CN115401209A - Preparation method of nano silver powder with controllable particle size - Google Patents
Preparation method of nano silver powder with controllable particle size Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000002245 particle Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000000843 powder Substances 0.000 title claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 224
- 239000004332 silver Substances 0.000 claims abstract description 130
- 229910052709 silver Inorganic materials 0.000 claims abstract description 130
- 239000013078 crystal Substances 0.000 claims abstract description 73
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 43
- 229940033123 tannic acid Drugs 0.000 claims abstract description 43
- 229920002258 tannic acid Polymers 0.000 claims abstract description 43
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 40
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 40
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 40
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000001509 sodium citrate Substances 0.000 claims abstract description 36
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 239000003637 basic solution Substances 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 48
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 40
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 6
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000011521 glass Substances 0.000 description 18
- 230000002572 peristaltic effect Effects 0.000 description 17
- 101710134784 Agnoprotein Proteins 0.000 description 15
- 238000009826 distribution Methods 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- -1 silver ions Chemical class 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000005591 charge neutralization Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000010956 nickel silver Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a preparation method of nano silver powder with controllable particle size, which comprises the following specific steps: s1, preparing a primary silver crystal grain solution by using a silver source solution, a sodium citrate solution and a tannic acid solution, and taking part of the primary silver crystal grain solution as a basic solution prepared by G1 generation superposition; s2, adjusting the temperature of the base solution to be not lower than 80 ℃, and adding deionized water, a sodium citrate solution, a tannic acid solution and a silver source solution into the base solution to obtain a silver crystal grain solution prepared by G1 generation superposition; s3, taking part of the silver crystal grain solution prepared by superposition of the previous generation as a basic solution prepared by superposition of the next generation, and repeating the step S2 to obtain a silver crystal grain solution prepared by the next generation; and (3) obtaining final silver crystal grain solution by a generation-by-generation superposition method, and carrying out solid-liquid separation, cleaning and drying on the final silver crystal grain solution to obtain the nano silver powder with controllable granularity. The invention can control the shape and the grain diameter of the nano silver powder, and has wide development prospect.
Description
Technical Field
The invention belongs to the field of photovoltaic silver paste and electronic paste, and particularly relates to a preparation method of nano silver powder with controllable particle size.
Background
The nano silver powder is a main conductive phase of low-temperature curing slurry and high-end electronic slurry of the solar cell, accounts for more than 70% of the content of the silver slurry, and has a huge market application space. However, the existing nano silver powder has the characteristics of small size, surface property and huge surface energy, so that the powder is in an unstable energy state during preparation, the particle size is not easy to control, the morphology is not uniform, the stability is poor, and the use requirements of high-end electronic slurry on uniform particle size distribution, high stability and excellent performance cannot be met.
At present, the preparation of the nano silver powder mainly comprises a physical method, a biological method and a chemical method. The physical method mainly comprises a mechanical ball milling method, an evaporation condensation method and a laser ablation method, wherein the mechanical ball milling method has high requirements on equipment and has less application due to harsh preparation conditions; the evaporation condensation method has high requirements on equipment and high energy consumption, and the prepared nano silver particles are easy to agglomerate; the laser ablation method needs special equipment and has high energy consumption, and the prepared nano silver particles inevitably contain a small amount of silver oxide and are less in application. The biological method mainly comprises a microbial reduction method and a plant reduction method. The microbial reduction method is a method for preparing nano-silver by reducing silver ions by using microorganisms such as certain bacteria, fungi and the like in the nature; the plant reduction method is a method for preparing the nano silver powder by reducing silver ions by using active effective components in plants as a reducing agent, but the material preparation process is complicated and is not suitable for industrial production. The chemical method mainly comprises a liquid phase chemical reduction method, a micro emulsion method, a solvothermal method, a template method, a seed crystal method, a light induction method and an electrochemical deposition method, wherein the liquid phase chemical reduction method is a common method for industrially preparing silver powder at low cost at present, has relatively low cost, simple process and high yield, is easy to realize industrialization, can prepare silver particles of 10-200nm, but is easy to agglomerate and has certain difficulty in solid-liquid separation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing nano silver powder with controllable particle size.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing nano silver powder with controllable particle size comprises the following specific steps:
s1, preparing a primary silver crystal grain solution by using a silver source solution, a sodium citrate solution and a tannic acid solution, and taking part of the primary silver crystal grain solution as a basic solution prepared by G1 generation superposition;
s2, adjusting the temperature of the basic solution to be not lower than 80 ℃, and adding deionized water, a sodium citrate solution, a tannic acid solution and a silver source solution into the basic solution to obtain a silver crystal grain solution prepared by G1 generation superposition;
s3, taking part of the silver crystal grain solution prepared by superposition of the previous generation as a basic solution prepared by superposition of the next generation, and repeating the step S2 to obtain a silver crystal grain solution prepared by the next generation; obtaining final silver crystal grain solution by a generation-by-generation superposition method, and carrying out solid-liquid separation, cleaning and drying on the final silver crystal grain solution to obtain nano silver powder with controllable granularity;
the algebra of the generation-by-generation superposition is more than or equal to 1.
