CN104722775A - Two-dimensional hollow palladium nanocrystal and preparation method thereof - Google Patents
Two-dimensional hollow palladium nanocrystal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a two-dimensional hollow palladium nanocrystal. A palladium nanoseed, a palladium precursor, a bromide ion modifier, a reductive agent and a dispersing agent are added into solvent for reacting, and accordingly the two-dimensional hollow palladium nanocrystal is prepared, wherein the palladium nanoseed is a palladium nanosheet. According to the preparation method, the nanosheet is used as the seed to be further reacted so that the two-dimensional hollow palladium nanocrystal can be prepared. Operating is easy, the reaction condition is mild, the reagent is low in price, the toxicity is small, and implementation is easy. The invention further discloses the two-dimensional hollow palladium nanocrystal prepared through the preparation method. The upper surface and the lower surface of the two-dimensional hollow palladium nanocrystal are {111} crystal faces, the thickness of the two-dimensional hollow palladium nanocrystal is 2-4 nm, the two-dimensional hollow palladium nanocrystal is of an ultrathin annular structure, the material specific area and the atom utilization rate are improved, and the catalytic performance of the palladium nanocrystal is effectively enhanced.
Description
Technical field
The present invention relates to the preparation field of noble metal nanometer material, particularly relate to a kind of two-dimentional hollow palladium nano-crystal and preparation method thereof.
Background technology
Palladium nano-crystal is as a kind of important noble metal nanometer material, the catalytic performance good due to it and comparatively cheap price are widely used in hydrogenation reaction, carbon-to-carbon coupling and the field such as carbon monoxide process, and some achievements in research in recent years also find that palladium nano-crystal also has potential application in surface plasma body resonant vibration etc.
Research shows, the pattern of palladium nano-crystal has a great impact its performance tool, the pattern controlling palladium nano-crystal is the focus studied in the industry always, at present existing a lot of bibliographical information is by the Pd nano particle of multiple nanostructured that utilized balance controlled method to prepare, comprise tetrahedron, cube, octahedron, decahedron, icosahedron, pyrometric cone, bar-shaped and nano flower etc., these nano particles mostly are the solid with three dimensional symmetry structure.
The three dimensional symmetry structure of palladium nano-crystal is for two-dimensional structure, and specific area and atom utilization are all lower, although the two-dimensional sheet structure of palladium early has report, its synthesis all needs, by this hypertoxic gas of carbon monoxide, to have certain danger.
Application number be 201010160739.0 Chinese patent application disclose a kind of synthetic method of palladium nano sheet, add palladium presoma, surface protectant, the organic salt of halogen-containing ion or the inorganic salts of halogen-containing ion in a solvent, obtain mixed liquor; Under mixed liquor being placed in CO atmosphere, being warming up to 10 ~ 200 DEG C, then cooling the temperature to room temperature, add acetone centrifugal purification, cleaning, obtains hexagon palladium nano sheet.The palladium nano sheet productive rate of the method synthesis is high, and uniform particle sizes, has superthin structure (about 1.8nm), specific area is comparatively large, and atom utilization is high, presents very high catalytic activity, but the method needs by hypertoxic gas CO, require very high for experimental situation and operating process.
Zhang Hui, Li Yi etc. are at Size-Controlled Synthesis of Pd Nanosheets for Tunable Plasmonic Properties (CrystEngComm, 2015,17,1833-1838) report another preparation method of palladium nano sheet in a literary composition.Palladium salt, softex kw (CTAB), tungsten carbonyl, citric acid (CA) and polyvinylpyrrolidone (PVP) are joined N by the method, react in N-dimethylformamide (DMF), prepare hexagon palladium nano sheet.The method uses tungsten carbonyl to instead of CO, and handling safety is simple, and obtained nanometer sheet thickness is thinner, only has about 1nm, substantially increases material specific surface area and atom utilization.
Hollow-core construction improves another effective way of material specific surface area and atom utilization, hollow-core construction and two-dimensional sheet structure combined and provide a kind of new approaches of synthesis.The preparation of easy, safe method is adopted to have the nanocrystalline of ultra-thin two-dimension structure and hollow-core construction concurrently, effectively can not only improve the catalytic performance of palladium nano-crystal, also facilitate the industrialization process of palladium nano-crystal to a certain extent, there is important learning value and realistic meaning.
