CN104028776A - Metal particles with three-dimensional dendritic crystal structures and preparation method for metal particles - Google Patents
Metal particles with three-dimensional dendritic crystal structures and preparation method for metal particles Download PDFInfo
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Abstract
The invention discloses metal particles with three-dimensional dendritic crystal structures and a preparation method for the metal particles. The preparation method comprises the following steps of (1) preparing reducing agent liquor and metal salt liquor under the condition that the molar concentration ratio of the reducing agent liquor to the metal salt liquor is 0.1-50; (2) dripping the reducing agent liquor and the metal salt liquor of which the volume is the same with the volume of the reducing agent liquor in a reaction container at constant speed at first speed V1 and second speed V2 respectively, vibrating mixed liquor in the reaction container at vibrating frequency of 10-50Hz in a reaction process, and generating sediments in the reaction container; and (3) filtering and cleaning the sediments, and drying the sediments in a vacuum manner so as to obtain the metal particles with the three-dimensional dendritic crystal structures. The first speed V1 and the second speed V2 are in a range of 0.1-20mL/min. By using the preparation method, a preparation process is simple, microstructures of the prepared metal particles can be 100 nanometers to 50 micrometers, and the shapes and the appearances of the prepared three-dimensional dendritic crystal structures can be conveniently controlled.
Description
[technical field]
The present invention relates to the preparation method of metallic particles, particularly relate to a kind of preparation method and metallic particles of the metallic particles with three-dimensional pine-tree structure.
[background technology]
In recent years, the noble metal of micro nano structure is subject to extensive concern.As important conduction and biological sensing material, the research of the micro-nano pattern of the materials such as gold, platinum, silver, copper is more extensive.Micro-nano precious metal material itself possesses good catalytic performance, electrical property etc., thereby in an increasingly wide range of applications at aspects such as electronics, chemistry, bioengineering, it can be used as catalyst carrier, biological medicine carrier, surface Raman enhancement scattering (SERS) base material, conducing composite material filler, super hydrophobic surface resist etc.
To precious metal material, for example research major part of the micro nano structure of silver concentrates on zero dimension silver nanoparticle ball, 1-dimention nano silver line and two dimension micron silver strip aspect at present.Obtain the nanometer-level silver structure of the patterns such as nano-silver thread, nanometer rods, nano cubic monocrystalline, nanometer regular polygon by changing surfactant and reducing agent.Concentrate on the preparation of nanosphere particle and the research of character for gold and platinum etc. are also more.For metallic copper, be mainly the research of nanosphere particle and NANO CRYSTAL COPPER WIRE.For the research of the micron order three-dimensional structure of precious metal material, owing to lacking effectively preparation means in batches, relatively less to its research.In addition, there is at present the synthetic method of the metallic particles of three-dimensional pine-tree structure about preparation, comprise electrochemical deposition, gamma-rays deposition, dielectric breakdown, gas-phase polymerization, ultraviolet ray irradiation reduction and ultrasonic wave assisted Reduction method etc., but said method has certain limitation, for example need special installation auxiliary, consuming time longer, particle surface cleanliness factor is low, and output is lower.In addition, because the templates that adopt auxiliary more, the stereoeffect of the 3-dimensional metal dendrite of preparation is poor, and the pattern control of dendrite a little less than.
[summary of the invention]
Technical problem to be solved by this invention is: make up above-mentioned the deficiencies in the prior art, a kind of preparation method and metallic particles of the metallic particles with three-dimensional pine-tree structure are proposed, preparation process is simple, the micro-structural of the metallic particles making can reach micron order (100nm～50 μ m), and can more easily control the pattern of the three-dimensional pine-tree structure of preparation.
Technical problem of the present invention is solved by following technical scheme:
A preparation method with the metallic particles of three-dimensional pine-tree structure, comprises the following steps: 1) prepare reductant solution and metal salt solution, described reductant solution is 0.1～50 with the ratio a of the molar concentration of described metal salt solution; 2) isopyknic described reductant solution and described metal salt solution are at the uniform velocity splashed in reaction vessel with First Speed V1 and second speed V2 respectively, described First Speed V1 and described second speed V2 are all in the scope of 0.1～20mL/min, in course of reaction, mixed solution in described reaction vessel is shaken with the frequency of oscillation of 10～50Hz, in described reaction vessel, generate precipitation; 3) described precipitation is filtered, cleaned, then carry out vacuum drying, make the metallic particles with three-dimensional pine-tree structure.
