CN104722775B - A kind of two dimension hollow palladium nano-crystal and preparation method thereof - Google Patents
A kind of two dimension hollow palladium nano-crystal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of two dimension hollow palladium nano-crystal, palladium nanometer seed, palladium presoma, bromide ion dressing agent, reducing agent and dispersant are joined in solvent and react, prepare two dimension hollow palladium nano-crystal；Described palladium nanometer seed is palladium nano sheet.Preparation method of the present invention just can prepare two dimension hollow palladium nano-crystal as seed through single step reaction using nanometer sheet, and simple to operate, reaction condition is gentle, and inexpensively, toxicity is little for agents useful for same, easily realizes.The invention also discloses the two-dimentional hollow palladium nano-crystal that described preparation method prepares, described two dimension hollow palladium nano-crystal upper and lower surface is { 111} crystal face, the thickness of two dimension hollow palladium nano-crystal is 2nm～4nm, described two dimension hollow palladium nano-crystal is a kind of ultra-thin circulus, improve material specific surface area and atom utilization, effectively enhance the catalytic performance of palladium nano-crystal.
Description
Technical field
The present invention relates to the preparation field of noble metal nanometer material, particularly relate to a kind of two dimension hollow palladium and receive
Meter Jing and preparation method thereof.
Background technology
Palladium nano-crystal as a kind of important noble metal nanometer material, due to its good catalytic performance and
The cheapest price is widely used in the necks such as hydrogenation reaction, carbon-to-carbon coupling and carbon monoxide process
Territory, some achievements in research in recent years also find palladium nano-crystal at aspects such as surface plasma body resonant vibrations also
There is potential application.
Research shows, its performance is had a very big impact by the pattern of palladium nano-crystal, controls palladium nano-crystal
The focus always studied in the industry of pattern, the most existing a lot of documents are reported by utilizing thermodynamics control
Method processed has prepared the Pd nano particle of multiple nanostructured, including tetrahedron, cube, eight
Face body, decahedron, icosahedron, pyrometric cone, bar-shaped and nano flower etc., these nano particles mostly are
There is the solid of three dimensional symmetry structure.
The three dimensional symmetry structure of palladium nano-crystal is for two-dimensional structure, and specific surface area and atom utilize
Rate is the most relatively low, although the two-dimensional sheet structure of palladium early has been reported that, but its synthesis is required for by an oxidation
Carbon this severe toxicity gas, has certain danger.
The Chinese patent application of Application No. 201010160739.0 discloses the conjunction of a kind of palladium nano sheet
One-tenth method, adds palladium presoma, surface protectant, organic salt containing halide ion in a solvent or contains
The inorganic salts of halide ion, obtain mixed liquor；Mixed liquor is placed under CO atmosphere, is warming up to 10～20
0 DEG C, then cool the temperature to room temperature, add acetone centrifugal purification, clean, obtain hexagon palladium nanometer
Sheet.The palladium nano sheet productivity of the method synthesis is high, and uniform particle sizes has superthin structure (about 1.8nm),
Specific surface area is relatively big, and atom utilization is high, presents the highest catalysis activity, but the method needs to borrow
Help severe toxicity gas CO, require the highest for experimental situation and operating process.
Zhang Hui, Li Yi etc. are at Size-Controlled Synthesis of Pd Nanosheets for Tun
In able Plasmonic Properties (CrystEngComm, a 2015,17,1833-1838) literary composition
Report another preparation method of palladium nano sheet.The method is by palladium salt, cetyl trimethyl bromine
Change ammonium (CTAB), tungsten carbonyl, citric acid (CA) and polyvinylpyrrolidone (PVP) and join N,
N-dimethylformamide (DMF) is reacted, prepares hexagon palladium nano sheet.The method makes
Instead of CO with tungsten carbonyl, operate safe and simple, and the nanometer sheet thickness prepared is thinner, only have
About 1nm, substantially increases material specific surface area and atom utilization.
Hollow-core construction is to improve material specific surface area and another effective way of atom utilization, by sky
Core structure and two-dimensional sheet structure combine and provide the new approaches of a kind of synthesis.Use easy, safety
Method preparation have the nanocrystalline of ultra-thin two-dimension structure and hollow-core construction concurrently, palladium can not only be effectively improved and receive
The catalytic performance of meter Jing, promotes the industrialization process of palladium nano-crystal the most to a certain extent, has weight
The learning value wanted and realistic meaning.