Summary of the invention
The invention provides a kind of preparation method of two-dimentional hollow palladium nano-crystal, described preparation method obtains two-dimentional hollow palladium nano-crystal using palladium nano sheet as seed, this preparation method is simple to operate, and reaction condition is gentle, easily realizes.
A preparation method for two-dimentional hollow palladium nano-crystal, joins palladium nanometer seed, palladium presoma, bromide ion dressing agent, reducing agent and dispersant in solvent and reacts, prepare two-dimentional hollow palladium nano-crystal; Described palladium nanometer seed is palladium nano sheet.
The mechanism that the present invention prepares two-dimentional hollow palladium nano-crystal is: the Br in bromide ion dressing agent
-to the side of palladium nano sheet (namely { 100} face), there is strong adsorption capacity, the side of palladium nano sheet is effectively protected, make the palladium atom be reduced can only grow upper and lower surface ({ 111} face) at palladium nano sheet, increase the thickness of palladium nano sheet; On the other hand, the oxygen dissolved in the bromide ion that provides of bromide ion dressing agent and solution forms oxide etch to Br
-/ O
2, because the side of palladium nano sheet is by available protecting, cannot with O
2contact, remaining Br in solution
-with O
2can only attack Pd{111} face.Because solution is carry out from periphery to center to the diffusion of palladium nano sheet, therefore the speed of growth of the palladium atom be reduced at peripheral position is obviously greater than the speed of growth in centre, the relation of this local epitaxial growth, part thinner on palladium nano sheet and core become the existence be the most easily etched, along with the carrying out of reaction, after finally causing the centre of palladium nano sheet to be fully oxidized etching, form hollow.
The selective longitudinal growth of preparation method of the present invention and oxide etch are carried out simultaneously, the two-dimentional hollow palladium nano-crystal of final acquisition.
Described palladium nano sheet adopts existing preparation method to obtain hexagon palladium nano sheet, but the nanometer sheet that the present invention does not get rid of other shapes of employing prepares two-dimentional hollow palladium nano-crystal.Palladium nano sheet seed is the factor preparing two-dimentional hollow palladium nano-crystal outbalance, because the side of palladium nano sheet modified by bromide ion dressing agent, palladium nano sheet can not cross growth, therefore the size of palladium nano sheet determines the size of two-dimentional hollow palladium nano-crystal, as preferably, the length of side of hexagon palladium nano sheet is 5 ~ 50nm.
The thickness effect etching speed of palladium nano sheet, palladium nano sheet is blocked up causes etching speed comparatively slow, is difficult to obtain the palladium nano-crystal of hollow, and as preferably, the thickness of palladium nano sheet is 0.8 ~ 1.8nm.
The concentration of palladium nano sheet affects etching degree, and palladium nano sheet excessive concentration causes etching imperfect, cannot realize hollow structure, and palladium nano sheet concentration is too low causes etching excessively, destroys nanometer sheet integrality, and as preferably, the concentration of described palladium nano sheet is 1.0 × 10
-3~ 3.0 × 10
-3mol/L.
Another key factor preparing two-dimentional hollow palladium nano-crystal is bromide ion dressing agent.If do not add bromide ion dressing agent in reaction system, the product obtained is the outer nanometer sheet slightly thickeied that makes a circle, and the mid portion of nanometer sheet remains solid, illustrates that not having bromide ion dressing agent to deposit oxide etch be in case impossible.
Described bromide ion dressing agent is selected from KBr, sodium bromide, TBAB or softex kw, as preferably, described bromide ion dressing agent is selected from KBr or softex kw, and the etching that preferred bromide ion dressing agent and dissolved oxygen form is stronger to etching power.