A kind of metallic particles with three-dimensional pine-tree structure making according to preparation method as above.
The beneficial effect that the present invention is compared with the prior art is:
The preparation method of the metallic particles with three-dimensional pine-tree structure of the present invention and metallic particles, realize micron order dendroid dendrite synthetic of metallic particles by solution phase method of reducing, control the concentration ratio of described metal salt solution and reductant solution and both charging rates, reaction solution is evenly mixed, thereby make the dendritic pine-tree structure of three-dimensional tree, the micro-structural making can reach micron order, and (100nm～50 μ m).And by controlling two parameters at particular range, concrete pattern that also can corresponding control three-dimensional structure is one-level fractal structure or multistage fractal result, and the pattern of micro-structural is had to good control.Further, by controlling reaction temperature, pH value, can control respectively diameter dimension and the multistage fractal structure of micro-structural.Preparation method of the present invention, preparation process is easy, and can more easily control the pattern of the three-dimensional pine-tree structure of preparation, by adjusting process and material rate, can, for different purposes designs the extensive dendrite material of preparing in batches different size and pattern, be easy to carry out industrialization and large-scale mass production.
[brief description of the drawings]
Fig. 1 is the system architecture schematic diagram of preparing metallic particles of the specific embodiment of the invention;
Fig. 2 is the X ray diffracting spectrum of the silver metal particles prepared of the experiment 1 of the specific embodiment of the invention;
Fig. 3 is the SEM SEM figure of the silver metal particles prepared of the experiment 1 of the specific embodiment of the invention;
Fig. 4 is the SEM SEM figure of the silver metal particles prepared of the experiment 2 of the specific embodiment of the invention;
Fig. 5 is the SEM SEM figure of the silver metal particles prepared of the experiment 3 of the specific embodiment of the invention;
Fig. 6 is that silver metal particles prepared by the experiment 3 of the specific embodiment of the invention is schemed through ultrasonic SEM after treatment;
Fig. 7 is the SEM figure of the silver metal particles prepared of the experiment 3 of the specific embodiment of the invention after sintering processes;
Fig. 8 is the SEM SEM figure of the silver metal particles prepared of the experiment 4 of the specific embodiment of the invention;
Fig. 9 is the SEM SEM figure of the silver metal particles prepared of the experiment 5 of the specific embodiment of the invention;
Figure 10 is the SEM SEM figure of the silver metal particles prepared of the experiment 6 of the specific embodiment of the invention;
Figure 11 is the SEM SEM figure of the silver metal particles prepared of the experiment 7 of the specific embodiment of the invention;
Figure 12 is the SEM SEM figure of the silver metal particles prepared of the experiment 8 of the specific embodiment of the invention;
Figure 13 is the X ray diffracting spectrum of the golden metallic particles prepared of the experiment 9 of the specific embodiment of the invention;
Figure 14 is the SEM SEM figure of the golden metallic particles prepared of the experiment 9 of the specific embodiment of the invention.
[detailed description of the invention]
Below in conjunction with detailed description of the invention and contrast accompanying drawing the present invention is described in further details.
The present invention proposes to prepare the metallic particles of three-dimensional pine-tree structure, and requirement is to be convenient to control particle size, particle diameter distribution and level pattern, realizes in enormous quantities synthetic simultaneously.The formation of dendrite is a kind of process of nonequilibrium state crystallization, the growth of 3-dimensional metal dendrite relates to the oriented growth of crystal, synthesize and still have larger difficulty for the batch of this kind of dendrite at present, not yet have ripe method stable mass to synthesize pattern homogeneous, the dendritic dendrite of monodispersed micron three-dimensional tree.The growth of dendrite is subject to the impact of thermodynamics and kinetics condition.The pattern of dendrite and the direction of growth can be controlled by controlling nucleation rate and the speed of growth.The thermokinetics condition required due to the growth of the each direction of dendrite and fractal level is different, only has reaction condition to control through strict, just can obtain the dendrite of different levels fractal structure.
