CN104028776B - A kind of preparation method and metallic particles with the metallic particles of three-dimensional pine-tree structure - Google Patents
A kind of preparation method and metallic particles with the metallic particles of three-dimensional pine-tree structure Download PDFInfo
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- 239000002184 metal Substances 0.000 claims abstract description 52
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- 238000001556 precipitation Methods 0.000 claims abstract description 17
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- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 13
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- 229910052737 gold Inorganic materials 0.000 claims description 9
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- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
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Abstract
The invention discloses a kind of preparation method and the metallic particles with the metallic particles of three-dimensional pine-tree structure, preparation method comprises the following steps: 1) prepare reductant solution and metal salt solution, and 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 instilled in reaction vessel with First Speed V1 and second speed V2 respectively, described First Speed V1 and described second speed V2 is 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, generates precipitation; 3) described precipitation is carried out filter, clean, then carry out vacuum drying, the obtained metallic particles with three-dimensional pine-tree structure.Preparation method of the present invention, preparation process is simple, and the micro-structural of obtained metallic particles can reach 100nm ~ 50 μm, and more easily can control the pattern of the three-dimensional pine-tree structure prepared.
Description
[technical field]
The present invention relates to the preparation method of metallic particles, particularly relate to a kind of preparation method and the metallic particles with the metallic particles of 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 excellent catalytic performance, electrical property etc., thus in an increasingly wide range of applications in electronics, chemistry, bioengineering etc., 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.
At present to precious metal material, the such as research major part of the micro nano structure of silver concentrates on zero dimension silver nanoparticle ball, 1-dimention nano silver line and two-dimentional micron silver strip aspect.The nanometer-level silver structure of the patterns such as nano-silver thread, nanometer rods, nano cubic monocrystalline, nanometer regular polygon is obtained by change surfactant and reducing agent.For gold and platinum etc. also more preparation and the property Quality Research concentrating on nanosphere particle.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 effective batch preparation means, relatively less to its research.In addition, there is about preparation the synthetic method of the metallic particles of three-dimensional pine-tree structure at present, comprise electrochemical deposition, gamma-rays deposition, dielectric breakdown, gas-phase polymerization, Ultraviolet radiation reduction and ultrasonic assistant reducing process etc., but said method has certain limitation, special installation is such as needed to assist, consuming time longer, particle surface cleanliness factor is low, and output is lower.In addition, owing to adopting template to assist, the stereoeffect of the 3-dimensional metal dendrite of preparation is poor more, and the pattern control of dendrite is more weak.
[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 the metallic particles with the metallic particles of three-dimensional pine-tree structure are proposed, preparation process is simple, the micro-structural of obtained metallic particles can reach micron order (100nm ~ 50 μm), and more easily can control the pattern of the three-dimensional pine-tree structure prepared.
Technical problem of the present invention is solved by following technical scheme:
Have a preparation method for the metallic particles of three-dimensional pine-tree structure, 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 instilled in reaction vessel with First Speed V1 and second speed V2 respectively, described First Speed V1 and described second speed V2 is 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, generates precipitation; 3) described precipitation is carried out filter, clean, then carry out vacuum drying, the obtained metallic particles with three-dimensional pine-tree structure.
The metallic particles with three-dimensional pine-tree structure that a kind of basis preparation method as above obtains.
The beneficial effect that the present invention is compared with the prior art is:
Preparation method and the metallic particles with the metallic particles of three-dimensional pine-tree structure of the present invention, the synthesis of the micron order dendroid dendrite of metallic particles is realized by solution phase method of reducing, control concentration ratio and both charging rates of described metal salt solution and reductant solution, by reaction solution Homogeneous phase mixing, thus the obtained dendritic pine-tree structure of three-dimensional tree, obtained micro-structural can reach micron order (100nm ~ 50 μm).And by controlling two parameter at particular range, can the concrete pattern of corresponding control three-dimensional structure be also one-level fractal structure or multistage fractal result, having good control to the pattern of micro-structural.Further, by controlling reaction temperature, pH value, the diameter dimension of micro-structural and multistage fractal structure can be controlled respectively.Preparation method of the present invention, preparation process is easy, and more easily can control the pattern of the three-dimensional pine-tree structure prepared, by adjusting process and material rate, can, for the different purposes design also extensive dendritic materials preparing different size and pattern in batches, be easy to carry out industrialization and large-scale mass production.
