palladium chloric acid as the palladium source, PVP has prepared the palladous oxide of Nano grade under microwave exposure as stablizer, palladous oxide prepared by this kind of method easily in reaction solution PVP be combined, again due to the PVP stable chemical nature, be difficult to adopt chemical process that it is removed, therefore the general supercentrifugal process that adopts separates repeatedly, and this just defines widespread use to a certain extent.
Summary of the invention
Purpose of the present invention will overcome the deficiencies in the prior art exactly, and the distributive law and the service efficiency that improve the surface-area of palladous oxide and then improve palladium by preparing nano level palladous oxide hollow ball, reach the purpose that takes full advantage of and improve the palladous oxide catalytic activity.
For solving above technical problem, the technical solution adopted in the present invention is: a kind of preparation method of nano oxidized palladium hollow ball comprises the following steps:
(1) preparation Palladous nitrate, glycine mixed aqueous solution;
(2) the pH value that adds a certain amount of aqueous sodium hydroxide solution to regulate mixed solution is alkalescence;
(3) will through the iron particle of palladium salt surface activation process, join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide;
(4) heating mixed aqueous solution to 85～95 ℃, and insulation;
(5) be added dropwise to a certain amount of oxidizing agent solution with given pace in mixed aqueous solution under mechanical stirring, make the spheroidal particle with iron core-palladous oxide shell structure;
(6) join molten deironing core mechanical stirring in acidic solution after the particle that will have iron core-palladous oxide shell structure take out to clean, make nano oxidized palladium hollow ball.
Further, described in step (1), Palladous nitrate concentration is 0.3mol/l, and the mol ratio of glycine and Palladous nitrate is 1: 1.
Further, described in step (2), the mixed aqueous solution pH value is 9.
Further, described in step (3), iron particle through the detailed process of palladium salt surface activation process is: at room temperature, iron particle is made an addition in certain density palladium nitrate aqueous solution, make a small amount of divalence palladium ion be deposited on the palladium activation point that the iron particle surface forms some amount at iron particle surface replacement iron atom, described palladium nitrate aqueous solution concentration is that 0.2mol/l, temperature are 40 ℃.
Further, described in step (3), the iron particle diameter range is 20～150nm.
Further, described in step (4), soaking time is 1 hour.
Further, described in step (5), speed is 4ml/m.
Further, the hydrogen peroxide that described in step (5), oxidizing agent solution is concentration 50%.
Further, the dilute hydrochloric acid solution that described in step (6), acidic solution is concentration 10%.
The effect that the present invention is useful is:
1, prepared palladous oxide is nanoscale, so specific surface area is larger, and catalytic performance is stronger.
2. prepared palladous oxide is hollow structure, and density is less, so sedimentation stability is good, in use can with the fine coupling of slurry.
3. prepared palladous oxide is hollow structure, and there is tiny cavity in housing simultaneously, therefore can increase surface-area, improves catalytic performance.
The accompanying drawing explanation
Fig. 1 is palladous oxide hollow ball preparation process schematic diagram of the present invention;
In the accompanying drawings:
The 10-iron particle; 20-palladium hydroxide/iron nuclear particle; 30-palladous oxide/iron nuclear particle; 40-palladous oxide hollow ball.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the present invention are further described.
Fig. 1 is palladous oxide hollow ball preparation process schematic diagram of the present invention, iron particle 10 through palladium salt surface activation process joins in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide through step S101, make palladium hydroxide in mixing solutions be adsorbed in the palladium activation point place on iron particle surface, form palladium hydroxide/iron nuclear particle 20.
Then more than step S102 heating mixed solution to 95 ℃, with given pace, in mixed solution, be added dropwise to oxygenant hydrogen oxide palladous oxide, the palladium hydroxide that makes constantly to be adsorbed in the nano-iron particle surface is that palladous oxide forms palladous oxide/iron nuclear particle 30 by slow oxidation.