The present invention is directed to insoluble relevant issues in production process and made large quantity research, proposed solution phase method of reducing.Different from other methods of preparing metallic dendrite, the present invention adopts the mode that metal salt solution and reducing agent is dripped simultaneously to mixing in redox reaction process, and the rate of addition that ensures metal salt solutions and reducing agent by some equipment within the specific limits, by regulating reactant concentration ratio and mixing velocity, there is single metallic particles that disperses three-dimensional pine-tree structure thereby make.According to nucleus growth mechanism, the hybrid mode of said method can make nucleus grow along certain crystal orientation under the effect of reducing agent, by the control to reaction condition, can obtain the controlled one-level of different morphologies to multistage fractal pine-tree structure.Stable process conditions of the present invention is reliable, and whole technological process simple possible, can realize continuous production, is suitable for the popularization of suitability for industrialized production.Because the cost of raw material adopting is low, more easily obtain, and the formation rate of three-dimensional micron dendrite is up to 99%, so greatly improved the economic benefit of producing.
As shown in Figure 1, for preparing the system architecture schematic diagram of metallic particles in this detailed description of the invention, when preparation, comprise the following steps:
(1) prepare reductant solution and metal salt solution, described reductant solution is 0.1～50 with the ratio a of the molar concentration of described metal salt solution.
Wherein, reducing agent has the effect of crystal face selection absorption, impel the particle that obtains of reduction along particular crystal plane oriented growth, can be one or more the mixing in hydrazine, phenylhydrazine, methyl hydrazine, ethyl hydrazine, 2-amino-3-mercaptopropionic acid, citric acid, sodium borohydride, formaldehyde, acetaldehyde, benzaldehyde, phenol, cresols, catechol, azanol, methyl hydroxylamine, ethyl azanol, hydroxylamine hydrochloride, hydrazine.The metal ion of metal salt solution is selected from one or more the mixing in silver, gold, nickel, copper, palladium, platinum, zinc, iridium, tin, indium.The anion of metal salt solution is selected from one or more the mixing in nitrate anion, sulfate radical, salt acid group, iodide ion, bromide ion, fluorine ion, acetate, phosphate radical, iodate, chlorate anions, hypochlorite, chlorate anions, bromate.When reducing agent is multiple mixing or metal salt solution while being multiple mixing, in reductant solution, in the molar concentration sum of each reducing agent and metal salt solution, the ratio of the molar concentration sum of each slaine is 0.1～50.In Fig. 1, in container 1 and 2, be respectively metal salt solution and the reductant solution preparing, the molar concentration of reductant solution is 0.1≤a≤50 with the ratio a of the molar concentration of metal salt solution.
Metal ion in metal salt solution is typically silver ion, gold ion and copper ion.For different metal ions, there is different anion pairings, for example, for silver ion, there are hypochlorite, nitrate anion etc. than better suited anion; For gold ion, be chlorate anions than better suited anion; For copper ion, preferably nitrate anion, chlorion, sulfate radical etc.And for different metal salt solutions, also to select different reducing agents, for example, for silver salt solution, applicable reducing agent has acetaldehyde, citric acid, azanol, hydrazine etc.; For golden salting liquid, applicable reducing agent is 2-amino-3-mercaptopropionic acid or sodium borohydride; For copper salt solution, applicable reducing agent is hydroxylamine hydrochloride or sodium borohydride.
2) isopyknic described reductant solution and described metal salt solution are at the uniform velocity splashed in reaction vessel with First Speed V1 and second speed V2 respectively, described First Speed V1 and described second speed V2 are all in the scope of 0.1～20mL/min, in course of reaction, mixed solution in described reaction vessel is vibrated with the frequency of oscillation of 10～50Hz, in described reaction vessel, generate precipitation.
As shown in Figure 1, for example, by adopting binary channels or multichannel continuous feeding equipment (peristaltic pump 5) to continue feed, solution also reacts rapidly in the tip mixes of channel output end mouth, splash in reaction vessel 6, reaction vessel 6 is placed in oscillator 7 and slightly vibrates, and after reaction a period of time, is precipitated thing.
