CN1883853A - Platinum metal nano-particle size control growth method - Google Patents
Platinum metal nano-particle size control growth method Download PDFInfo
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- CN1883853A CN1883853A CN 200610088168 CN200610088168A CN1883853A CN 1883853 A CN1883853 A CN 1883853A CN 200610088168 CN200610088168 CN 200610088168 CN 200610088168 A CN200610088168 A CN 200610088168A CN 1883853 A CN1883853 A CN 1883853A
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Abstract
Provided is a controlled growing method of platinum or palladium metal nano-grain size. The present invention uses dialysis purified monodispersive nanometer platinum or palladium metal grain of small diameter as a crystal seed, effectively controls the size of the platinum metal nano-grain crystal nucleus in the epitaxial growth direction through circulation with hydrogen absorption, reduction and dialysis methods relying on the hydrogen absorption character of platinum or palladium metal and obtains uniformly distributed platinum metal nano-grains with different sizes within relatively bigger granular diameter.
Description
Technical field
The present invention relates in environment amenable aqueous systems platinum (Pt) or palladium (Pd) method of metal nanoparticles in the preparation platinum group, particularly a kind of can be in certain particle size range inner control platinum group the method for platinum (Pt) or the growth of palladium (Pd) metal nanoparticle size.
Background technology
The nanometer platinum metal, particularly platinum (Pt) or palladium (Pd) cause people's common concern because of having high catalytic activity, and the size of platinum (Pt) or palladium (Pd) metal nanoparticle particle diameter directly influences its catalytic activity (Radha N, Mostafa A.E1-Sayed J.Phys.Chem.B.2003,07:12416; Rakesh K S, Parvesh S, Amarnath M.Journal of Colloid and lnteface Science, 2003,265:134; Claus P, Hofmeister H., Phys.Chem.B, 1999,103:2766 ﹠amp; Y, Boone E, E1-Sayed M A.Langmuir, 2002,18:4921), it is significant undoubtedly therefore the nano particle size of platinum metal to be carried out controlledly synthesis.In the prior art, the metal nanoparticle size was carried out the most successful example of controlledly synthesis can be described as gold nano grain (Daniel M C, Astruc D.Chem.Rev., 2004,104:293 ﹠amp in the past; Brust M, Kiely C.J.Colloids andsurfaces A:Physicochemical and Engineering Aspects, 2002,202:44O9).Yet relative gold nano grain, platinum in the platinum metal (Pt) or the research in this respect of palladium (Pd) nano particle are also less.People such as Toshima are by changing protective agent PVP (polyvinylpyrrolidone) and chloroplatinic acid (H
2PtCI
6) proportioning change platinum (Pt) nano particle size (Toshima N, Shiraishi Y, Nakayama M, et al.Inorganica chimica Acta, 2000,300-302:964).With usually the same, the preparation of platinum (Pt) nano particle is with the increase of protective agent consumption, and particle grain size diminishes, but the nano particle size variation of this method acquisition can not effectively control, perhaps controlled ability a little less than.And in certain change of size scope effectively in the control platinum metal technical scheme of the nano particle size of platinum (Pt) or palladium (Pd) do not appear in the newspapers as yet.
Summary of the invention
The invention provides a kind of control growing method of platinum metal nano-particle size, its objective is will be in environment amenable aqueous systems, obtain a kind of platinum (Pt) or palladium (Pd) nanoparticle growth size and good method of distribution uniformity in the platinum metal of in certain change of size scope, effectively controlling, to overcome the prior art deficiency.