Compactness extent finally by step S103 by the addition ratio control iron particle surface oxidation palladium shell of palladium salt and iron particle in the adjusting mixed solution, make in the palladous oxide shell to exist a certain amount of small hole.To there is the palladous oxide of iron core-palladous oxide shell structure/iron nuclear particle 30 and join in dilute hydrochloric acid after taking out and cleaning, and utilize palladous oxide to be insoluble to dilute hydrochloric acid, and make dilute hydrochloric acid pass through the molten deironing core of hole in the palladous oxide shell, make nano oxidized palladium hollow ball 40.
Embodiment 1:
Make with the sodium borohydride reduction ferrous sulfate iron particle that diameter is about 150nm in water.It is in 0.2mol/l, the temperature palladium nitrate aqueous solution that is 40 ℃ that the 10g nano-iron particle made is joined to 400ml concentration, and mechanical stirring 10 minutes.Preparation 400ml Palladous nitrate, glycine mixed aqueous solution, wherein, Palladous nitrate concentration is 0.3mol/l, and the mol ratio of glycine and Palladous nitrate is 1: 1, and the pH value that adds a certain amount of aqueous sodium hydroxide solution to regulate mixed solution is 9.To through the iron particle of palladium salt surface activation process, join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide, heating mixed solution to 95 ℃ insulation 1 hour, simultaneously under mechanical stirring, to take the speed of 4ml/m in mixed solution, be added dropwise to the hydrogen peroxide 300ml that concentration is 50%, make spherical palladous oxide with iron core-palladous oxide shell structure/iron nuclear particle.Add in the hydrochloric acid soln that concentration is 10% and follow mechanical stirring 10 minutes thering is the spherical palladous oxide of iron core-palladous oxide shell structure/iron nuclear particle, obtaining nano oxidized palladium hollow ball.
Embodiment 2:
Make with the sodium borohydride reduction ferrous sulfate iron particle that diameter is about 20nm in water.It is in 0.2mol/l, the temperature palladium nitrate aqueous solution that is 40 ℃ that the 10g nano-iron particle made is joined to 400ml concentration, and mechanical stirring 10 minutes.Preparation 400ml Palladous nitrate, glycine mixed aqueous solution, wherein, Palladous nitrate concentration is 0.3mol/l, and the mol ratio of glycine and Palladous nitrate is 1: 1, and the pH value that adds a certain amount of aqueous sodium hydroxide solution to regulate mixed solution is 9.To through the iron particle of palladium salt surface activation process, join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide, heating mixed solution to 85 ℃ insulation 1 hour, simultaneously under mechanical stirring, to take the speed of 4ml/m in mixed solution, be added dropwise to the hydrogen peroxide 300ml that concentration is 50%, make spherical palladous oxide with iron core-palladous oxide shell structure/iron nuclear particle.Add in the hydrochloric acid soln that concentration is 10% and follow mechanical stirring 10 minutes thering is the spherical palladous oxide of iron core-palladous oxide shell structure/iron nuclear particle, obtaining nano oxidized palladium hollow ball.
Embodiment 3:
Make with the sodium borohydride reduction ferrous sulfate iron particle that diameter is about 50nm in water.It is in 0.2mol/l, the temperature palladium nitrate aqueous solution that is 40 ℃ that the 10g nano-iron particle made is joined to 400ml concentration, and mechanical stirring 10 minutes.Preparation 400ml Palladous nitrate, glycine mixed aqueous solution, wherein, Palladous nitrate concentration is 0.3mol/l, and the mol ratio of glycine and Palladous nitrate is 1: 1, and the pH value that adds a certain amount of aqueous sodium hydroxide solution to regulate mixed solution is 9.To through the iron particle of palladium salt surface activation process, join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide, heating mixed solution to 90 ℃ insulation 1 hour, simultaneously under mechanical stirring, to take the speed of 4ml/m in mixed solution, be added dropwise to the hydrogen peroxide 300ml that concentration is 50%, make spherical palladous oxide with iron core-palladous oxide shell structure/iron nuclear particle.Add in the hydrochloric acid soln that concentration is 10% and follow mechanical stirring 10 minutes thering is the spherical palladous oxide of iron core-palladous oxide shell structure/iron nuclear particle, obtaining nano oxidized palladium hollow ball.