In preparation process, the ratio a that controls the molar concentration of reductant solution and metal salt solution is 0.1～50, control the charging rate not random scope arranging in the scope of 0.1～20mL/min respectively of metal salt solution and reducing agent, but in the time that concentration and speed are in above-mentioned scope, abundant degree that can corresponding control reduction reaction.If the ratio of concentration is too large or charging rate is too fast, reduction reaction is abundant not, and the metallic particles precipitation of generation is not pine-tree structure, but granular structure in irregular shape.If the ratio of concentration is too little or charging rate is too slow, reduction reaction speed, dendritic growth is too fast, not controlled, and the pine-tree structure finally obtaining will be irregular club shaped structure, instead of three-dimensional tree is dendritic.Therefore, in 3-dimensional metal dendrite batch preparation technology, key factor is the control to reactant concentration scope and the control to continuous feeding speed, strictly ratio and the charging rate of the concentration of reductant solution and metal salt solution in control course of reaction, could finally obtain the dendritic pine-tree structure of three-dimensional tree of wanting.It should be noted that, the transfer rate in the passage of continuous feeding equipment of metal salt solution and reducing agent is unimportant, as long as the speed (First Speed V1 and second speed V2) being added drop-wise in reaction vessel is 0.1～20mL/min, coordinate concentration ratio can make the dendritic pine-tree structure of the three-dimensional tree of finally wanting.
In reaction, coordinate frequency of oscillation to vibrate at 10～50Hz, can make reactant fully mix, guarantee that the dendrite generating is even.
3) described precipitation is filtered, cleaned, then carry out vacuum drying, make the metallic particles with three-dimensional pine-tree structure.
The extensive batch that this detailed description of the invention provides is prepared the method for micron 3-dimensional metal dendrite, the metallic particles making has three-dimensional pine-tree structure, and be micro-nano rank, this pattern, because specific area is larger, can be widely used in biology, chemistry and electrical application.Preparation process is easy, and the equipment investment of use is few, energy consumption is low, productive rate is high, and the metallic particles making has higher mechanical strength and good low-temperature sintering characteristic.The micro-structural of the metallic particles of the preparation method of this detailed description of the invention to preparation has also good control.Be specially:
Preferably, by regulating concentration ratio and charging rate, the concrete fractal pattern of the three-dimensional pine-tree structure of can corresponding control preparing:
Step 1) in regulate described a exist: 1≤a < 8, step 2) in control described First Speed V1 and described second speed V2 and exist: 0.5mL/min≤V1 < 5mL/min, 0.5mL/min≤V2 < 5mL/min, thereby step 3) in the three-dimensional pine-tree structure of the described metallic particles that makes there is one-level fractal structure.
Step 1) in regulate described a exist: 8≤a < 40, step 2) in control described First Speed V1 and described second speed V2 and exist: 5mL/min≤V1 < 15mL/min, 5mL/min≤V2 < 15mL/min, thereby step 3) in the three-dimensional pine-tree structure of the described metallic particles that makes there is secondary fractal structure.
Step 1) in regulate described a exist: 40≤a≤50, step 2) in control described First Speed V1 and described second speed V2 and exist: 15mL/min≤V1≤20mL/min, 15mL/min≤V2≤20mL/min, thereby step 3) in the three-dimensional pine-tree structure of the described metallic particles that makes there are three grades of fractal structures.
By above-mentioned setting, can set corresponding steps for different preparation requirements and the application scenarios of metallic particles, thereby the extensive dendrite material of preparing in batches different size and pattern is easy to carry out industrialization and large-scale mass production.For example, if wish to produce the three-dimensional dendrite with secondary fractal structure, can corresponding adjusting a when preparation at 8≤a < 40, speed is at 5mL/min≤V < 15mL/min, the three-dimensional dendrite of the metallic particles making have secondary fractal structure pattern.Compare existing preparation method and cannot require directed production according to preparation, this preferably arranges can realize directed production control, is convenient to industrialization batch production.
Preferably similar, also the pH of adjustable reaction temperature and mixed solution realizes respectively directed control, specific as follows:
By regulating reaction temperature, the diameter dimension of the three-dimensional pine-tree structure of can corresponding control preparing: regulate described reaction temperature T to exist :-10 DEG C≤T≤25 DEG C, thus the diameter d of the three-dimensional pine-tree structure of the described metallic particles making is in the scope of 100nm≤d≤15 μ m; Regulate described reaction temperature T to exist: 25 DEG C of < T≤80 DEG C, thus the diameter d of the three-dimensional pine-tree structure of the described metallic particles making is in the scope of 15 μ m < d≤50 μ m.By the adjusting to reaction temperature, temperature changes in the scope of-10 DEG C to 80 DEG C, and the diameter d that can control the dendrite of the metallic particles of preparation changes in the scope of 100nm≤d≤50 μ m.