Further, in step S1, the specific steps are:
s1.1, mixing and diluting a sodium citrate aqueous solution and a tannic acid aqueous solution in a volume ratio of 1 (1-0.75) by 1.6-15 times, and heating to boil to obtain a mixed solution;
s1.2, dropwise adding a silver source solution accounting for 0.6-6% of the mixed solution into the mixed solution, and after dropwise adding, keeping the temperature for 10-30 min to obtain a primary silver crystal grain solution.
Further, the silver source solution is dripped into the mixed solution at the dripping speed of 100 r/min-160 r/min.
Further, in step S1, the concentration of the sodium citrate aqueous solution is 40 mM-60 mM, the concentration of the tannic acid aqueous solution is 5 mM-15 mM, and the concentration of the silver source solution is 40 mM-60 mM.
Further, in step S1, the silver source solution is a silver nitrate solution, a silver chloride solution, or a silver sulfate solution.
Furthermore, in the step S2, the ratio of the sodium citrate solution to the tannic acid solution is 1.
Further, in the step S2, the silver source solution is dripped into the mixed solution containing the base solution, deionized water, a sodium citrate solution and a tannic acid solution at a dripping speed of 100 r/min-160 r/min, and the heat preservation reaction is carried out for 30 min-60 min, so as to obtain the silver crystal grain solution prepared by G1 generation superposition.
Further, in step S2, the temperature of the base solution is adjusted to 90 ℃ to 100 ℃.
Furthermore, in the process of preparing the nano silver powder by superposition, the volume of the silver crystal grain solution prepared by superposition of the next generation is the same as that of the silver crystal grain solution prepared by superposition of the previous generation.
Furthermore, in the preparation process of each generation of silver crystal grain solution, the dosage of the base solution is equal to the total amount of the deionized water, the sodium citrate solution, the tannic acid solution and the silver source solution.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a method for preparing silver powder with controllable particle size, which comprises the steps of preparing a primary silver crystal grain solution by adopting a silver source solution, a sodium citrate solution and a tannic acid solution, reducing silver ions into simple substance silver by using a part of tannic acid, combining the other part of tannic acid and sodium citrate through long-chain molecules to form a sodium citrate-tannic acid polymer, carrying out charge neutralization coating on the surface of silver atoms after the sodium citrate-tannic acid polymer is contacted with the silver atoms, continuously coating along with the growth of the silver atoms, precipitating and separating out redundant products through high molecules to obtain the primary silver crystal grain solution, carrying out superposition preparation for obtaining the silver powder with different particle sizes, adjusting a reaction solution system and the number of silver cores of each generation according to use requirements, carrying out controllable preparation on the silver powder with certain target particle size through iterative reaction, controlling the particle size and the spherical shape of the product, obtaining the silver powder with the particle size of 84-500 nm according to the product requirements, and solving the problems that the silver powder in the prior art is difficult to control the particle size, the shape and the stability is poor.
Furthermore, the silver grain solution prepared at the previous time is used as the reaction solution prepared by each superposition, the number of growth cores in the reaction system is controlled by adjusting the using amount of the silver grain solution, and then the distribution of new silver ions is influenced in the dynamic reaction process after the reaction solution is added, so that the newly added silver ions can effectively grow on the existing grains, the growth speed is accelerated, the formation of new cores is reduced, the nano silver powder grains effectively grow, the nano silver powder with larger grain size can grow after each iterative reaction, and the product has uniform grain size.