The concentration of bromide ion dressing agent affects size and the etching speed of two-dimentional hollow palladium nano-crystal, and the bromide ion dressing agent of high concentration easily causes etching excessively, destroys the structure of two-dimentional hollow palladium nano-crystal; The bromide ion dressing agent of low concentration fully can not modify the side of palladium nano sheet, causes palladium nano sheet cross growth.As preferably, the concentration of bromide ion dressing agent is 8.0 × 10
-3~ 4.0 × 10
-2mol/L.
In the preparation method of two-dimentional hollow palladium nano-crystal, the selection of reaction temperature is also very important, and too low growth and the etching of causing of temperature all cannot be carried out; Temperature is too high to be caused by force etched, and the growth of palladium atom is not selective; As preferably, reaction temperature is 80 ~ 120 DEG C.
As preferred further, reaction temperature is 80 ~ 100 DEG C, and at preferred temperature, growth and etching are all normally carried out.
The reaction time of described preparation method is too short, and palladium nano-crystal centre is solid construction; Reaction time is long, easily causes palladium nano-crystal by force etched, destroys the structure of hollow two dimension palladium nano-crystal.As preferably, the reaction time is 1 ~ 2h.
If do not add palladium presoma in reaction system, the product obtained is the irregular hollow palladium nano-crystal of a large amount of cut, and due to the thickness that nanometer sheet is ultra-thin, once the space that etching produces is excessive, the overall structure of nanometer sheet will become very fragile, finally cause the structural damage of hollow two dimension palladium nano-crystal, therefore need in reaction system to add a certain amount of palladium presoma, described palladium presoma is selected from palladium acetylacetonate, palladium or palladium nitrate.
The concentration of palladium presoma affects the thickness of two-dimentional hollow palladium nano-crystal, and as preferably, the concentration of palladium presoma is 1.0 × 10
-3~ 3.0 × 10
-3mol/L.
Described reducing agent is selected from ascorbic acid or ethylene glycol, and described reducing agent is comparatively gentle, can control the speed of reacting.
The concentration of reducing agent can affect rate of reduction, and rate of reduction affects thickness and the uniformity of palladium nano-crystal, and as preferably, the concentration of reducing agent is 1.0 × 10
-2~ 3.0 × 10
-2mol/L, under preferred concentration, the thickness of the two-dimentional hollow palladium nano-crystal obtained is 2 ~ 4nm, and size is comparatively even.
Add dispersant in described reaction system, can prevent palladium nano-crystal from assembling.Described dispersant is selected from polyvinylpyrrolidone, polymine or dodecyl sodium sulfate; The concentration of dispersant is 1.0 × 10
-2~ 5.0 × 10
-2mol/L.
Consider palladium nano sheet, palladium presoma, bromide ion dressing agent, reducing agent and dispersant dissolubility in a solvent, dispersiveness and stability.Described solvent is selected from DMF, DMA, water or phenmethylol.
As preferably, the preparation method of two dimension hollow palladium nano-crystal is as follows: palladium nano sheet, palladium acetylacetonate, softex kw, ascorbic acid and polyvinylpyrrolidone are joined N, react in N-dimethylformamide, prepare two-dimentional hollow palladium nano-crystal, reaction temperature is 80 ~ 100 DEG C, and the reaction time is 1 ~ 2h; Under optimum condition, the thickness of obtained two-dimentional hollow palladium nano-crystal is 2 ~ 4nm.
As preferably, the concentration of palladium nano sheet is 1.0 × 10
-3~ 1.5 × 10
-3mol/L, the concentration of palladium acetylacetonate is 1.0 × 10
-3~ 1.5 × 10
-3mol/L, the concentration of softex kw is 8.2 × 10
- 3~ 3.3 × 10
-2mol/L, the concentration of ascorbic acid is 2.5 × 10
-2~ 3.0 × 10
-2mol/L, the concentration of polyvinylpyrrolidone is 4.0 × 10
-2~ 5.0 × 10
-2mol/L.
The two-dimentional hollow palladium nano-crystal that the present invention also provides described preparation method to obtain, the upper and lower surface of described two-dimentional hollow palladium nano-crystal is that { 111} crystal face, thickness is 2 ~ 4nm.Two-dimentional hollow palladium nano-crystal provided by the invention improves material specific surface area and atom utilization, effectively enhances the catalytic performance of palladium.