For achieving the above object, the technical solution used in the present invention is: a kind of control growing method of platinum metal nano-particle size, in aqueous systems, it is nanocrystalline as nucleus that the particle diameter of purifying with dialysis is less than or equal to platinum or the palladium metal of 3nm, controls growth by following steps:
(1), inhales hydrogen
With platinum or palladium metal is nanocrystalline is dispersed in the aqueous systems as nucleus, feed hydrogen, make platinum or palladium metal nano particle fully inhale hydrogen;
(2), reduction
Platinum or palladium metal Nano sol behind the suction hydrogen are transferred in the container of another reagent that adds corresponding platinum metal in advance, stirred, fully reaction; The reagent and the consumption of described corresponding platinum metal are as follows:
Reagent at the corresponding platinum metal of platinum Nano sol is selected chloroplatinic acid, and molecular formula is H
2PtCI
6, concentration is 1～9mmol/L, the best is 2～5mmol/L;
At the reagent selective chlorination palladium of the corresponding platinum metal of palladium metal Nano sol, molecular formula is PdCl
2Concentration is 1～9mmol/L, and the best is 2～5mmol/L; Perhaps select acid chloride, molecular formula is Pd (CH
3COO)
2, concentration is 1～9mmol/L, the best is 2～5mmol/L;
(3), dialysis
Remove the ion of unreacted platinum metal reagent with redistilled water fully by dialysis process, finish the one step growth of platinum or palladium metal nano particle, the nano particle that obtains growing up;
Repeat above-mentioned suction hydrogen, reduction and dialysis step, obtain the platinum or the palladium metal nano particle of different growth particle diameters.
Related content in the such scheme is explained as follows:
1, in the such scheme, the nanocrystalline particle diameter of described platinum or palladium metal is 0.5～3nm.
2, nanocrystalline for purify platinum or palladium metal, make unnecessary NaBH
4Do not influence follow-up suction hydrogen reduction extension on nucleus with other ion, can utilize dialysis to purify in advance singly to disperse, stable metallic nano crystal colloidal sol.
3, carry out on nanocrystalline in order to guarantee that reduction is grown in, must make the nanocrystalline abundant suction hydrogen of platinum metal.
4, not form new nucleus in order guaranteeing in the operating process of follow-up suction hydrogen, promptly not generate new little nano particle, adding will dialyse after the platinum metal reagent solution reacts at every turn fully removes unnecessary unreacted metal reagent ion.
5, certain, in order to control the growth of platinum or palladium metal nano particle, at first should prepare single nanometer platinum metal particle of small particle diameter that disperses as crystal seed.And this method can adopt prior art to prepare.
The principle of the invention is: the nanometer platinum of single dispersion small particle diameter that utilizing dialyses purifies or palladium metal particle are as crystal seed, has the character of absorption hydrogen by means of platinum or palladium metal, adopt the method for inhaling hydrogen, reduction, dialysis, pass through cycle-index, effectively control epitaxially grown size on the platinum metal nano-particle nucleus, in certain particle size range, obtain the platinum metal nano-particle of different-grain diameter with this, its size distribution is than homogeneous.
Because the utilization of such scheme, the present invention compared with prior art has following advantage and effect:
1, the present invention has used simple and effective suction hydrogen to restore method in aqueous systems, controls growth by cycle-index, in certain particle size range, obtains the platinum metal nano-particle of different-grain diameter, and the particle size range of control growth is 1.5～14nm.
2, since the present invention after each growth circulation finishes, adopt complete dialysis process to remove unnecessary unreacted platinum metal reagent ion, guaranteed not form new nucleus in the operating process of follow-up suction hydrogen, promptly do not generate new little nano particle, therefore the platinum metal nano-particle size distribution that obtains is than homogeneous.
Description of drawings
Accompanying drawing 1 is inhaled the progressively growth flow chart that hydrogen reduction generates platinum metal nano-particle for nano particle of the present invention.Wherein, M represents that platinum metal is nanocrystalline.
Accompanying drawing 2 is TEM (transmission electron microscope) photo of the platinum metal nano-particle of the different number of times growths of embodiment one and embodiment two one group, and wherein, the No.0 photo represents that platinum is nanocrystalline; The No.5 photo is represented the platinum metal nano-particle behind 5 secondary growths; The No.10 photo is represented the platinum metal nano-particle behind 10 secondary growths; The No.15 photo is represented the platinum metal nano-particle behind 15 secondary growths.