Summary of the invention
The invention provides the preparation method of a kind of two dimension hollow palladium nano-crystal, described preparation method is with palladium
Nanometer sheet prepares two dimension hollow palladium nano-crystal as seed, and this preparation method is simple to operate, reaction condition
Gentleness, easily realizes.
A kind of two dimension hollow palladium nano-crystal preparation method, by palladium nanometer seed, palladium presoma, bromine from
Sub-dressing agent, reducing agent and dispersant join in solvent and react, and prepare two dimension hollow palladium
Nanocrystalline；Described palladium nanometer seed is palladium nano sheet.
The present invention prepares the mechanism of two dimension hollow palladium nano-crystal: the Br in bromide ion dressing agent-To palladium
The side of nanometer sheet (i.e. 100} face) and there is strong adsorption capacity, the side of palladium nano sheet is had
Protect to effect so that the palladium atom being reduced can only be grown in the upper and lower surface ({ 1 of palladium nano sheet
11} face), increase the thickness of palladium nano sheet；On the other hand, bromide ion dressing agent provide bromide ion with
The oxygen composition oxide etch dissolved in solution is to Br-/O2, owing to the side of palladium nano sheet is by effectively
Protection, it is impossible to O2Contact, remaining Br in solution-With O2Can only attack Pd{111} face.Due to
Solution is to carry out from periphery to center to the diffusion of palladium nano sheet, and the palladium atom being therefore reduced is in periphery
The speed of growth at position is significantly greater than the speed of growth in centre, the pass of this local epitaxial growth
System, part relatively thin on palladium nano sheet i.e. core becomes the existence being easiest to be etched, along with instead
The carrying out answered, the centre finally resulting in palladium nano sheet is fully oxidized formation hollow after etching.
Preparation method selectivity longitudinal growth of the present invention and oxide etch are carried out simultaneously, finally obtain two dimension
Hollow palladium nano-crystal.
Described palladium nano sheet uses existing preparation method to obtain hexagon palladium nano sheet, but the present invention is not
Get rid of the nanometer sheet preparation two dimension hollow palladium nano-crystal using other shapes.Palladium nano sheet seed is to prepare
The factor that two dimension hollow palladium nano-crystal is the most important, owing to the side of palladium nano sheet modified by bromide ion dressing agent
Face, palladium nano sheet will not cross growth, therefore the size of palladium nano sheet determines two dimension hollow palladium nano-crystal
Size, 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 relatively slow, no
The palladium nano-crystal of the hollow that is easy to get, 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, palladium nano sheet concentration is too low causes etching excessively, destroys nanometer sheet integrality,
As preferably, the concentration of described palladium nano sheet is 1.0 × 10-3～3.0 × 10-3mol/L。
Another key factor of preparation two dimension hollow palladium nano-crystal is bromide ion dressing agent.If reaction
Being added without bromide ion dressing agent in system, the product obtained is the outer nanometer sheet slightly thickeied that makes a circle,
The mid portion of nanometer sheet remains solid, illustrates in the presence of not having bromide ion dressing agent
Oxide etch is impossible.
Described bromide ion dressing agent is selected from KBr, sodium bromide, TBAB or cetyl three
Methyl bromide ammonium, as preferably, described bromide ion dressing agent is selected from KBr or cetyl trimethyl
Ammonium bromide, the etching that preferred bromide ion dressing agent and dissolved oxygen form is higher to etching power.
The size of the concentration impact two dimension hollow palladium nano-crystal of bromide ion dressing agent and etching speed, highly concentrated
The bromide ion dressing agent of degree easily causes etching excessively, destroys the structure of two dimension hollow palladium nano-crystal；Low
The side of palladium nano sheet can not fully be modified by the bromide ion dressing agent of concentration, causes palladium nano sheet laterally to give birth to
Long.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 dimension hollow palladium nano-crystal, the selection of reaction temperature is the most particularly significant, temperature
Spend low cause growth and etching all cannot be carried out；Temperature is too high cause etching too strong, the life of palladium atom
Long do not have selectivity；As preferably, reaction temperature is 80～120 DEG C.