By regulating the pH of mixed solution described in reaction vessel, the concrete fractal pattern of the three-dimensional pine-tree structure of also can corresponding control preparing: regulate the pH of described mixed solution to exist: 3.5≤pH≤5.5, thus the three-dimensional pine-tree structure of the described metallic particles making has one-level fractal structure; Regulate the pH of described mixed solution to exist: 5.5 < pH≤7.5, thus the three-dimensional pine-tree structure of the described metallic particles making has secondary fractal structure; Regulate the pH of described mixed solution to exist: 7.5 < pH≤11, thus the three-dimensional pine-tree structure of the described metallic particles making has three grades of fractal structures.By the adjusting to mixed solution pH, pH changes in 3 to 11 scope, the pattern that can control the dendrite of the metallic particles of preparation be that one-level is fractal, secondary is fractal or three grades fractal.
The preparation method of the metallic particles of this detailed description of the invention, with respect to the preparation method of other metallic particles, can realize mass synthetic, and be a kind of relatively cost-saving, raise the efficiency and the method for environmental protection.Single dendrite that disperses micron 3-dimensional metal dendrite to compare other synthetic method gained of gained, there is the controlled three-dimensional structure of pattern, by regulating different parameters, can accurately control the fractal pattern of micro-structural and the size of metallic dendrite, therefore, the metallic particles of the three-dimensional dendrite of gained can be widely used in the fields such as bio-sensing, chemical catalysis.
Specific experiment example is set as follows, verifies the pine-tree structure of the metallic particles that this detailed description of the invention makes.
Experiment 1: the liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (0.05mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 1), at the uniform velocity splash in reaction vessel with the speed of identical 0.5mL/min by binary channels continuous feeding equipment, when reaction, temperature is 25 DEG C of room temperatures, regulating the pH value of mixed solution is 5.5, in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag1a.
As shown in Figure 2, as can be seen from Figure 2, the degree of crystallinity of the silver-colored dendrite of metallic particles is higher for the X ray diffracting spectrum XRD of silver metal particles Ag1a.The SEM SEM of silver metal particles Ag1a schemes as shown in Figure 3, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 1 to 3 micron.The pattern of dendrite is one-level fractal structure, is independently " branch ".
Experiment 2: the liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (1mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 20), at the uniform velocity splash in reaction vessel with the speed of identical 8mL/min by binary channels continuous feeding equipment, when reaction, temperature is 25 DEG C of room temperatures, regulating the pH value of mixed solution is 4, in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag1b.
Distribution of shapes and Fig. 2 of the X ray diffracting spectrum of silver metal particles Ag1b are similar, and the relative altitude that is each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, therefore no longer repeat to provide picture, and also the degree of crystallinity of known silver-colored dendrite is higher.The SEM SEM of silver metal particles Ag1b schemes as shown in Figure 4, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 1 to 3 micron.The pattern of dendrite is one-level fractal structure, is independently " branch ".
Experiment 3: similar with the method for experiment 1, difference is to change concentration ratio and charging rate.
The liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (0.4mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 8), at the uniform velocity splash in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, when reaction, temperature is 25 DEG C of room temperatures, regulating the pH value of mixed solution is 5.5, in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag2a.
Distribution of shapes and Fig. 2 of the X ray diffracting spectrum of silver metal particles Ag2a are similar, and the relative altitude that is each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, therefore no longer repeat to provide picture, and also the degree of crystallinity of known silver-colored dendrite is higher.The SEM SEM of silver metal particles Ag2a schemes as shown in Figure 5, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 4 to 6 microns.The pattern of dendrite is secondary fractal structure, grow again one-level " branch ", and the dimension scale of two-layer configuration is identical in " branch " structure, is about 1:1 to 3:1, and the angle of every two-layer configuration is about 45 ° to 90 °.
Fig. 6 is silver metal particles Ag2a process 15min, the SEM figure ultrasonic after treatment of 53kHz, and silver-colored dendrite still has good complete shape and appearance as can be known from Fig. 6, shows that silver metal particles Ag2a can stand ultrasonic processing, has higher mechanical strength.