Accompanying drawing 3 is TEM (transmission electron microscope) photo of the palladium metal nano particle of the different number of times growths of embodiment three and embodiment four one group, and wherein, the No.1 photo is represented the palladium metal nano particle behind 1 secondary growth; The No.5 photo is represented the palladium metal nano particle behind 5 secondary growths; The No.10 photo is represented the palladium metal nano particle behind 10 secondary growths; The No.15 photo is represented the palladium metal nano particle behind 15 secondary growths.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one:
1. the Pt nanoparticle crystal seed is synthetic
Get 8.6mL H
2PtCI
6(6.1mmol/L) solution takes by weighing 86mg PVP (polyvinylpyrrolidone), and the PVP mean molecule quantity is 40,000, add in people's beaker, the amount of PVP is to add 15 times of chloroplatinic acid amount at first, add redistilled water to 58ml, under constantly stirring, slowly drip the 1%NaBH of new preparation
4Solution 2ml, solution become transparent grey black by faint yellow at once, and have a large amount of bubbles to emerge, and continue stirred for several hour, remove unnecessary NaBH with the redistilled water dialysis
4With other ion, make platinum colloidal sol as the Pt nanoparticle crystal seed.
2. the control of Pt nanoparticle growth
Synthetic platinum colloidal sol is added the people in flask, and logical hydrogen 1h makes Pt nanoparticle fully inhale hydrogen, and the platinum colloidal sol behind the suction hydrogen is transferred to the 0.8ml H that another adds in advance
2PtCI
6(6.1mmol/L) in the solution flask, stir, fully react 3h after, with the redistilled water dialysis, finish the one step growth of platinum grain like this, the Pt nanoparticle that obtains growing up.Allow the platinum grain continued growth, repeat above-mentioned suction hydrogen, reduction, dialysis, obtain the Pt nanoparticle behind the different growth number of times.Committed step is to add the unnecessary chloroplatinic acid of will dialysing fully after chloroplatinic acid reacts at every turn, could guarantee so not form new nucleus in the operating process of follow-up suction hydrogen, does not promptly generate new little nano particle.The platinum metal nano-particle of different number of times growths is referring to shown in Figure 2.
Embodiment two:
1. the Pt nanoparticle crystal seed is synthetic
Get 8.6mL H
2PtCI
6(6.1mmol/L) solution takes by weighing 117mg PVP (polyvinylpyrrolidone), and the PVP mean molecule quantity is 40,000, add in people's beaker, the amount of PVP is to add 20 times of chloroplatinic acid amount at first, add redistilled water then to 58ml, under constantly stirring, slowly drip the 1%NaBH of new preparation
4Solution 2ml, solution become transparent grey black by faint yellow at once, and have a large amount of bubbles to emerge, and continue stirred for several hour, remove unnecessary NaBH with the redistilled water dialysis
4With other ion, make platinum colloidal sol as the Pt nanoparticle crystal seed.
2. the control of Pt nanoparticle growth
Synthetic platinum colloidal sol is added the people in flask, and logical hydrogen 1h makes Pt nanoparticle fully inhale hydrogen, and the platinum colloidal sol behind the suction hydrogen is transferred to the 0.8ml H that another adds in advance
2PtCl
6(6.1mmol/L) in the solution flask, stir, fully react 3h after, with the redistilled water dialysis, finish the one step growth of platinum grain like this, the Pt nanoparticle that obtains growing up.Allow the platinum grain continued growth, repeat above-mentioned suction hydrogen, reduction, dialysis, obtain the Pt nanoparticle behind the different growth number of times.Committed step is to add the unnecessary chloroplatinic acid of will dialysing fully after people's chloroplatinic acid reacts at every turn, could guarantee so not form new nucleus in the operating process of follow-up suction hydrogen, does not promptly generate new little nano particle.The platinum metal nano-particle of different number of times growths is referring to shown in Figure 2.