Compared with prior art, the present invention has following beneficial effect:
Palladium nanometer seed, palladium presoma, bromide ion dressing agent, reducing agent and dispersant join in solvent and react by preparation method that the present invention adopts in the lump, simple to operate, and reaction condition is gentle, and inexpensively, toxicity is little for agents useful for same, easily realizes.
Two-dimentional hollow palladium nano-crystal provided by the invention is a kind of ultra-thin circulus, improves material specific surface area and atom utilization, effectively enhances the catalytic performance of palladium.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of the palladium nano sheet of embodiment 1 step one preparation, wherein: transmission electron microscope (TEM) figure that figure (a) is palladium nano sheet, figure (b) are palladium nano sheet attachment side view on the carbon nanotubes;
Fig. 2 is the transmission electron microscope figure of two-dimentional hollow palladium nano-crystal prepared by embodiment 1; Wherein: the transmission electron microscope figure that figure (a) and figure (b) is different amplification; High resolution transmission electron microscopy (HRTEM) figure that figure (c) is the two-dimentional upper and lower surface of hollow palladium nano-crystal; The high resolution transmission electron microscopy figure that figure (d) is two-dimentional hollow palladium nano-crystal side;
Fig. 3 reacts the transmission electron microscope figure of the palladium nano-crystal that different time obtains for embodiment 1; Wherein:
Figure (a), figure (b), figure (c), figure (d) are respectively the transmission electron microscope figure of the palladium nano-crystal that 5min, 10min, 30min and 1h obtain, and the figure in the upper right corner is corresponding high multiple transmission electron microscope figure;
Fig. 4 is the transmission electron microscope figure that embodiment 1 reacts the palladium nano-crystal that 24h obtains;
Fig. 5 is the palladium nano sheet of embodiment 2 and 3 preparation and the transmission electron microscope figure of two-dimentional hollow palladium nano-crystal; Wherein:
Figure (a) and figure (c) is respectively the transmission electron microscope figure of two-dimentional hollow palladium nano-crystal prepared by the palladium nano sheet of embodiment 2 step one preparation and step 2;
Figure (b) and figure (d) is respectively the transmission electron microscope figure of two-dimentional hollow palladium nano-crystal prepared by the palladium nano sheet of embodiment 3 step one preparation and step 2.
Fig. 6 is the transmission electron microscope figure of the palladium nano-crystal prepared under different situations; Wherein: when Fig. 6 (a) is not for adding bromide ion dressing agent, when Fig. 6 (b) is not for adding palladium presoma.
Detailed description of the invention
Embodiment 1
Step one, 16mg palladium acetylacetonate, 60mg softex kw, 100mg tungsten carbonyl, 90mg citric acid and 30mg polyvinylpyrrolidone are dissolved in 10mL N, in N-dimethylformamide, stirring 1h makes each material fully dissolve, reactant liquor is transferred in 25mL round-bottomed flask, under 80 DEG C of conditions, reacts 1h.After having reacted, reactant liquor is centrifugal, obtain hexagon palladium nano sheet.As shown in Figure 1, the thickness of hexagon palladium nano sheet is 1nm to palladium nano sheet pattern, and average side length is 15.7nm.
Step 2, by the 4mg palladium nano sheet that obtains in step one and 4mg palladium acetylacetonate, 60mg softex kw, 50mg ascorbic acid and 50mg polyvinylpyrrolidone (M
w=30000) join in 10mL DMF, stir 10min and palladium acetylacetonate, cetyl ammonium bromide, ascorbic acid and polyvinylpyrrolidone are fully dissolved, reactant liquor is transferred in 25mL round-bottomed flask, at 80 DEG C, reacts 1h.The reactant liquor that takes a morsel is centrifugal, obtains two-dimentional hollow palladium nano-crystal, preparation TEM sample, by its pattern of transmission electron microscope observation, as schemed shown in (a) and figure (b) in Fig. 2; Figure (c) and figure (d) is the high resolution transmission electron microscopy figure of the upper and lower surface of palladium nano-rings and side, the spacing of lattice marked in figure shows that palladium nano-rings upper and lower surface is so that { 111} crystal face exposes crystal face for it, and the thickness of two-dimentional hollow palladium nano-crystal only has 2nm, average side length is 15.7nm.