Fig. 7 is the SEM figure of silver metal particles Ag2a after 150 DEG C of sintering generation sintering phenomenons.Fig. 7 a and Fig. 7 b are respectively after sintering the SEM figure under different micro-multiplication factor, in figure, scale is respectively 600nm and 100nm, the main body pattern of silver-colored dendrite is still good as can be seen from Figure 7, but there is sintering phenomenon in branch end, show that silver metal particles Ag2a can stand the low-temperature sintering of 150 DEG C, there is good low-temperature sintering characteristic, can be applied to the engineering fields such as conductive silver paste.
Experiment 4: similar with the method for experiment 2, difference is to change change pH values, in experiment 2, pH value is 4, in experiment 4, pH value is 7.
The liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (1mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 20), at the uniform velocity splash in reaction vessel with the speed of identical 8mL/min by binary channels continuous feeding equipment, when reaction, temperature is room temperature, regulating the pH value of mixed solution is 7 (in 5.5～7.5 scopes), in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 300Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag2b.
Distribution of shapes and Fig. 2 of the X ray diffracting spectrum of silver metal particles Ag2b are similar, and the relative altitude that is each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, therefore no longer repeat to provide picture, and also the degree of crystallinity of known silver-colored dendrite is higher.The SEM SEM of silver metal particles Ag2a schemes as shown in Figure 8, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 4 to 6 microns.The pattern of dendrite is secondary fractal structure, grow again one-level " branch ", and the dimension scale of two-layer configuration is identical in " branch " structure, is about 1:1 to 3:1, and the angle of every two-layer configuration is about 45 ° to 90 °.
Experiment 5: similar with the method for experiment 1, difference is to change concentration ratio and charging rate.
The liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (2mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 40), liquor argenti nitratis ophthalmicus is at the uniform velocity splashed in reaction vessel with the speed of 0.5mL/min by binary channels continuous feeding equipment, speed with 15mL/min at the uniform velocity splashes into hydroxylamine solution in reaction vessel, when reaction, temperature is 25 DEG C of room temperatures, regulating the pH value of mixed solution is 5.5, in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag3a.
Distribution of shapes and Fig. 2 of the X ray diffracting spectrum of silver metal particles Ag3a are similar, and the relative altitude that is each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, therefore no longer repeat to provide picture, and also the degree of crystallinity of known silver-colored dendrite is higher.The SEM SEM of silver metal particles Ag3a schemes as shown in Figure 9, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 8 to 10 microns.The pattern of dendrite is three grades of fractal structures, grow again one-level " branch " after growing one-level " branch ", and the dimension scale of every two-layer configuration is identical, is about 1:1 to 3:1 in " branch " structure, and the angle of every two-layer configuration is about 45 ° to 90 °.
Experiment 6: similar with the method for experiment 2, difference is to change change pH values, in experiment 2, pH value is 4, in experiment 4, pH value is 10.
The liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (1mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 20), at the uniform velocity splash in reaction vessel with the speed of identical 8mL/min by binary channels continuous feeding equipment, when reaction, temperature is room temperature, regulating the pH value of mixed solution is 10 (in 7.5～11 scopes), in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag3b.
Distribution of shapes and Fig. 2 of the X ray diffracting spectrum of silver metal particles Ag3b are similar, and the relative altitude that is each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, therefore no longer repeat to provide picture, and also the degree of crystallinity of known silver-colored dendrite is higher.The SEM SEM of silver metal particles Ag3b schemes as shown in figure 10, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 8 to 10 microns.The pattern of dendrite is three grades of fractal structures, grow again one-level " branch " after growing one-level " branch ", and the dimension scale of every two-layer configuration is identical, is about 1:1 to 3:1 in " branch " structure, and the angle of every two-layer configuration is about 45 ° to 90 °.
Experiment 1, experiment 3 and experiment 5 in more above-mentioned 6 experiments, only regulate the value of ratio a of the molar concentration of reductant solution and metal salt solution and the value of speed, can realize the control that pine-tree structure changes in one-level fractal (Ag1a), secondary fractal (Ag2a) and three grades fractal ((Ag3a)).
Experiment 2, experiment 4 and experiment 6 in more above-mentioned 6 experiments, the pH value that regulates separately mixed solution, also can realize the control that pine-tree structure changes in one-level fractal (Ag1b), secondary fractal (Ag2b) and three grades fractal (Ag3b).