Drawings
FIG. 1 shows the particle size test results of the silver nanoparticles obtained after one-generation stacking in example 1;
FIG. 2 is the result of particle size measurement of silver nanoparticles after second generation stacking in example 1;
FIG. 3 shows the results of particle size measurement of silver nanoparticles in example 1 after three generations of silver nanoparticles are stacked;
FIG. 4 shows the result of particle size measurement of silver nanoparticles after four generations of silver powder are stacked in example 1;
FIG. 5 is a general trend chart of the controlled preparation of the silver nanopowder in example 1;
FIG. 6 is a scanning electron microscope topography of the silver nanoparticles prepared in example 1;
FIG. 7 shows the particle size test results of the silver nanoparticles obtained after one-generation stacking in example 2;
FIG. 8 shows the results of particle size testing of silver nanoparticles obtained after second-generation stacking in example 2;
FIG. 9 shows the particle size test results of the silver nanoparticles obtained after three generations of the silver nanoparticles are stacked in example 2;
FIG. 10 shows the result of particle size measurement of silver nanoparticles in example 2 after four generations of stacking;
FIG. 11 is a general trend chart of the controlled preparation of the nano-silver powder in example 2 for iterative growth;
FIG. 12 is a scanning electron microscope topography of the silver nanoparticles prepared in example 2.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
The invention provides a preparation method of silver powder with controllable particle size, aiming at the problems of difficult control of silver powder particle size, uneven morphology and poor stability at the present stage, and the preparation method comprises the following steps of firstly preparing mother liquor of a silver source solution, a reducing agent and a dispersing agent to prepare a reaction solution;
then adding silver source solution, reducing agent and dispersant mother liquor according to a certain reaction proportion, and carrying out preliminary synthesis preparation of nano silver powder to obtain a primary nano silver powder sample with a certain particle size (less than 100 nm).
If larger-size nano silver powder particles are needed, iterative superposition preparation reaction can be carried out: before the added reaction liquid is prepared by superposition each time, a certain amount of original reaction liquid is required to be taken out to control the number of growth cores in a reaction system, and then the distribution of new silver ions is influenced in the dynamic reaction process after the reaction liquid is added, so that the newly added silver ions can effectively grow on the existing crystal grains, the growth speed is accelerated, the formation of new cores is reduced, and the crystal grains of the nano silver powder effectively grow.
The nano silver powder with larger granularity can be grown after each iteration reaction, and the product has uniform appearance and granularity.
The reaction iteration times can be designed according to the granularity requirement, and the controllable preparation of the granularity of the nano silver powder is realized.
The preparation method comprises the following specific steps:
1. preparing mother liquor:
firstly, preparing silver source solution (Ag) with a certain concentration + ) The silver source can be silver salts such as silver nitrate, silver chloride, silver sulfate and the like, preferably silver nitrate;
subsequently weighing a certain amount of sodium citrate SC (C) 6 H 5 Na 3 O 7 ·2H 2 O) is used as a coating agent and a solution with a certain concentration is prepared;
finally preparing a reducing agent solution, preferably tannic acid TA (C) 76 H 52 O 46 )。
The above three solutions: the concentrations of the silver nitrate solution, the sodium citrate solution and the tannic acid solution are 50-60 mM, 50-60 mM and 10-15 mM, preferably 50mM, 50mM and 10mM respectively.
2. Primary silver grain synthesis (G0 synthesis):
mixing and diluting a sodium citrate solution and a tannic acid solution in a volume ratio of 1 (1-0.75) by 1.6-15 times to obtain a mixed solution, adding the mixed solution into a three-neck round-bottom flask, heating to boil to prevent a reaction solution from evaporating, connecting a condenser to the three-neck flask for reflux, and heating to boil by using a heating device with a magnetic stirring function; then, a peristaltic pump is used to take silver source solution which accounts for 0.6 to 6 percent of the volume of the mixed solution and drop the silver source solution at a constant speed, the dropping speed is 100 to 160r/min, and a standard No. 13 peristaltic pump tube with the inner diameter of 0.8mm is used. After the dropwise addition is finished, the temperature is kept for 15-30 min, preferably 15min, and the primary silver crystal grain solution is obtained.