The content that above-described embodiment is illustrated should be understood to these embodiment only for being illustrated more clearly in the present invention, and be not used in, limit the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
Claims (10)
1. the preparation method of a nano oxidized palladium hollow ball, is characterized in that, comprises the following steps:
(1) preparation Palladous nitrate, glycine mixed aqueous solution;
(2) the pH value that adds a certain amount of aqueous sodium hydroxide solution to regulate mixed solution is alkalescence;
(3) will through the iron particle of palladium salt surface activation process, join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide;
(4) heating mixed aqueous solution to 85～95 ℃, and insulation;
(5) be added dropwise to a certain amount of oxidizing agent solution with given pace in mixed aqueous solution under mechanical stirring, make the spheroidal particle with iron core-palladous oxide shell structure;
(6) join molten deironing core mechanical stirring in acidic solution after the particle that will have iron core-palladous oxide shell structure take out to clean, make nano oxidized palladium hollow ball.
2. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, described in step (1), Palladous nitrate concentration is 0.3mol/l, and the mol ratio of glycine and Palladous nitrate is 1: 1.
3. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, described in step (2), the mixed aqueous solution pH value is 9.
4. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, it is characterized in that, described in step (3), iron particle through the detailed process of palladium salt surface activation process is: at room temperature, iron particle is made an addition in the palladium nitrate aqueous solution of finite concentration and temperature, make a small amount of divalence palladium ion be deposited on the palladium activation point that the iron particle surface forms some amount at iron particle surface replacement iron atom.
5. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 5, is characterized in that, described palladium nitrate aqueous solution concentration is that 0.2mol/l, temperature are 40 ℃.
6. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, described in step (3), the iron particle diameter range is 20～150nm.
7. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, described in step (4), soaking time is 1 hour.
8. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, described in step (5), speed is 4ml/m.
9. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, the hydrogen peroxide that described in step (5), oxidizing agent solution is concentration 50%.
10. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, the dilute hydrochloric acid solution that described in step (6), acidic solution is concentration 10%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104264134A (en) * | 2014-09-19 | 2015-01-07 | 无锡长辉机电科技有限公司 | Formula of acid-based colloidal palladium activation solution |
| CN105293592A (en) * | 2014-07-30 | 2016-02-03 | 上海三爱思试剂有限公司 | Preparation method for nano palladium oxide |
| CN113772752A (en) * | 2021-08-04 | 2021-12-10 | 中国科学院广州地球化学研究所 | PdO2Preparation method of irregular conical nano-particle material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101552064A (en) * | 2008-12-16 | 2009-10-07 | 北京理工大学 | Method for preparing hollow magnetic ball |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101552064A (en) * | 2008-12-16 | 2009-10-07 | 北京理工大学 | Method for preparing hollow magnetic ball |
Non-Patent Citations (2)
| Title |
|---|
| ZHIHUI BAN ET AL.: "The synthesis of core-shell iron@gold nanoparticles and their characterization", 《J. MATER.CHEM.》, 31 December 2005 (2005-12-31) * |
| 余建民: "《贵金属化合物及配合物合成手册》", 28 February 2009, article "4.4.6 氧化钯", pages: 98-99 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293592A (en) * | 2014-07-30 | 2016-02-03 | 上海三爱思试剂有限公司 | Preparation method for nano palladium oxide |
| CN105293592B (en) * | 2014-07-30 | 2017-10-27 | 上海三爱思试剂有限公司 | A kind of preparation method of nano palladium oxide |
| CN104264134A (en) * | 2014-09-19 | 2015-01-07 | 无锡长辉机电科技有限公司 | Formula of acid-based colloidal palladium activation solution |
| CN113772752A (en) * | 2021-08-04 | 2021-12-10 | 中国科学院广州地球化学研究所 | PdO2Preparation method of irregular conical nano-particle material |
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