Experiment 7: with the method similar (be all that a is 8, speed is 5mL/min) of experiment 3, difference is to change reaction temperature: experiment 3 is 25 DEG C of room temperatures, and experiment 7 is 0 DEG C.
The liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (0.4mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 8), at the uniform velocity splash in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, when reaction, temperature is 0 DEG C, regulating the pH value of mixed solution is 5.5, in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag2c.
Distribution of shapes and Fig. 2 of the X ray diffracting spectrum of silver metal particles Ag2c are similar, and the relative altitude that is each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, therefore no longer repeat to provide picture, and also the degree of crystallinity of known silver-colored dendrite is higher.The SEM SEM of silver metal particles Ag2c schemes as shown in figure 11, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 1 to 2 micron.The pattern of dendrite is also secondary fractal structure, grows again one-level " branch " in " branch " structure.
From testing 7 and experiment 3 contrast, under identical experiment condition, reduce reaction temperature, can obtain the micron 3-dimensional metal dendrite that size is less.
Experiment 8: with the method similar (be all that a is 8, speed is 5mL/min) of experiment 3, difference is to change reaction temperature: experiment 3 is 25 DEG C of room temperatures, and experiment 8 is 50 DEG C.
The liquor argenti nitratis ophthalmicus of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (0.4mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 8), at the uniform velocity splash in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, when reaction, temperature is 50 DEG C, regulating the pH value of mixed solution is 5.5, in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly celadon precipitation.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 27g silver metal particles Ag2d.
Distribution of shapes and Fig. 2 of the X ray diffracting spectrum of silver metal particles Ag2d are similar, and the relative altitude that is each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, therefore no longer repeat to provide picture, and also the degree of crystallinity of known silver-colored dendrite is higher.The SEM SEM of silver metal particles Ag2d schemes as shown in figure 12, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 10 to 15 microns.The pattern of dendrite is also secondary fractal structure, grows again one-level " branch " in " branch " structure.
From testing 8 and experiment 3 contrast, under identical experiment condition, improve reaction temperature, can obtain the micron 3-dimensional metal dendrite that size is larger.
Experiment 9: for preparing golden dendrite.
The chlorauric acid solution of the each 5L of same volume (0.05mol/L) and hydroxylamine solution (0.4mol/L) are put into respectively to container 1 and 2 (the ratio a of the reductant concentration of reaction and the molar concentration of metal salt solution is 8), at the uniform velocity splash in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, when reaction, temperature is 25 DEG C of room temperatures, regulating the pH value of mixed solution is 6.5, in course of reaction, utilize mixer oscillator that mixed liquor is slightly vibrated, surge frequency range is 30Hz.In test tube, generate rapidly black precipitate.Sediment is filtered and spent Ion Cleaning 2-3 time, then carry out vacuum drying preservation, make 49.25g gold metallic particles Au.
As shown in figure 13, as can be seen from Figure 13, the degree of crystallinity of the golden dendrite of golden metallic particles Au is higher for the X ray diffracting spectrum of gold metallic particles Au.The SEM SEM of gold metallic particles Au schemes as shown in figure 14, and gained dendrite is more even as we know from the figure, is three-dimensional tree dendritic morphology, and diameter is 4 to 6 microns.The pattern of dendrite is also secondary fractal structure, grow again one-level " branch ", and the dimension scale of two-layer configuration is basic identical in " branch " structure, is about 1:1 to 3:1, and the angle of every two-layer configuration is about 45 ° to 90 °.
It should be noted that, in the experiment arranging in this detailed description of the invention, be all prepared with twin-channel feed arrangement 5, but can improve easily, adopt the multiple reactions in parallel of multichannel feed arrangement, as long as be 0.1～50 according to aforementioned manner controlled concentration than a in each reaction, speed, in the scope of 0.1～20mL/min, all can obtain the 3-dimensional metal dendrite of corresponding microstructure appearance.By the multiple reactions of parallel connection, make to react between reducing agent and metal salt solution, multiple identical reactions are carried out simultaneously, thereby significantly improve preparation efficiency, conveniently carry out industry and amplify, batch production.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, make without departing from the inventive concept of the premise some substituting or obvious modification, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a preparation method with the metallic particles of three-dimensional pine-tree structure, is characterized in that: comprise the following steps: 1) prepare reductant solution and metal salt solution, described reductant solution is 0.1～50 with the ratio a of the molar concentration of described metal salt solution; 2) isopyknic described reductant solution and described metal salt solution are at the uniform velocity splashed in reaction vessel with First Speed V1 and second speed V2 respectively, described First Speed V1 and described second speed V2 are all in the scope of 0.1～20mL/min, in course of reaction, mixed solution in described reaction vessel is shaken with the frequency of oscillation of 10～50Hz, in described reaction vessel, generate precipitation; 3) described precipitation is filtered, cleaned, then carry out vacuum drying, make the metallic particles with three-dimensional pine-tree structure.