The synthesis reaction mechanism is as follows: one part of tannic acid firstly reduces silver ions into simple substance silver, and the other part of tannic acid and sodium citrate are combined through long-chain molecules to form a sodium citrate-tannic acid polymer, and after the tannic acid and the sodium citrate polymer are contacted with silver atoms, the charge neutralization coating is carried out on the surfaces of the silver atoms, the silver atoms grow up and are continuously coated, and redundant products are precipitated and separated out through high-molecular precipitation.
And 3, G1 generation stacking preparation:
adjusting the temperature of the primary silver crystal grain solution to an optimal reaction temperature, taking part of the primary silver crystal grain solution as a basic solution, adding deionized water, a sodium citrate solution and a tannic acid solution into the basic solution, dropwise adding a silver source solution at a constant speed of 100-160 r/min by using a peristaltic pump to obtain a first precursor, adjusting the final reaction volume of the first precursor to be the same as and constant to the volume of the primary silver crystal grain solution, carrying out heat preservation reaction for 30-60 min to obtain a silver crystal grain solution prepared by G1 generation superposition, and completing G1 generation superposition preparation.
Preparation of G2 generation by superposition
Adjusting the temperature of the silver crystal solution prepared by G1 generation superposition to the optimal reaction temperature, taking part of the silver crystal solution prepared by G1 generation superposition as a base solution prepared by G2 generation superposition, adding deionized water, a sodium citrate solution and a tannic acid solution into the base solution, dropwise adding a silver source solution at a constant speed of 100-160 r/min by using a peristaltic pump to obtain a second precursor, adjusting the final reaction volume of the second precursor to be the same as and constant as the volume of the silver crystal solution prepared by G1 generation superposition, carrying out heat preservation reaction for 30-60 min to obtain the silver crystal solution prepared by G2 generation superposition, and completing the G2 generation superposition preparation.
5. Using part of silver crystal grain solution prepared by superposition of the previous generation as basic solution prepared by superposition of the next generation, repeating the step 4 to carry out superposition reaction, and calculating G3, G4 \8230, 8230, wherein after each superposition is finished, the particle diameter of the nano silver powder is increased by 5-80 nm, and the final generation silver crystal grain solution is obtained by a generation-by-generation superposition method;
6. and (3) centrifuging, washing with water for 2 times, washing with alcohol for 2 times, centrifuging, and drying at a centrifugal rotation speed of 4000-6000r, preferably 4000r, for 4min to obtain dry and loose nano silver powder particles.
According to the technical scheme, the particle size and the morphology of each generation of product can be controlled by a generation-by-generation superposition preparation reaction mode, the number of superimposed generations is at least 1 generation, and the nano silver powder with the particle size of 84-500 nm can be controllably prepared by carrying out multiple times of superposition according to the product requirements.
Preferably, the optimum reaction temperature is set to 90-100 ℃ (e.g., 90 ℃, 95 ℃, 100 ℃), preferably 90 ℃;
preferably, the using amount of the basic solution in the superposition reaction process is equal to the total amount of the added deionized water, the added silver nitrate solution, the added sodium citrate solution and the added tannic acid solution;
preferably, the dosage ratio of the sodium citrate solution to the tannic acid solution in the superposition reaction process is as follows: 1, the dosage ratio of the tannic acid solution to the silver nitrate solution is as follows: 1, (1.3-3.3);
preferably, the volume of the silver crystal grain solution prepared by the superposition of the previous generation is the same as that of the silver crystal grain solution prepared by the superposition of the next generation, so that the stability of a reaction system can be ensured, the quantity of silver atoms which become cores can be controlled, and the distribution of the silver atoms in the growth and nucleation process can be more effectively regulated and controlled.
Example 1: taking the target silver powder particle size of 200nm (D50 =200 ± 20 nm) as an example:
1. preparing mother liquor:
selecting silver nitrate (AgNO) with highest solubility in liquid phase system and more stable than other silver salts from silver sources such as silver halide, silver nitrate, silver sulfate and the like 3 ) Is a silver source.
First, 50mM silver nitrate (AgNO) was prepared in 200ml 3 Ag +) solution: weighing 1.699g of silver nitrate into a glass bottle, adding 200ml of deionized water into the bottle, and putting the glass bottle with the solution into an ultrasonic machine for ultrasonic treatment to fully dissolve the solute.