In order to study the formation mechenism of this special two-dimentional hollow palladium nano-crystal structure, the sign of transmission electron microscope has been carried out to the sample reacting different time, at initial reaction stage (Fig. 3 (a), reaction time is 5min), the pattern of nanometer sheet seems not change, but amplifying to examine to sample can find (Fig. 3 (a) upper right corner illustration), the contrast at nanometer sheet edge is darker than center, represents and has had some palladium atomic depositions to arrive the periphery on the upper and lower surface of nanometer sheet.When reaction proceeds to 10min (Fig. 3 (b)), more palladium atomic deposition is to the periphery on the upper and lower surface of nanometer sheet, and this local epitaxy causes the contrast difference mutation of nanometer sheet center and surrounding to obtain more and more obvious.Meanwhile, the Br existed in system
-with the O in air
2composition oxide etch pair, from Fig. 3 (a), the hole that just can some be found in nanometer sheet little or pit.And due to Br
-to Pd the adsorption capacity that 100} face is strong, the side of nanometer sheet is effectively protected, cannot with O
2contact.Remaining Br in solution
-with O
2can only attack Pd{111} face.And due to the relation of local epitaxial growth, part thinner in nanometer sheet and core become the position be the most easily etched, along with the carrying out of reaction is fallen by oxide etch gradually.Extend to 30min (Fig. 3 c) when reacted, the pattern of hexagon nano-rings basically forms, and middle hole also expands gradually with obvious.After reaction 1h (Fig. 3 d), most nanometer sheet has been transformed into the nano-rings that pattern is good.
If will continue in the reaction time to extend to 24h, the palladium nano-crystal obtained as shown in Figure 4, only more remaining random fragment and granules, the oxide etch of transition finally can destroy whole palladium nano-rings, and this also confirms the existence of oxide etch system from a side.
Embodiment 2
Step one, 16mg palladium acetylacetonate, 60mg softex kw, 100mg tungsten carbonyl, 170mg citric acid and 30mg polyvinylpyrrolidone are dissolved in 10mL N, in N-dimethylformamide, stirring 1h makes each material fully dissolve, reactant liquor is transferred in 25mL round-bottomed flask, under 80 DEG C of conditions, reacts 1h.After having reacted, reactant liquor is centrifugal, obtain hexagon palladium nano sheet.Palladium nano sheet pattern is as shown in Fig. 5 (a).The thickness of hexagon palladium nano sheet is 1.0nm, and average side length is 6.4nm.
Step 2, by the 4mg palladium nano sheet that obtains in step one and 4mg palladium acetylacetonate, 30mg softex kw, 50mg ascorbic acid and 50mg polyvinylpyrrolidone (M
w=30000) join at 10mLN, in N-dimethylformamide, stir 10min and palladium acetylacetonate, cetyl ammonium bromide, ascorbic acid and polyvinylpyrrolidone are fully dissolved, reactant liquor is transferred in 25mL round-bottomed flask, at 80 DEG C, reacts 1h.After having reacted, the reaction solution that takes a morsel is centrifugal, obtains two-dimentional hollow palladium nano-crystal, and preparation TEM sample, by its pattern of transmission electron microscope observation, as shown in Fig. 5 (c), the thickness of two-dimentional hollow palladium nano-crystal is 2nm, and average side length is 6.4nm.
Embodiment 3
Step one, 16mg palladium acetylacetonate, 60mg softex kw, 100mg tungsten carbonyl, 50mg citric acid and 30mg polyvinylpyrrolidone are joined 10mL N, in N-dimethylformamide, stirring 1h makes each material fully dissolve, reactant liquor is transferred in 25mL round-bottomed flask, under 80 DEG C of conditions, reacts 1h.After having reacted, reactant liquor is centrifugal, obtain hexagon palladium nano sheet.Palladium nano sheet pattern is as shown in Fig. 5 (b).The thickness of hexagon palladium nano sheet is 1.1nm, and average side length is 24.5nm.