2. the preparation method of the metallic particles with three-dimensional pine-tree structure according to claim 1, it is characterized in that: described step 1) in regulate described a exist: 1≤a < 8, described step 2) in control described First Speed V1 and described second speed V2 and exist: 0.5mL/min≤V1 < 5mL/min, 0.5mL/min≤V2 < 5mL/min, thereby described step 3) in the three-dimensional pine-tree structure of the described metallic particles that makes there is one-level fractal structure; Described step 1) in regulate described a exist: 8≤a < 40, described step 2) in control described First Speed V1 and described second speed V2 and exist: 5mL/min≤V1 < 15mL/min, 5mL/min≤V2 < 15mL/min, thereby described step 3) in the three-dimensional pine-tree structure of the described metallic particles that makes there is secondary fractal structure; Described step 1) in regulate described a exist: 40≤a≤50, described step 2) in control described First Speed V1 and described second speed V2 and exist: 15mL/min≤V1≤20mL/min, 15mL/min≤V2≤20mL/min, thereby described step 3) in the three-dimensional pine-tree structure of the described metallic particles that makes there are three grades of fractal structures.
3. the preparation method of the metallic particles with three-dimensional pine-tree structure according to claim 1, it is characterized in that: described step 2) in also comprise adjusting reaction temperature in course of reaction: regulate described reaction temperature T to exist :-10 DEG C≤T≤25 DEG C, thereby the diameter d of the three-dimensional pine-tree structure of the described metallic particles making is in the scope of 100nm≤d≤15 μ m; Regulate described reaction temperature T to exist: 25 DEG C of < T≤80 DEG C, thus the diameter d of the three-dimensional pine-tree structure of the described metallic particles making is in the scope of 15 μ m < d≤50 μ m.
4. the preparation method of the metallic particles with three-dimensional pine-tree structure according to claim 1, it is characterized in that: described step 2) in also comprise the pH that regulates described mixed solution in course of reaction: regulate the pH of described mixed solution to exist: 3.5≤pH≤5.5, thereby the three-dimensional pine-tree structure of the described metallic particles making has one-level fractal structure; Regulate the pH of described mixed solution to exist: 5.5 < pH≤7.5, thus the three-dimensional pine-tree structure of the described metallic particles making has secondary fractal structure; Regulate the pH of described mixed solution to exist: 7.5 < pH≤11, thus the three-dimensional pine-tree structure of the described metallic particles making has three grades of fractal structures.
5. the preparation method of the metallic particles with three-dimensional pine-tree structure according to claim 1, is characterized in that: in described metal salt solution, metal ion is silver ion, and anion is hypochlorite or nitrate anion; In described metal salt solution, metal ion is gold ion, and anion is chlorate anions; In described metal salt solution, metal ion is copper ion, and anion is nitrate anion, chlorion or sulfate radical.
6. the preparation method of the metallic particles with three-dimensional pine-tree structure according to claim 1, is characterized in that: described metal salt solution is silver salt solution, and described reducing agent is acetaldehyde, citric acid, azanol or hydrazine; Described metal salt solution is golden salting liquid, and described reducing agent is 2-amino-3-mercaptopropionic acid or sodium borohydride; Described metal salt solution is copper salt solution, and described reducing agent is hydroxylamine hydrochloride or sodium borohydride.
7. the metallic particles with three-dimensional pine-tree structure making according to the preparation method described in claim 1～6.
8. metallic particles according to claim 7, is characterized in that: the three-dimensional pine-tree structure of described metallic particles has one-level, secondary or three grades of fractal structures.
9. metallic particles according to claim 7, is characterized in that: the diameter d of the three-dimensional pine-tree structure of described metallic particles is in the scope of 100nm≤d≤50 μ m.
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