2.941g of sodium citrate (C) are then weighed out 6 H 5 Na 3 O 7 ·2H 2 O, SC) is added into a glass bottle, 200ml of deionized water is added into the bottle, the glass bottle filled with the solution is placed into an ultrasonic machine for ultrasonic treatment to fully dissolve the solute, and 50mM and 200ml of sodium citrate solution is prepared.
Finally, 10mM, 200ml of tannic acid (C) was prepared 76 H 52 O 46 TA) solution: weighing 3.402g of tannic acid, adding into a glass bottle, adding 200ml of deionized water into the bottle, and putting the glass bottle with the solution into an ultrasonic machine for ultrasonic treatment to fully dissolve the solute.
2. Primary silver grain synthesis (G0 synthesis):
mixing 20ml sodium citrate water solution and 20ml tannic acid water solution, diluting to 200ml volume to obtain mixed solution, heating to boil in a three-neck round bottom flask, refluxing with a condenser, heating with a heating device with magnetic stirring function (stirring at 450 r/min), and uniformly dripping 4ml AgNO at speed of 100r and 32s with a peristaltic pump 3 The solution (as shown in Table 1G 0) was incubated for 15min after the addition.
And 3, G1 generation stacking preparation:
setting the temperature of the solution to 90 ℃, taking out 80ml of the solution (the taking amount is shown in the table 1G 1) by using a LongPumpYZ 1515X-A type peristaltic pump (the rotating speed is 300r, the time is 18 s), injecting 60ml of deionized water by using a pipette gun, respectively adding 2ml of SC solution and 6ml of TA solution by using the pipette gun after the solution is heated to be stable at 90 ℃, dropwise adding 12ml of AgNO at constant speed for 64s by using the peristaltic pump at 100r and dropwise adding 12ml of TA solution at constant speed 3 Solution to obtain the first precursorAnd driving a body, adjusting the final reaction volume of the first precursor to be the same as the volume of the primary silver crystal grain solution, namely 200ml, carrying out heat preservation reaction for 10min to obtain a silver crystal grain solution prepared by G1 generation superposition, and finishing the G1 generation superposition preparation.
And 4, G2 generation stacking preparation:
taking out 80ml of silver crystal grain solution (the dosage is shown in Table 1G 2) prepared by superposition of G1 generation, injecting 56ml of deionized water by using a liquid transfer gun, after the solution is heated up to be stabilized at 90 ℃, respectively adding 2ml of SC solution and 6ml of TA solution by using the liquid transfer gun, dropwise adding 16ml of AgNO at constant speed for 60s at 160r by using a peristaltic pump 3 And (3) obtaining a second precursor, adjusting the final reaction volume of the second precursor to be the same as the volume of the silver crystal grain solution prepared by G1 generation superposition, namely 200ml, carrying out heat preservation reaction for 10min to obtain a silver crystal grain solution prepared by G2 generation superposition, and finishing the G2 generation superposition preparation.
5. Taking the silver crystal grain solution prepared by G2 generation superposition as a base solution prepared by G3 generation superposition, carrying out the superposition reaction according to the raw material dosage shown in the table 1G3 to obtain a silver crystal grain solution prepared by G3 generation superposition, and finishing the preparation of G3 generation superposition;
6. taking the silver crystal grain solution prepared by G3 generation superposition as a base solution prepared by G4 generation superposition, carrying out the superposition reaction according to the raw material dosage shown in the table 1G4 to obtain a silver crystal grain solution prepared by G4 generation superposition, and finishing the preparation of G4 generation superposition;
and 7, after the G4 generation superposition preparation is finished, centrifuging, washing with water for 2 times, washing with alcohol for 2 times, centrifuging, and drying the silver crystal grain solution prepared by G4 generation superposition, wherein the rotating speed of each centrifugation is 6000r, and the time is 4min, so that the dry and loose nano silver powder particles are obtained.
TABLE 1 superimposed preparation protocol drug dosage (unit: ml)
There are two marker lines in the granulometry profile: 1. the particle size distribution curve is also called as a particle size distribution frequency curve, and is a wavy smooth frequency curve formed by drawing corresponding points according to the percentage content of each particle size on a piece of coordinate paper taking the particle size as an abscissa and the percentage content as an ordinate and connecting the points of each particle size; 2. the percentage overlap line is a quantitative curve that superimposes all particle size percentages within the range, with an endpoint of 100%.