[accompanying drawing explanation]
Fig. 1 is the system architecture schematic diagram preparing metallic particles of the specific embodiment of the invention;
Fig. 2 is the X ray diffracting spectrum of silver metal particles prepared by the experiment 1 of the specific embodiment of the invention;
Fig. 3 is the SEM SEM figure of silver metal particles prepared by the experiment 1 of the specific embodiment of the invention;
Fig. 4 is the SEM SEM figure of silver metal particles prepared by the experiment 2 of the specific embodiment of the invention;
Fig. 5 is the SEM SEM figure of silver metal particles prepared by the experiment 3 of the specific embodiment of the invention;
Fig. 6 is the SEM figure of silver metal particles after ultrasonic process prepared by the experiment 3 of the specific embodiment of the invention;
Fig. 7 is the SEM figure of silver metal particles after sintering processes prepared by the experiment 3 of the specific embodiment of the invention;
Fig. 8 is the SEM SEM figure of silver metal particles prepared by the experiment 4 of the specific embodiment of the invention;
Fig. 9 is the SEM SEM figure of silver metal particles prepared by the experiment 5 of the specific embodiment of the invention;
Figure 10 is the SEM SEM figure of silver metal particles prepared by the experiment 6 of the specific embodiment of the invention;
Figure 11 is the SEM SEM figure of silver metal particles prepared by the experiment 7 of the specific embodiment of the invention;
Figure 12 is the SEM SEM figure of silver metal particles prepared by the experiment 8 of the specific embodiment of the invention;
Figure 13 is the X ray diffracting spectrum of golden metallic particles prepared by the experiment 9 of the specific embodiment of the invention;
Figure 14 is the SEM SEM figure of golden metallic particles prepared by the experiment 9 of the specific embodiment of the invention.
[detailed description of the invention]
Contrast accompanying drawing below in conjunction with detailed description of the invention the present invention is described in further details.
The present invention proposes the metallic particles preparing three-dimensional pine-tree structure, and requirement is convenient to control particle size, domain size distribution and level pattern, realizes synthesis in enormous quantities 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, still there is larger difficulty in the batch synthesis at present for this kind of dendrite, not yet has the ripe dendritic dendrite of method stable mass synthesis homogeneous, the monodispersed micron three-dimensional tree of pattern.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 control nucleation rate and the speed of growth.Due to each direction of dendrite and fractal level growth needed for thermokinetics condition different, only have 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, propose solution phase method of reducing.Different from the method that other prepare metallic dendrite, the present invention adopts mode metal salt solution and reducing agent being dripped simultaneously mixing in redox reaction process, and ensure the rate of addition of metal salt solution and reducing agent within the specific limits by some equipment, by regulating reactant concentration ratio and mixing velocity, thus the obtained metallic particles with the three-dimensional pine-tree structure of single dispersing.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 seepage, is suitable for the popularization of suitability for industrialized production.Because the cost of raw material adopted is low, more easily obtain, and the formation rate of three dimensional micron dendrite is up to 99%, so substantially increase the economic benefit of production.
As shown in Figure 1, for preparing the system architecture schematic diagram of metallic particles in this detailed description of the invention, comprise the following steps during preparation:
(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 reducing and obtain 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, ethylhydroxyl amine, 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 is multiple mixing, in reductant solution, the molar concentration sum of each reducing agent is 0.1 ~ 50 with the ratio of the molar concentration sum of each slaine in metal salt solution.Be the metal salt solution and reductant solution that prepare respectively in container 1 and 2 in Fig. 1, 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 comparatively typically silver ion, gold ion and copper ion.For different metal ions, there is different anion pairings, such as, for silver ion, have hypochlorite, nitrate anion etc. than better suited anion; For gold ion, be chlorate anions than better suited anion; For copper ion, preferred nitrate anion, chlorion, sulfate radical etc.And for different metal salt solutions, different reducing agents also to be selected, such as, 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 instilled in reaction vessel with First Speed V1 and second speed V2 respectively, described First Speed V1 and described second speed V2 is 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, generates precipitation.