As further preferably, reaction temperature is 80～100 DEG C, at preferred temperature, growth and
Etching is all normally carried out.
The reaction time of described preparation method is too short, and palladium nano-crystal centre is solid construction；Reaction
Overlong time, easily causes palladium nano-crystal etching too strong, destroys the structure of hollow two dimension palladium nano-crystal.
As preferably, the reaction time is 1～2h.
If being added without palladium presoma in reaction system, the product obtained is the irregular empty of a large amount of cut
Heart palladium nano-crystal, and due to the ultra-thin thickness of nanometer sheet, the space once etching generation is excessive, receives
The overall structure of rice sheet will become the most fragile, ultimately result in the broken of hollow two dimension palladium nano-crystal structure
Bad, therefore reaction system needs to add a certain amount of palladium presoma, described palladium presoma is selected from levulinic
Ketone palladium, palladium or palladium nitrate.
The thickness of the concentration impact two dimension hollow palladium nano-crystal of palladium presoma, as preferably, palladium presoma
Concentration be 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 the gentleest, it is possible to
Control the speed of reaction.
The concentration of reducing agent can affect rate of reduction, and rate of reduction affects the thickness and all of palladium nano-crystal
Even property, as preferably, the concentration of reducing agent is 1.0 × 10-2～3.0 × 10-2Mol/L, in preferred concentration
Under, the thickness of the two-dimentional hollow palladium nano-crystal obtained is 2～4nm, and size is the most uniform.
Described reaction system adds dispersant, it is possible to prevent palladium nano-crystal from assembling.Described dispersion
Agent is selected from polyvinylpyrrolidone, ethylene imine or dodecyl sodium sulfate；The concentration of dispersant is
1.0×10-2～5.0 × 10-2mol/L。
In view of palladium nano sheet, palladium presoma, bromide ion dressing agent, reducing agent and dispersant at solvent
In dissolubility, dispersiveness and stability.Described solvent is selected from DMF, N,
N-dimethylacetylamide, water or phenmethylol.
As preferably, the preparation method of two dimension hollow palladium nano-crystal is as follows: by palladium nano sheet, levulinic
Ketone palladium, cetyl trimethylammonium bromide, ascorbic acid and polyvinylpyrrolidone join N, N
Dimethylformamide reacts, prepare two dimension hollow palladium nano-crystal, reaction temperature be 80～
100 DEG C, the reaction time is 1～2h；Under optimum condition, the thickness of the two-dimentional hollow palladium nano-crystal prepared
Degree is 2～4nm.
As preferably, the concentration of palladium nano sheet is 1.0 × 10-3～1.5 × 10-3Mol/L, palladium acetylacetonate
Concentration is 1.0 × 10-3～1.5 × 10-3Mol/L, the concentration of cetyl trimethylammonium bromide 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, polyethylene pyrrole
The concentration of pyrrolidone is 4.0 × 10-2～5.0 × 10-2mol/L。
The present invention also provides for the two-dimentional hollow palladium nano-crystal that described preparation method prepares, described two dimension hollow
The upper and lower surface of palladium nano-crystal is that { 111} crystal face, thickness is 2～4nm.The two dimension that the present invention provides
Hollow palladium nano-crystal improves material specific surface area and atom utilization, effectively enhances the catalytic of palladium
Energy.
Compared with prior art, the method have the advantages that
The preparation method that the present invention uses is by palladium nanometer seed, palladium presoma, bromide ion dressing agent, also
Former dose joins reaction in solvent in the lump with dispersant, and simple to operate, reaction condition is gentle, examination used
Inexpensively, toxicity is little in agent, easily realizes.