FIG. 1 is a result of particle size measurement of the silver powder after one generation stacking in example 1, wherein the silver powder is in a nucleation stage, the particle size D50 is about 89nm, and the overall distribution is narrow;
FIG. 2 is a result of particle size measurement of the silver powder after the second generation stacking in example 1, wherein the silver powder is in the nucleation and growth stage, the particle size D50 is about 159nm, the overall distribution is narrower, and the particle size distribution is more concentrated;
FIG. 3 is a result of particle size measurement of the silver powder obtained after three generations of silver powder are stacked in example 1, wherein the silver powder is in a growth stage, the particle size D50 is about 167nm, and the overall distribution is concentrated and uniform;
FIG. 4 is a result of particle size measurement of the silver nanoparticles in the fourth generation of the silver nanoparticles of example 1, wherein the silver nanoparticles are in the growth stage, have a particle size D50 of about 205nm, are uniformly and integrally distributed, and have reached a target particle size (200. + -. 20 nm);
fig. 5 is a general trend chart of the controllable preparation iterative growth of the silver powder in example 1, and it can be clearly seen from the chart that the variation trend of the nucleation growth particle size growth of the silver powder in a 200ML reaction solution system is increased, and the particle size of the silver powder basically grows linearly with the increase of the iterative preparation times;
fig. 6 is a topography of the silver nanoparticle prepared in example 1, which shows that the prepared silver nanoparticle is spherical, has good dispersibility, no agglomeration, high stability and uniform particle size, and the technical scheme can effectively and controllably prepare the silver nanoparticle.
Example 2: taking the particle size of the target silver powder as 200nm (D50 =200 +/-20 nm) as an example:
1. preparing mother liquor:
the silver sources such as silver halide, silver nitrate, silver sulfate and the like are selected to have highest solubility in a liquid phase system and are more stable than other silver saltsDefinite silver nitrate (AgNO) 3 ) Is a silver source.
First, 50mM silver nitrate (AgNO) was prepared in 200ml 3 Ag +) solution: weighing 1.699g of silver nitrate into a glass bottle, adding 200ml of deionized water into the bottle, and putting the glass bottle with the solution into an ultrasonic machine for ultrasonic treatment to fully dissolve the solute.
5.882g of sodium citrate (C) are subsequently weighed out 6 H 5 Na 3 O 7 ·2H 2 O, SC) is added into a glass bottle, 400ml of deionized water is added into the bottle, the glass bottle filled with the solution is placed into an ultrasonic machine for ultrasonic treatment to fully dissolve the solute, and 50mM and 400ml of sodium citrate solution are prepared.
Finally, 10mM, 400ml of tannic acid (C) was prepared 76 H 52 O 46 TA) solution: weighing 6.804g of tannic acid, adding into a glass bottle, adding 400ml of deionized water into the bottle, and putting the glass bottle with the solution into an ultrasonic machine for ultrasonic treatment to fully dissolve the solute.
2. Primary silver grain synthesis (G0 synthesis):
mixing 60ml sodium citrate water solution and 45ml tannic acid water solution, diluting to 600ml volume to obtain mixed solution, heating to boil in a three-neck round bottom flask, refluxing with a condenser, heating with a magnetic stirring device (stirring at 500 r/min), and uniformly adding 12ml AgNO dropwise into the mixed solution at constant speed by peristaltic pump 100r,96s 3 The solution (as shown in Table 2G 0) was incubated for 15min after the addition was complete.
And 3, G1 generation stacking preparation:
setting the solution temperature at 95 ℃, taking out 240ml of solution (the taking amount is shown in table 2G 1) by using a LongPumpYZ 1515X-A type peristaltic pump (the rotating speed is 300r, the time is 55 s), injecting 192ml of deionized water by using a pipette gun, respectively adding 6ml of SC solution and 18ml of TA solution by using the pipette gun after the solution is heated up to be stable at 90 ℃, dropwise adding 192s and 24ml of AgNO at constant speed by using the peristaltic pump at 100r 3 And (3) obtaining a first precursor, adjusting the final reaction volume of the first precursor to be the same as the volume of the primary silver crystal grain solution, namely 600ml, carrying out heat preservation reaction for 30min to obtain a silver crystal grain solution prepared by superposing G1 generation, and finishing the superposing preparation of G1 generation.