Step 2, by the 4mg palladium nano sheet that obtains in step one and 4mg palladium acetylacetonate, 120mg softex kw, 50mg ascorbic acid and 50mg polyvinylpyrrolidone (M
w=30000) join in 10mL DMF, stir 10min and palladium acetylacetonate, cetyl ammonium bromide, ascorbic acid and polyvinylpyrrolidone are fully dissolved, reactant liquor is transferred in 25mL round-bottomed flask, at 80 DEG C, reacts 1h.After having reacted, the reactant liquor that takes a morsel is centrifugal, obtains two-dimentional hollow palladium nano-crystal, and preparation TEM sample, by its pattern of transmission electron microscope observation, as shown in Fig. 5 (d), two-dimentional hollow palladium nano-crystal thickness is 2nm, and average side length is 24.5nm.
In order to study the effect of bromide ion dressing agent and palladium presoma, carry out corresponding check experiment.When the softex kw in the reaction system of embodiment 3 is removed; product is the outer nanometer sheet (as ringlet in Fig. 6 (a)) slightly thickeied that makes a circle; the nanometer sheet (in Fig. 6 (a) great circle) that a small amount of size obviously becomes large can also be found simultaneously; this makes nanometer sheet side lack protection; cause some palladium atomic depositions to nanometer sheet side, there occurs cross growth.
When the palladium acetylacetonate in the reaction system of embodiment 3 is removed, product is the irregular hollow-core construction (Fig. 6 (b)) of a large amount of cut, this shows that oxide etch is from the upper and lower surface of nanometer sheet, but due to the thickness that nanometer sheet is ultra-thin, once the space that etching produces is excessive, the overall structure of nanometer sheet will become very fragile, finally cause structural damage.
Claims (10)
1. a preparation method for two-dimentional hollow palladium nano-crystal, is characterized in that, palladium nanometer seed, palladium presoma, bromide ion dressing agent, reducing agent and dispersant is joined in solvent and reacts, prepare two-dimentional hollow palladium nano-crystal; Described palladium nanometer seed is palladium nano sheet.
2. the preparation method of two-dimentional hollow palladium nano-crystal as claimed in claim 1, is characterized in that, described palladium nano sheet is hexagon palladium nano sheet, and the length of side is 5 ~ 50nm, and thickness is 0.8 ~ 1.8nm.
3. the preparation method of two-dimentional hollow palladium nano-crystal as claimed in claim 1, is characterized in that, reaction temperature is 80 ~ 120 DEG C, and the reaction time is 1 ~ 2h.
4. the preparation method of two-dimentional hollow palladium nano-crystal as claimed in claim 1, is characterized in that, the concentration of palladium nano sheet is 1.0 × 10
-3~ 3.0 × 10
-3mol/L.
5. the preparation method of two-dimentional hollow palladium nano-crystal as claimed in claim 1, is characterized in that, described palladium presoma is selected from palladium acetylacetonate, palladium or palladium nitrate, the concentration 1.0 × 10 of palladium presoma
-3~ 3.0 × 10
-3mol/L.
6. the preparation method of two-dimentional hollow palladium nano-crystal as claimed in claim 1, is characterized in that, described bromide ion dressing agent is selected from KBr, sodium bromide, TBAB or softex kw, and the concentration of bromide ion dressing agent is 8.0 × 10
-3~ 4.0 × 10
-2mol/L.
7. the preparation method of two-dimentional hollow palladium nano-crystal as claimed in claim 1, it is characterized in that, described reducing agent is selected from ascorbic acid or ethylene glycol, and the concentration of reducing agent is 1.0 × 10
-2~ 3.0 × 10
-2mol/L.
8. the preparation method of two-dimentional hollow palladium nano-crystal as claimed in claim 1, it is characterized in that, described dispersant is selected from polyvinylpyrrolidone, polymine or dodecyl sodium sulfate, and the concentration of dispersant is 1.0 × 10
-2~ 5.0 × 10
-2mol/L;
Described solvent is selected from DMF, DMA, water or phenmethylol.