The two-dimentional hollow palladium nano-crystal that the present invention provides is a kind of ultra-thin circulus, improves material ratio
Surface area and atom utilization, effectively enhance 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: figure (a) is transmission electron microscope (TEM) figure of palladium nano sheet, and figure (b) is palladium nano sheet
Attachment side view on the carbon nanotubes；
Fig. 2 is the transmission electron microscope figure of the two-dimentional hollow palladium nano-crystal of embodiment 1 preparation；Wherein:
Figure (a) and the transmission electron microscope figure that figure (b) is different amplification；Figure (c) is received for two dimension hollow palladium
High resolution transmission electron microscopy (HRTEM) figure on the brilliant upper and lower surface of rice；Figure (d) is two dimension hollow palladium
The high resolution transmission electron microscopy figure of nanocrystalline side；
Fig. 3 reacts the transmission electron microscope of the palladium nano-crystal that different time is obtained by embodiment 1
Figure；Wherein:
Figure (a), figure (b), figure (c), figure (d) are respectively 5min, 10min, 30min and 1
The transmission electron microscope figure of the palladium nano-crystal that h obtains, the figure in the upper right corner is corresponding high multiple transmission
Electron microscope picture；
Fig. 4 is the transmission electron microscope figure that embodiment 1 reacts the palladium nano-crystal that 24h obtains；
Fig. 5 is palladium nano sheet and the transmitted electron of two dimension hollow palladium nano-crystal of embodiment 2 and 3 preparation
Microscope figure；Wherein:
Prepared by the palladium nano sheet of figure (a) and figure (c) respectively embodiment 2 step one preparation and step 2
The transmission electron microscope figure of two dimension hollow palladium nano-crystal；
Prepared by the palladium nano sheet of figure (b) and figure (d) respectively embodiment 3 step one preparation and step 2
The transmission electron microscope figure of two dimension hollow palladium nano-crystal.
Fig. 6 is the transmission electron microscope figure of the palladium nano-crystal prepared under different situations；Wherein:
When Fig. 6 (a) is for being added without bromide ion dressing agent, when Fig. 6 (b) is for being added without palladium presoma.
Detailed description of the invention
Embodiment 1
Step one, by 16mg palladium acetylacetonate, 60mg cetyl trimethylammonium bromide, 100mg
Tungsten carbonyl, 90mg citric acid and 30mg polyvinylpyrrolidone are dissolved in 10mL N, N dimethyl
In formamide, stirring 1h makes each material fully dissolve, and reactant liquor is transferred to 25mL round bottom and burns
In Ping, under the conditions of 80 DEG C, react 1h.After having reacted, reactant liquor is centrifuged, it is thus achieved that hexagon
Palladium nano sheet.Palladium nano sheet pattern is as it is shown in figure 1, the thickness of hexagon palladium nano sheet is 1nm, flat
All length of sides are 15.7nm.
Step 2, the 4mg palladium nano sheet and 4mg palladium acetylacetonate, the 60mg that will obtain in step one
Cetyl trimethylammonium bromide, 50mg ascorbic acid and 50mg polyvinylpyrrolidone (Mw=3
0000) join in 10mL DMF, stirring 10min make palladium acetylacetonate,
Cetyl ammonium bromide, ascorbic acid and polyvinylpyrrolidone fully dissolve, and are transferred to by reactant liquor
In 25mL round-bottomed flask, at 80 DEG C, react 1h.Take a small amount of reactant liquor to be centrifuged, obtain two dimension hollow
Palladium nano-crystal, prepares TEM sample, by its pattern of transmission electron microscope observation, as schemed (a) in Fig. 2
Shown in figure (b)；Figure (c) and figure (d) are the high-resolution transmission electricity of the upper and lower surface of palladium nano-rings and side
Sub-microscope figure, the spacing of lattice marked in figure shows that palladium nano-rings upper and lower surface is so that { 111} crystal face is
It exposes crystal face, and the thickness of two dimension hollow palladium nano-crystal only has 2nm, and average side length is 15.7nm.
In order to study the formation mechenism of this special two-dimentional hollow palladium nano-crystal structure, to having reacted not
The sign of transmission electron microscope has been carried out, in initial reaction stage (Fig. 3 (a), reaction time with the sample of time
For 5min), the pattern of nanometer sheet does not appears to change, can but examine sample amplification
To find (Fig. 3 (a) upper right corner illustration), the contrast at nanometer sheet edge is more deeper than center,
Represent the periphery having had some palladium atomic depositions to arrive the upper and lower surface of nanometer sheet.When reaction proceeds to
During 10min (Fig. 3 (b)), the periphery of more palladium atomic deposition to the upper and lower surface of nanometer sheet,
This local epitaxy causes the contrast difference mutation of nanometer sheet center and surrounding to obtain more and more obvious.Same with this
Time, Br present in system-With the O in air2Composition oxide etch pair, from the beginning of Fig. 3 (a),
Just can find some little hole or pits in nanometer sheet.And due to Br-{ 100} to Pd
The adsorption capacity that face is strong, the side of nanometer sheet is effectively protected, it is impossible to O2Contact.
