CN103449538B - Preparation method of nano palladium oxide hollow spheres - Google Patents
Preparation method of nano palladium oxide hollow spheres Download PDFInfo
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- CN103449538B CN103449538B CN201310275079.4A CN201310275079A CN103449538B CN 103449538 B CN103449538 B CN 103449538B CN 201310275079 A CN201310275079 A CN 201310275079A CN 103449538 B CN103449538 B CN 103449538B
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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
In orthodox car three-way catalyst, generate the way of palladous oxide particle with katalysis and be a certain amount of palladium salt is made an addition to by the slurry of catalyst coat powder and weakly acidic aqueous solution mixed preparing and be coated on support of the catalyst surface, then the carrier that is coated with catalyzer is heated to 500 DEG C and carries out above sintering.In sintering process, the palladium salt in slurry is the palladous oxide particle that is attached to 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 of preparing 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, like this form precious metal alloys catalytic activity relatively a little less than, this alloy and metal oxide containing precious metals are because particle is larger simultaneously, surface-area is relatively little, will cause the precious metal of particle inner core part directly to contact with exhaust gas component, reduce effectively making full use of of precious metal, the waste that causes precious metal to use.
The palladous oxide preparation method who exists is at present 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 using palladium chloric acid as 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 PVP stable chemical nature, be difficult to adopt chemical process to be removed, therefore generally adopt supercentrifugal process repeatedly to separate, this just defines widespread use to a certain extent.
Summary of the invention
Object 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 object that makes full use of and improve 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) adding a certain amount of aqueous sodium hydroxide solution to regulate the pH value of mixed solution is alkalescence;
(3) will join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide through the iron particle of palladium salt surface activation process;
(4) heating mixed aqueous solution to 85～95 DEG C, and insulation;
(5) under mechanical stirring, in mixed aqueous solution, be added dropwise to a certain amount of oxidizing agent solution with given pace, make the spheroidal particle with iron core-palladous oxide shell structure;
(6) by have iron core-palladous oxide shell structure particle take out clean after join molten deironing core mechanical stirring in acidic solution, 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), 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 of iron particle surface formation some amount at iron particle surface replacement iron atom, described palladium nitrate aqueous solution concentration is that 0.2mol/L, temperature are 40 DEG C.
Further, described in step (3), 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/min.
Further, described in step (5), oxidizing agent solution is the hydrogen peroxide of concentration 50%.
Further, described in step (6), acidic solution is the dilute hydrochloric acid solution of concentration 10%.
The effect that the present invention is useful is:
1, prepared palladous oxide is nanoscale, and therefore specific surface area is larger, and catalytic performance is stronger.
2. prepared palladous oxide is hollow structure, and density is less, and therefore sedimentation stability is good, in use can with the fine coupling of slurry.
3. prepared palladous oxide is hollow structure, and housing exists tiny cavity simultaneously, therefore can increase surface-area, improves catalytic performance.
Brief description of the drawings
Fig. 1 is palladous oxide hollow ball preparation process schematic diagram of the present invention;
In the accompanying drawings:
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 DEG C, be added dropwise to oxygenant hydrogen oxide palladous oxide with given pace in mixed solution, the palladium hydroxide that makes to be constantly adsorbed in nano-iron particle surface is that palladous oxide forms palladous oxide/iron nuclear particle 30 by slow oxidation.
By regulating the compactness extent of the addition ratio control iron particle surface oxidation palladium shell of palladium salt and iron particle in mixed solution, make to exist in palladous oxide shell a certain amount of small hole finally by step S103.After palladous oxide/iron nuclear particle 30 with iron core-palladous oxide shell structure is taken out to cleaning, join in dilute hydrochloric acid, utilize palladous oxide to be insoluble to dilute hydrochloric acid, make dilute hydrochloric acid pass through the molten deironing core of hole in palladous oxide shell, make nano oxidized palladium hollow ball 40.
Embodiment 1:
In water, make with sodium borohydride reduction ferrous sulfate the iron particle that diameter is about 150nm.It is that 0.2mol/L, temperature are in the palladium nitrate aqueous solution of 40 DEG C that the 10g nano-iron particle making 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 adding a certain amount of aqueous sodium hydroxide solution to regulate the pH value of mixed solution is 9.To join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide through the iron particle of palladium salt surface activation process, heating mixed solution to 95 DEG C insulation 1 hour, simultaneously under mechanical stirring to being added dropwise to the hydrogen peroxide 300mL of concentration as 50% taking the speed of 4mL/min in mixed solution, make spherical palladous oxide/iron nuclear particle with iron core-palladous oxide shell structure.By spherical palladous oxide/iron nuclear particle with iron core-palladous oxide shell structure, to add concentration to be in 10% hydrochloric acid soln and follow mechanical stirring 10 minutes, obtains nano oxidized palladium hollow ball.