As shown in Figure 1, feed is continued by adopting binary channels or multichannel continuous feeding equipment (such as peristaltic pump 5), solution also reacts rapidly in the tip mixes of channel output end mouth, in instillation reaction vessel 6, reaction vessel 6 is placed in oscillator 7 and carries out slight oscillatory, is precipitated thing after reaction a period of time.
In preparation process, the ratio a controlling the molar concentration of reductant solution and metal salt solution is 0.1 ~ 50, the scope that the charging rate controlling metal salt solution and reducing agent is not arbitrarily arranged respectively in the scope of 0.1 ~ 20mL/min, but when concentration and speed are in above-mentioned scope, can the abundant degree of corresponding control reduction reaction.If the ratio of concentration is too large or charging rate is too fast, then 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, then reduction reaction speed, dendritic growth is too fast, not controlled, and the pine-tree structure finally obtained 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 to the control of reactant concentration scope and the control to continuous feeding speed, need the strict ratio and the charging rate that control the concentration of reductant solution and metal salt solution in course of reaction, the dendritic pine-tree structure of three-dimensional tree that could finally obtain 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) be added drop-wise in reaction vessel is 0.1 ~ 20mL/min, then coordinate concentration ratio can obtain the dendritic pine-tree structure of the three-dimensional tree finally wanted.
In reaction, coordinate frequency of oscillation to vibrate at 10 ~ 50Hz, reactant can be made fully to mix, guarantee that the dendrite generated is even.
3) described precipitation is carried out filter, clean, then carry out vacuum drying, the obtained metallic particles with three-dimensional pine-tree structure.
The extensive batch that this detailed description of the invention provides prepares the method for micron 3-dimensional metal dendrite, obtained metallic particles has three-dimensional pine-tree structure, and be micro-nano rank, this pattern is comparatively large due to specific area, 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 obtained metallic particles has higher mechanical strength and excellent low-temperature sintering characteristic.The micro-structural of preparation method to the metallic particles of preparation of this detailed description of the invention has also good control.Be specially:
Preferably, by regulating concentration ratio and charging rate, can the corresponding concrete fractal pattern controlling the three-dimensional pine-tree structure of preparation:
Step 1) in regulate described a exist: 1≤a < 8, step 2) in control described First Speed V1 and described second speed V2 exist: 0.5mL/min≤V1 < 5mL/min, 0.5mL/min≤V2 < 5mL/min, thus step 3) in the three-dimensional pine-tree structure of obtained described metallic particles 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 exist: 5mL/min≤V1 < 15mL/min, 5mL/min≤V2 < 15mL/min, thus step 3) in the three-dimensional pine-tree structure of obtained described metallic particles 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 exist: 15mL/min≤V1≤20mL/min, 15mL/min≤V2≤20mL/min, thus step 3) in the three-dimensional pine-tree structure of obtained described metallic particles there are three grades of fractal structures.
By above-mentioned setting, corresponding steps can be set for the application scenarios of different preparation requirements and metallic particles, thus extensive batch prepares the dendritic materials of different size and pattern, is easy to carry out industrialization and large-scale mass production.Such as, if wish to produce the three-dimensional dendrite with secondary fractal structure, during preparation can corresponding adjustment a at 8≤a < 40, speed is at 5mL/min≤V < 15mL/min, and namely the three-dimensional dendrite of obtained metallic particles have secondary fractal structure pattern.Compare existing preparation method and cannot require directed production according to preparation, this preferably arranges and can realize oriented control production, is convenient to industrialization batch production.
Preferably similar, also the pH of adjustable reaction temperature and mixed solution realizes oriented control respectively, specific as follows:
By regulating reaction temperature, can the corresponding diameter dimension of three-dimensional pine-tree structure controlling preparation: 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 obtained described metallic particles is in the scope of 100nm≤d≤15 μm; 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 obtained described metallic particles is in the scope of 15 μm of < d≤50 μm.By the adjustment 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 prepared changes in the scope of 100nm≤d≤50 μm.