Remaining Br in solution-With O2Can only attack Pd{111} face.And due to the relation of local epitaxial growth,
Part relatively thin in nanometer sheet i.e. core becomes the position being easiest to be etched, along with entering of reaction
Row is fallen by gradually oxide etch.30min (Fig. 3 c), hexagon nano-rings is extended between when reacted
Pattern basically form, middle hole the most gradually expands and obvious.After reaction 1h (Fig. 3 d),
Most nanometer sheet are converted to the nano-rings that pattern is good.
If will continue in the reaction time to extend to 24h, the palladium nano-crystal obtained be as shown in Figure 4, the most surplus
More lower random fragments and little particle, the oxide etch of transition eventually destroys whole palladium nanometer
Ring, this also confirms the existence of oxide etch system from a side.
Embodiment 2
Step one, by 16mg palladium acetylacetonate, 60mg cetyl trimethylammonium bromide, 100
Mg tungsten carbonyl, 170mg citric acid and 30mg polyvinylpyrrolidone are dissolved in 10mL N, N bis-
In NMF, stirring 1h makes each material fully dissolve, and reactant liquor is transferred to 25mL circle
In end flask, under the conditions of 80 DEG C, react 1h.After having reacted, reactant liquor is centrifuged, it is thus achieved that six
Limit shape palladium nano sheet.Shown in palladium nano sheet pattern such as Fig. 5 (a).The thickness of hexagon palladium nano sheet is 1.
0nm, average side length is 6.4nm.
Step 2, the 4mg palladium nano sheet and 4mg palladium acetylacetonate, the 30mg that will obtain in step one
Cetyl trimethylammonium bromide, 50mg ascorbic acid and 50mg polyvinylpyrrolidone (Mw=3
0000) join in 10mLN, N-dimethylformamide, stirring 10min make palladium acetylacetonate,
Cetyl ammonium bromide, ascorbic acid and polyvinylpyrrolidone fully dissolve, and are transferred to by reactant liquor
In 25mL round-bottomed flask, at 80 DEG C, react 1h.After having reacted, take a small amount of reaction solution and be centrifuged,
Obtain two dimension hollow palladium nano-crystal, prepare TEM sample, by its pattern of transmission electron microscope observation,
As shown in Fig. 5 (c), the thickness of two dimension hollow palladium nano-crystal is 2nm, and average side length is 6.4nm.
Embodiment 3
Step one, by 16mg palladium acetylacetonate, 60mg cetyl trimethylammonium bromide, 100
Mg tungsten carbonyl, 50mg citric acid and 30mg polyvinylpyrrolidone join 10mL N, N bis-
In NMF, stirring 1h makes each material fully dissolve, and reactant liquor is transferred to 25mL circle
In end flask, under the conditions of 80 DEG C, react 1h.After having reacted, reactant liquor is centrifuged, it is thus achieved that six
Limit shape palladium nano sheet.Shown in palladium nano sheet pattern such as Fig. 5 (b).The thickness of hexagon palladium nano sheet is 1.
1nm, average side length is 24.5nm.
Step 2, by the 4mg palladium nano sheet that obtains in step one and 4mg palladium acetylacetonate, 120
Mg cetyl trimethylammonium bromide, 50mg ascorbic acid and 50mg polyvinylpyrrolidone (Mw
=30000) join in 10mL DMF, stirring 10min make palladium acetylacetonate,
Cetyl ammonium bromide, ascorbic acid and polyvinylpyrrolidone fully dissolve, and are transferred to by reactant liquor
In 25mL round-bottomed flask, at 80 DEG C, react 1h.After having reacted, take a small amount of reactant liquor and be centrifuged,
Obtain two dimension hollow palladium nano-crystal, prepare TEM sample, by its pattern of transmission electron microscope observation,
As shown in Fig. 5 (d), two dimension hollow palladium nano-crystal thickness is 2nm, and average side length is 24.5nm.