Embodiment three:
1. the palladium nano-particles crystal seed is synthetic
Get 8.6ml PdCl
2(6.1mmol/L) solution takes by weighing 86mg PVP (polyvinylpyrrolidone), and the PVP mean molecule quantity is 40,000, add in people's beaker, the amount of PVP is to add 15 times of palladium bichloride amount at first, add redistilled water to 58ml, under constantly stirring, slowly drip the 1%NaBH of new preparation
4Solution 2ml, solution become transparent grey black by faint yellow at once, and have a large amount of bubbles to emerge, and continue stirred for several hour, remove unnecessary NaBH with the redistilled water dialysis
4With other ion, make palladium metal colloidal sol as the palladium nano-particles crystal seed.
2. the control of palladium nano-particles growth
Synthetic palladium colloidal sol is added the people in flask, and logical hydrogen 1h makes palladium nano-particles fully inhale hydrogen, and the palladium colloidal sol behind the suction hydrogen is transferred to the 0.8ml PdCl that another adds in advance
2(6.1mmol/L) in the solution flask, stir, fully react 3h after, with the redistilled water dialysis, finish the one step growth of palladium particle like this, the palladium nano-particles that obtains growing up.Allow the continued growth of palladium particle, repeat above-mentioned suction hydrogen, reduction, dialysis, obtain the palladium nano-particles behind the different growth number of times.Committed step is to add the unnecessary palladium bichloride of will dialysing fully after people's palladium bichloride reacts at every turn, could guarantee so not form new nucleus in the operating process of follow-up suction hydrogen, does not promptly generate new little nano particle.The palladium metal nano particle of different number of times growths is referring to shown in Figure 3.
Embodiment four:
1. the palladium nano-particles crystal seed is synthetic
Get 8.6ml PdCl
2(6.1mmol/L) solution takes by weighing 117mg PVP (polyvinylpyrrolidone), and the PVP mean molecule quantity is 40,000, add in people's beaker, the amount of PVP is to add 15 times of palladium bichloride amount at first, add redistilled water to 58mL, under constantly stirring, slowly drip the 1%NaBH of new preparation
4Solution 2ml, solution become transparent grey black by faint yellow at once, and have a large amount of bubbles to emerge, and continue stirred for several hour, remove unnecessary NaBH with the redistilled water dialysis
4With other ion, make palladium metal colloidal sol as the palladium nano-particles crystal seed.
2. the control of palladium nano-particles growth
Synthetic palladium colloidal sol is added the people in flask, and logical hydrogen 1h makes palladium nano-particles fully inhale hydrogen, and the palladium colloidal sol behind the suction hydrogen is transferred to the 0.8ml PdCl that another adds in advance
2(6.1mmol/L) in the solution flask, stir, fully react 3h after, with the redistilled water dialysis, finish the one step growth of palladium particle like this, the palladium nano-particles that obtains growing up.Allow the continued growth of palladium particle, repeat above-mentioned suction hydrogen, reduction, dialysis, obtain the palladium nano-particles behind the different growth number of times.Committed step is to add the unnecessary palladium bichloride of will dialysing fully after people's palladium bichloride reacts at every turn, could guarantee so not form new nucleus in the operating process of follow-up suction hydrogen, does not promptly generate new little nano particle.The palladium metal nano particle of different number of times growths is referring to shown in Figure 3.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (3)
1, a kind of control growing method of platinum metal nano-particle size is characterized in that: in aqueous systems, it is nanocrystalline as nucleus that the particle diameter of purifying with dialysis is less than or equal to platinum or the palladium metal of 3nm, controls growth by following steps:
(1), inhales hydrogen
With platinum or palladium metal is nanocrystalline is dispersed in the aqueous systems as nucleus, feed hydrogen, make platinum or palladium metal nano particle fully inhale hydrogen;
(2), reduction
Platinum or palladium metal Nano sol behind the suction hydrogen are transferred in the container of another reagent that adds corresponding platinum metal in advance, stirred, fully reaction; The reagent and the consumption of described corresponding platinum metal are as follows:
Reagent at the corresponding platinum metal of platinum Nano sol is selected chloroplatinic acid, and molecular formula is H
2PtCI
6, concentration is 1～9mmol/L;
At the reagent selective chlorination palladium of the corresponding platinum metal of palladium metal Nano sol, molecular formula is PdCl
2Concentration is 1～9mmol/L, perhaps selects acid chloride, and molecular formula is Pd (CH
3COO)
2, concentration is 1～9mmol/L;
(3), dialysis
Remove the ion of unreacted platinum metal reagent with redistilled water fully by dialysis process, finish the one step growth of platinum or palladium metal nano particle, the nano particle that obtains growing up;
Repeat above-mentioned suction hydrogen, reduction and dialysis step, obtain the platinum or the palladium metal nano particle of different growth particle diameters.