By regulating the pH of mixed solution described in reaction vessel, also can the corresponding concrete fractal pattern of three-dimensional pine-tree structure controlling preparation: regulate the pH of described mixed solution to exist: 3.5≤pH≤5.5, thus the three-dimensional pine-tree structure of obtained described metallic particles 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 obtained described metallic particles have secondary fractal structure; Regulate the pH of described mixed solution to exist: 7.5 < pH≤11, thus the three-dimensional pine-tree structure of obtained described metallic particles have three grades of fractal structures.By the adjustment to mixed solution pH, pH changes in the scope of 3 to 11, the pattern of dendrite that can control the metallic particles prepared 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, relative to the preparation method of other metallic particles, can realize mass synthesis, and be a kind of relatively cost-saving, raise the efficiency and the method for environmental protection.The single dispersing micron 3-dimensional metal dendrite of gained compares the dendrite of other synthetic method gained, there is the three-dimensional structure of morphology controllable, by regulating different parameters, accurately can 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 bio-sensing, the fields such as 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 obtains.
Experiment 1: the liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (0.05mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 1), at the uniform velocity instilled in reaction vessel with the speed of identical 0.5mL/min by binary channels continuous feeding equipment, during reaction, temperature is room temperature 25 DEG C, the pH value regulating mixed solution is 5.5, utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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.As shown in Figure 3, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 1 to 3 microns for the SEM SEM figure of silver metal particles Ag1a.The pattern of dendrite is one-level fractal structure, is independently " branch ".
Experiment 2: the liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (1mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 20), at the uniform velocity instilled in reaction vessel with the speed of identical 8mL/min by binary channels continuous feeding equipment, during reaction, temperature is room temperature 25 DEG C, the pH value regulating mixed solution is 4, utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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 just the relative altitude of each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, and therefore no longer repeat to provide picture, also the degree of crystallinity of known silver-colored dendrite is higher.As shown in Figure 4, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 1 to 3 microns for the SEM SEM figure of silver metal particles Ag1b.The pattern of dendrite is one-level fractal structure, is independently " branch ".
Experiment 3: similar with the method for experiment 1, difference changes concentration ratio and charging rate.
The liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (0.4mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 8), at the uniform velocity instilled in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, during reaction, temperature is room temperature 25 DEG C, the pH value regulating mixed solution is 5.5, utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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 just the relative altitude of each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, and therefore no longer repeat to provide picture, also the degree of crystallinity of known silver-colored dendrite is higher.As shown in Figure 5, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 4 to 6 microns for the SEM SEM figure of silver metal particles Ag2a.The pattern of dendrite is secondary fractal structure, " branch " structure grows again one-level " branch ", and the dimension scale of two-layer configuration is identical, is about 1:1 to 3:1, and the angle of every two-layer configuration is about 45 ° to 90 °.
Fig. 6 is the SEM figure of silver metal particles Ag2a after the ultrasonic process of 15min, 53kHz, and silver-colored dendrite still has good pattern integrality as can be known from Fig. 6, shows that silver metal particles Ag2a can stand ultrasonic process, has higher mechanical strength.
Fig. 7 is that silver metal particles Ag2a, through 150 DEG C of sintering, the SEM figure after sintering phenomenon occurs.Fig. 7 a and Fig. 7 b are respectively the SEM figure under the rear different micro-multiplication factor of sintering, 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 branch end there occurs sintering phenomenon, show that silver metal particles Ag2a can stand the low-temperature sintering of 150 DEG C, there is excellent low-temperature sintering characteristic, can the engineering fields such as conductive silver paste be applied to.
Experiment 4: similar with the method for experiment 2, difference changes pH value, and in experiment 2, pH value is 4, and in experiment 4, pH value is 7.
The liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (1mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 20), at the uniform velocity instilled in reaction vessel with the speed of identical 8mL/min by binary channels continuous feeding equipment, during reaction, temperature is room temperature, the pH value regulating mixed solution is 7 (in the scopes of 5.5 ~ 7.5), utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 300Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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 just the relative altitude of each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, and therefore no longer repeat to provide picture, also the degree of crystallinity of known silver-colored dendrite is higher.As shown in Figure 8, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 4 to 6 microns for the SEM SEM figure of silver metal particles Ag2a.The pattern of dendrite is secondary fractal structure, " branch " structure grows again one-level " branch ", and the dimension scale of two-layer configuration is identical, 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 changes concentration ratio and charging rate.
The liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (2mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 40), liquor argenti nitratis ophthalmicus is at the uniform velocity instilled in reaction vessel with the speed of 0.5mL/min by binary channels continuous feeding equipment, with the speed of 15mL/min, hydroxylamine solution is at the uniform velocity instilled in reaction vessel, during reaction, temperature is room temperature 25 DEG C, the pH value regulating mixed solution is 5.5, utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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 just the relative altitude of each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, and therefore no longer repeat to provide picture, also the degree of crystallinity of known silver-colored dendrite is higher.As shown in Figure 9, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 8 to 10 microns for the SEM SEM figure of silver metal particles Ag3a.The pattern of dendrite is three grades of fractal structures, grows again one-level " branch " after " branch " structure growing one-level " branch ", and the dimension scale of every two-layer configuration is identical, and be about 1:1 to 3:1, the angle of every two-layer configuration is about 45 ° to 90 °.
Experiment 6: similar with the method for experiment 2, difference changes pH value, and in experiment 2, pH value is 4, and in experiment 4, pH value is 10.
The liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (1mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 20), at the uniform velocity instilled in reaction vessel with the speed of identical 8mL/min by binary channels continuous feeding equipment, during reaction, temperature is room temperature, the pH value regulating mixed solution is 10 (in the scopes of 7.5 ~ 11), utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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 just the relative altitude of each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, and therefore no longer repeat to provide picture, also the degree of crystallinity of known silver-colored dendrite is higher.As shown in Figure 10, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 8 to 10 microns for the SEM SEM figure of silver metal particles Ag3b.The pattern of dendrite is three grades of fractal structures, grows again one-level " branch " after " branch " structure growing one-level " branch ", and the dimension scale of every two-layer configuration is identical, and be about 1:1 to 3:1, the angle of every two-layer configuration is about 45 ° to 90 °.
Experiment 1 in more above-mentioned 6 experiments, experiment 3 and experiment 5, only regulate the value of ratio a and the value of speed of the molar concentration of reductant solution and metal salt solution, pine-tree structure can be realized in one-level fractal (Ag1a), secondary fractal (Ag2a) and three grades fractal ((Ag3a)) middle control changed.
Experiment 2 in more above-mentioned 6 experiments, experiment 4 and experiment 6, the pH value of independent adjustment mixed solution, also can realize pine-tree structure in one-level fractal (Ag1b), secondary fractal (Ag2b) and three grades fractal (Ag3b) middle control changed.
Experiment 7: similar with the method for experiment 3 (are all a be 8, speed is 5mL/min), difference changes reaction temperature: experiment 3 is room temperature 25 DEG C, and experiment 7 is 0 DEG C.
The liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (0.4mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 8), at the uniform velocity instilled in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, during reaction, temperature is 0 DEG C, the pH value regulating mixed solution is 5.5, utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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 just the relative altitude of each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, and therefore no longer repeat to provide picture, also the degree of crystallinity of known silver-colored dendrite is higher.As shown in figure 11, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 1 to 2 microns for the SEM SEM figure of silver metal particles Ag2c.The pattern of dendrite is also secondary fractal structure, " branch " structure grows again one-level " branch ".
From experiment 7 and the contrast of testing 3, under identical experiment condition, reduce reaction temperature, the micron 3-dimensional metal dendrite that size is less can be obtained.
Experiment 8: similar with the method for experiment 3 (are all a be 8, speed is 5mL/min), difference changes reaction temperature: experiment 3 is room temperature 25 DEG C, and experiment 8 is 50 DEG C.
The liquor argenti nitratis ophthalmicus (0.05mol/L) of each for same volume 5L and hydroxylamine solution (0.4mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 8), at the uniform velocity instilled in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, during reaction, temperature is 50 DEG C, the pH value regulating mixed solution is 5.5, utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Celadon precipitation is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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 just the relative altitude of each crest is variant, and the 2 θ number of degrees that each crest is corresponding are still identical, and therefore no longer repeat to provide picture, also the degree of crystallinity of known silver-colored dendrite is higher.As shown in figure 12, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 10 to 15 microns for the SEM SEM figure of silver metal particles Ag2d.The pattern of dendrite is also secondary fractal structure, " branch " structure grows again one-level " branch ".