Embodiment 2:
In water, make with sodium borohydride reduction ferrous sulfate the iron particle that diameter is about 20nm.It is that 0.2mol/L, temperature are in the palladium nitrate aqueous solution of 40 DEG C that the 10g nano-iron particle making 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 adding a certain amount of aqueous sodium hydroxide solution to regulate the pH value of mixed solution is 9.To join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide through the iron particle of palladium salt surface activation process, heating mixed solution to 85 DEG C insulation 1 hour, simultaneously under mechanical stirring to being added dropwise to the hydrogen peroxide 300mL of concentration as 50% taking the speed of 4mL/min in mixed solution, make spherical palladous oxide/iron nuclear particle with iron core-palladous oxide shell structure.By spherical palladous oxide/iron nuclear particle with iron core-palladous oxide shell structure, to add concentration to be in 10% hydrochloric acid soln and follow mechanical stirring 10 minutes, obtains nano oxidized palladium hollow ball.
Embodiment 3:
In water, make with sodium borohydride reduction ferrous sulfate the iron particle that diameter is about 50nm.It is that 0.2mol/L, temperature are in the palladium nitrate aqueous solution of 40 DEG C that the 10g nano-iron particle making 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 adding a certain amount of aqueous sodium hydroxide solution to regulate the pH value of mixed solution is 9.To join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide through the iron particle of palladium salt surface activation process, heating mixed solution to 90 DEG C insulation 1 hour, simultaneously under mechanical stirring to being added dropwise to the hydrogen peroxide 300mL of concentration as 50% taking the speed of 4mL/min in mixed solution, make spherical palladous oxide/iron nuclear particle with iron core-palladous oxide shell structure.By spherical palladous oxide/iron nuclear particle with iron core-palladous oxide shell structure, to add concentration to be in 10% hydrochloric acid soln and follow mechanical stirring 10 minutes, obtains 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, limit the scope of the invention and be not used in, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the amendment of the various equivalent form of values of the present invention.
Claims (9)
1. a preparation method for nano oxidized palladium hollow ball, is characterized in that, comprises the following steps:
(1) preparation Palladous nitrate, glycine mixed aqueous solution;
(2) adding a certain amount of aqueous sodium hydroxide solution to regulate the pH value of mixed solution is alkalescence;
(3) will join in the mixed aqueous solution of Palladous nitrate, glycine and sodium hydroxide through the iron particle of palladium salt surface activation process;
(4) heating mixed aqueous solution to 85～95 DEG C, and insulation;
(5) under mechanical stirring, in mixed aqueous solution, be added dropwise to a certain amount of oxidizing agent solution with given pace, make the spheroidal particle with iron core-palladous oxide shell structure;
(6) by have iron core-palladous oxide shell structure particle take out clean after join molten deironing core mechanical stirring in acidic solution, make nano oxidized palladium hollow ball;
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 of iron particle surface formation some amount at iron particle surface replacement iron atom.
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), mixed aqueous solution pH value is 9.
4. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, at described iron particle, in the detailed process of palladium salt surface activation process, palladium nitrate aqueous solution concentration is that 0.2mol/L, temperature are 40 DEG C.
5. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, described in step (3), iron particle diameter range is 20～150nm.
6. 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.
7. 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/min.
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), oxidizing agent solution is the hydrogen peroxide of concentration 50%.
9. the preparation method of a kind of nano oxidized palladium hollow ball according to claim 1, is characterized in that, described in step (6), acidic solution is the dilute hydrochloric acid solution of concentration 10%.
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| 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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| CN101552064A (en) * | 2008-12-16 | 2009-10-07 | 北京理工大学 | Method for preparing hollow magnetic ball |
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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 (3)
| Title |
|---|
| Zhihui Ban et al..The synthesis of core-shell iron@gold nanoparticles and their characterization.《J. Mater.Chem.》.2005,全文. |
| Zhihui Ban et al..The synthesis of core-shell irongold nanoparticles and their characterization.《J. Mater.Chem.》.2005,全文. * |
| 余建民.4.4.6 氧化钯.《贵金属化合物及配合物合成手册》.2009,第98-99页. * |
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