9. the preparation method of the two-dimentional hollow palladium nano-crystal as described in as arbitrary in claim 1 ~ 8, it is characterized in that, palladium nano sheet, palladium acetylacetonate, softex kw, ascorbic acid and polyvinylpyrrolidone are joined N, react in N-dimethylformamide, prepare two-dimentional hollow palladium nano-crystal, reaction temperature is 80 ~ 100 DEG C, and the reaction time is 1 ~ 2h.
10. the two-dimentional hollow palladium nano-crystal that obtains of preparation method as claimed in claim 9, it is characterized in that, described two-dimentional hollow palladium nano-crystal upper and lower surface is that { 111} crystal face, the thickness of two-dimentional hollow palladium nano-crystal is 2 ~ 4nm.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559911A (en) * | 2004-02-20 | 2005-01-05 | 浙江大学 | Process for preparing hollow ball of single dispersion cadmium sulfide |
| CN101817090A (en) * | 2010-04-23 | 2010-09-01 | 厦门大学 | Synthesis method of palladium nano sheet |
| CN102059128A (en) * | 2010-11-22 | 2011-05-18 | 济南大学 | Nanometer porous palladium alloy catalyst and preparation method thereof |
| CN102699347A (en) * | 2012-06-25 | 2012-10-03 | 安徽理工大学 | Method for preparing palladium nanometer sheet with optical property |
| CN102847952A (en) * | 2012-10-22 | 2013-01-02 | 安徽理工大学 | Method for preparing polyhedral nano palladium material through ethanol reduction |
| CN102872861A (en) * | 2012-10-22 | 2013-01-16 | 安徽理工大学 | Method for preparing nano-palladium electro-catalyst by ethanol reduction |
| WO2014077043A1 (en) * | 2012-11-14 | 2014-05-22 | 三井金属鉱業株式会社 | Silver powder |
| CN103857484A (en) * | 2012-05-11 | 2014-06-11 | Lg化学株式会社 | Method for manufacturing hollow metal nanoparticles, and hollow metal nanoparticles manufactured thereby |
| TW201430167A (en) * | 2012-11-30 | 2014-08-01 | Mitsui Mining & Smelting Co | Silver-coated copper powder, and method for producing same |
-
2015
- 2015-03-11 CN CN201510106358.7A patent/CN104722775B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559911A (en) * | 2004-02-20 | 2005-01-05 | 浙江大学 | Process for preparing hollow ball of single dispersion cadmium sulfide |
| CN101817090A (en) * | 2010-04-23 | 2010-09-01 | 厦门大学 | Synthesis method of palladium nano sheet |
| CN102059128A (en) * | 2010-11-22 | 2011-05-18 | 济南大学 | Nanometer porous palladium alloy catalyst and preparation method thereof |
| CN103857484A (en) * | 2012-05-11 | 2014-06-11 | Lg化学株式会社 | Method for manufacturing hollow metal nanoparticles, and hollow metal nanoparticles manufactured thereby |
| CN102699347A (en) * | 2012-06-25 | 2012-10-03 | 安徽理工大学 | Method for preparing palladium nanometer sheet with optical property |
| CN102847952A (en) * | 2012-10-22 | 2013-01-02 | 安徽理工大学 | Method for preparing polyhedral nano palladium material through ethanol reduction |
| CN102872861A (en) * | 2012-10-22 | 2013-01-16 | 安徽理工大学 | Method for preparing nano-palladium electro-catalyst by ethanol reduction |
| WO2014077043A1 (en) * | 2012-11-14 | 2014-05-22 | 三井金属鉱業株式会社 | Silver powder |
| TW201430167A (en) * | 2012-11-30 | 2014-08-01 | Mitsui Mining & Smelting Co | Silver-coated copper powder, and method for producing same |
Non-Patent Citations (2)
| Title |
|---|
| HUI ZHANG,ET AL: "Noble-Metal Nanocrystals with Concave Surfaces:Synthesis and Applications", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| YI LI,ET AL: "Size-controlled synthesis of Pd nanosheets for tunable plasmonic properties", 《CRYSTENGCOMM》 * |
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