From experiment 8 and the contrast of testing 3, under identical experiment condition, improve reaction temperature, the micron 3-dimensional metal dendrite that size is larger can be obtained.
Experiment 9: for preparing golden dendrite.
The chlorauric acid solution (0.05mol/L) of each for same volume 5L and hydroxylamine solution (0.4mol/L) are put into respectively container 1 and 2 (the ratio a of the reductant concentration namely reacted and the molar concentration of metal salt solution is 8), at the uniform velocity instilled in reaction vessel with the speed of identical 5mL/min by binary channels continuous feeding equipment, during reaction, temperature is room temperature 25 DEG C, the pH value regulating mixed solution is 6.5, utilize mixer oscillator that mixed liquor is carried out slight oscillatory in course of reaction, surge frequency range is 30Hz.Black precipitate is generated rapidly in test tube.Sediment is carried out filtering and spending Ion Cleaning 2-3 time, then carries out vacuum drying preservation, obtained 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.As shown in figure 14, gained dendrite is comparatively even as we know from the figure, and be three-dimensional tree dendritic morphology, diameter is 4 to 6 microns for the SEM SEM figure of gold metallic particles Au.The pattern of dendrite is also secondary fractal structure, " branch " structure grows again one-level " branch ", and the dimension scale of two-layer configuration is substantially identical, 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, all be prepared with twin-channel feed arrangement 5 in the experiment arranged in this detailed description of the invention, but can improve easily, adopt the multiple reaction 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 reaction of parallel connection, make to react between reducing agent and metal salt solution, multiple identical reaction is carried out simultaneously, thus significantly improves preparation efficiency, conveniently carries out industry and amplifies, 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 some substituting or obvious modification without departing from the inventive concept of the premise, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. have a preparation method for the metallic particles of three-dimensional pine-tree structure, it 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 instilled in reaction vessel with First Speed V1 and second speed V2 respectively, described First Speed V1 and described second speed V2 is 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, generates precipitation; 3) described precipitation is carried out filter, clean, then carry out vacuum drying, the obtained metallic particles with three-dimensional pine-tree structure.
2. the preparation method with the metallic particles of 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 exist: 0.5mL/min≤V1 < 5mL/min, 0.5mL/min≤V2 < 5mL/min, thus described step 3) in the three-dimensional pine-tree structure of obtained described metallic particles 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 exist: 5mL/min≤V1 < 15mL/min, 5mL/min≤V2 < 15mL/min, thus described step 3) in the three-dimensional pine-tree structure of obtained described metallic particles 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 exist: 15mL/min≤V1≤20mL/min, 15mL/min≤V2≤20mL/min, thus described step 3) in the three-dimensional pine-tree structure of obtained described metallic particles there are three grades of fractal structures.
3. the preparation method with the metallic particles of three-dimensional pine-tree structure according to claim 1, it is characterized in that: described step 2) in also comprise adjustment reaction temperature in course of reaction: 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 obtained described metallic particles is in the scope of 100nm≤d≤15 μm; 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 obtained described metallic particles is in the scope of 15 μm of < d≤50 μm.
4. the preparation method with the metallic particles of three-dimensional pine-tree structure according to claim 1, it is characterized in that: described step 2) in also comprise in course of reaction and regulate the pH of described mixed solution: 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 obtained 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 obtained described metallic particles have secondary fractal structure; Regulate the pH of described mixed solution to exist: 7.5 < pH≤11, thus the three-dimensional pine-tree structure of obtained described metallic particles have three grades of fractal structures.
5. the preparation method with the metallic particles of 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 with the metallic particles of 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 one or more the mixing in acetaldehyde, citric acid, azanol or hydrazine; Described metal salt solution is golden salting liquid, and described reducing agent is one or more the mixing in 2-amino-3-mercaptopropionic acid or sodium borohydride; Described metal salt solution is copper salt solution, and described reducing agent is one or more the mixing in hydroxylamine hydrochloride or sodium borohydride.
7. the metallic particles with three-dimensional pine-tree structure that obtains of the preparation method according to any one of 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 μm.
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