2, the control growing method of platinum metal nano-particle size according to claim 1 is characterized in that: the nanocrystalline particle diameter of platinum or palladium metal is 0.5～3nm.
3, the control growing method of platinum metal nano-particle size according to claim 1 is characterized in that: in the described reduction step, chloroplatinic acid concentration is 2～5mmol/L; Palladium bichloride concentration is 2～5mmol/L; Acid chloride concentration is 2～5mmol/L.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775638A (en) * | 2010-03-24 | 2010-07-14 | 中国科学院长春应用化学研究所 | Preparation method of palladium nano crystal |
| CN101450380B (en) * | 2007-12-03 | 2010-10-06 | 国家纳米科学中心 | Preparation method of bimetal nano rod of branched gold core/platinum shell structure |
| CN102211198A (en) * | 2011-05-25 | 2011-10-12 | 云南大学 | Method for synthesizing water-soluble Pt: ZnSe(S) alloyed nanometer crystal by using hydro-thermal method |
| CN105689725A (en) * | 2016-02-04 | 2016-06-22 | 中国科学院金属研究所 | Method for preparing metal palladium or palladium alloy nanowires |
| CN109865845A (en) * | 2019-03-29 | 2019-06-11 | 无锡英特派金属制品有限公司 | The preparation method of high-density palladium powder |
| CN110479250A (en) * | 2019-08-30 | 2019-11-22 | 上海交通大学 | A method of one-dimensional platinum base nano material is prepared based on reducibility gas auxiliary |
-
2006
- 2006-06-30 CN CN 200610088168 patent/CN1883853A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450380B (en) * | 2007-12-03 | 2010-10-06 | 国家纳米科学中心 | Preparation method of bimetal nano rod of branched gold core/platinum shell structure |
| CN101775638A (en) * | 2010-03-24 | 2010-07-14 | 中国科学院长春应用化学研究所 | Preparation method of palladium nano crystal |
| CN102211198A (en) * | 2011-05-25 | 2011-10-12 | 云南大学 | Method for synthesizing water-soluble Pt: ZnSe(S) alloyed nanometer crystal by using hydro-thermal method |
| CN102211198B (en) * | 2011-05-25 | 2013-05-22 | 云南大学 | Method for synthesizing water-soluble Pt: ZnSe(S) alloyed nanometer crystal by using hydro-thermal method |
| CN105689725A (en) * | 2016-02-04 | 2016-06-22 | 中国科学院金属研究所 | Method for preparing metal palladium or palladium alloy nanowires |
| CN109865845A (en) * | 2019-03-29 | 2019-06-11 | 无锡英特派金属制品有限公司 | The preparation method of high-density palladium powder |
| CN110479250A (en) * | 2019-08-30 | 2019-11-22 | 上海交通大学 | A method of one-dimensional platinum base nano material is prepared based on reducibility gas auxiliary |
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