In order to study bromide ion dressing agent and the effect of palladium presoma, carry out corresponding check experiment.
When being removed by the cetyl trimethylammonium bromide in the reaction system of embodiment 3, product is peripheral
One encloses the nanometer sheet (such as ringlet in Fig. 6 (a)) that slightly thickeies, simultaneously it has also been found that a small amount of size
Substantially becoming big nanometer sheet (great circle in Fig. 6 (a)), this is owing to not having bromide ion to make in system
Obtain nanometer sheet side and lack protection, cause some palladium atomic depositions to nanometer sheet side, there occurs laterally
Growth.
When being removed by the palladium acetylacetonate in the reaction system of embodiment 3, product is a large amount of cuts
Irregular hollow-core construction (Fig. 6 (b)), this shows that oxide etch is from the beginning of the upper and lower surface of nanometer sheet
, but due to the ultra-thin thickness of nanometer sheet, the space once etching generation is excessive, nanometer sheet whole
Body structure will become the most fragile, ultimately result in structural damage.
Claims (4)
1. a two-dimentional hollow palladium nano-crystal, it is characterised in that described two-dimentional hollow palladium nano-crystal
Upper and lower surface is that { 111} crystal face, the thickness of two dimension hollow palladium nano-crystal is 2～4nm；
Described two dimension hollow palladium nano-crystal preparation method include, by palladium nanometer seed, palladium presoma,
Bromide ion dressing agent, reducing agent and dispersant join in solvent and react, and prepare in two dimension
Empty palladium nano-crystal；
Described palladium nanometer seed is palladium nano sheet, and thickness is 0.8～1.8nm, and the concentration of palladium nano sheet is
1.0×10-3～3.0 × 10-3mol/L；
Palladium presoma is selected from palladium acetylacetonate, palladium or palladium nitrate, the concentration 1.0 × 1 of palladium presoma
0-3～3.0 × 10-3mol/L；
Bromide ion dressing agent is selected from KBr, sodium bromide, TBAB or cetyl trimethyl
Ammonium bromide, the concentration of bromide ion dressing agent is 8.0 × 10-3～4.0 × 10-2mol/L；
Reducing agent is selected from ascorbic acid or ethylene glycol, and the concentration of reducing agent is 1.0 × 10-2～3.0 × 10-2mo
l/L；
Dispersant is selected from polyvinylpyrrolidone, ethylene imine or dodecyl sodium sulfate, dispersant
Concentration be 1.0 × 10-2～5.0 × 10-2mol/L；
Reaction temperature is 80～120 DEG C, and the reaction time is 1～2h.
2. two dimension hollow palladium nano-crystal as claimed in claim 1, it is characterised in that described palladium
Nanometer sheet is hexagon palladium nano sheet, and the length of side is 5～50nm.
3. two dimension hollow palladium nano-crystal as claimed in claim 1, it is characterised in that described is molten
Agent is selected from DMF, DMA, water or phenmethylol.
4. the two-dimentional hollow palladium nano-crystal as described in claims 1 to 3 is arbitrary, it is characterised in that will
Palladium nano sheet, palladium acetylacetonate, cetyl trimethylammonium bromide, ascorbic acid and polyvinyl pyrrole
Alkanone joins in DMF reacts, and prepares two dimension hollow palladium nano-crystal,
Reaction temperature is 80～100 DEG C, and the reaction time is 1～2h.
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| CN105332050A (en) * | 2015-11-30 | 2016-02-17 | 中国科学技术大学 | Palladium nanocrystals and synthesis method thereof |
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| CN109759081A (en) * | 2019-02-20 | 2019-05-17 | 华侨大学 | A kind of preparation method and applications of two dimension multi-element metal nano material |
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| CN102847952B (en) * | 2012-10-22 | 2014-11-05 | 安徽理工大学 | Method for preparing polyhedral nano palladium material through ethanol reduction |
| JP2014098186A (en) * | 2012-11-14 | 2014-05-29 | Mitsui Mining & Smelting Co Ltd | Silver powder |
| JP5785532B2 (en) * | 2012-11-30 | 2015-09-30 | 三井金属鉱業株式会社 | Silver-coated copper powder and method for producing the same |
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