And 4, G2 generation stacking preparation:
after 240ml of solution is taken out (the amount is shown in Table 2G 2), 180ml of deionized water is injected by using a pipette gun, after the solution is heated to be stable at 100 ℃, 6ml of SC solution and 18ml of TA solution are respectively added by using the pipette gun, and 180s 36ml of AgNO is dropwise added at constant speed of 160r by using a peristaltic pump 3 Obtaining a second precursor, adjusting the final reaction volume of the second precursor to be the same as the volume of the silver crystal grain solution prepared by G1 generation superposition, namely 600ml, performing heat preservation reaction for 30min to obtain a silver crystal grain solution prepared by G2 generation superposition, and finishing G2 generation superposition preparation;
5. taking the silver crystal grain solution prepared by G2 generation superposition as a base solution prepared by G3 generation superposition, carrying out the superposition reaction according to the raw material dosage shown in the table 2G3 to obtain a silver crystal grain solution prepared by G3 generation superposition, and finishing the preparation of G3 generation superposition;
6. taking the silver crystal grain solution prepared by G3 generation superposition as a base solution prepared by G4 generation superposition, carrying out the superposition reaction according to the raw material dosage shown in the table 2G4 to obtain a silver crystal grain solution prepared by G4 generation superposition, and finishing the G4 generation superposition preparation;
and 7, after the G4 generation superposition preparation is finished, centrifuging, washing for 2 times with water, washing for 2 times with alcohol, centrifuging and drying the silver crystal grain solution prepared by the G4 generation superposition, wherein the centrifugal rotating speed is 4000r each time, and the time is 4min, so that the dry and loose nano silver powder particles are obtained.
TABLE 2 superimposed preparation protocol drug dosage (unit: ml)
| Algebra | Dosage of | Adding H2O | Adding SC | Addition of TA | Adding Ag + | Speed and dripping time of peristaltic pump |
| G0 | \ | 483 | 60 | 45 | 12 | 100r/96s |
| G1 | 240 | 192 | 6 | 18 | 24 | 100r/192s |
| G2 | 240 | 180 | 6 | 18 | 36 | 160r/180s |
| G3 | 240 | 168 | 6 | 18 | 48 | 160r/240s |
| G4 | 240 | 156 | 6 | 18 | 60 | 160r/300s |
FIG. 7 is a result of particle size testing of the silver powder after one generation stacking in example 2, wherein the silver powder is in the nucleation stage, the particle size D50 is about 84nm, and the overall distribution is narrow;
FIG. 8 shows the result of particle size measurement of the silver powder obtained by stacking the second generation silver powder in example 2, wherein the silver powder is in the nucleation and growth stage, the particle size D50 is about 159nm, the overall distribution is narrower, and the particle size distribution is more concentrated;
FIG. 9 shows the particle size test result of the silver powder after three superimposed generations in example 2, wherein the silver powder is in the growth stage, the particle size D50 is about 176nm, and the overall particle size distribution is concentrated and uniform;
FIG. 10 is the result of particle size testing of the silver powder after the fourth generation stacking in example 2, wherein the silver powder is in the growth stage, the particle size D50 is about 215nm, the overall distribution is more uniform, and the target particle size (200 + -20 nm) is achieved;
FIG. 11 is a general trend chart of controllable preparation iterative growth of silver nanoparticles in example 2, from which it is apparent that the variation trend of nucleation growth particle size growth of silver nanoparticles is shown after the amount of the reaction system is increased, and the particle size of silver nanoparticles is substantially linearly increased with the increase of iterative preparation times in a 600ML reaction system;
fig. 12 is a scanning electron microscope morphology graph of the silver nanoparticles prepared in example 2, which shows that the prepared silver nanoparticles are substantially spherical, have good dispersibility, no agglomeration, high stability and uniform particle size, and the technical scheme can effectively and controllably prepare the silver nanoparticles.
Example 3: taking the target silver powder particle size of 500nm (D50 =500 ± 20 nm) as an example:
1. preparing mother liquor:
selecting silver nitrate (AgNO) with highest solubility in liquid phase system and more stable than other silver salts from silver sources such as silver halide, silver nitrate, silver sulfate and the like 3 ) Is a silver source.
First, 60mM silver nitrate (AgNO) was prepared in 200ml 3 Ag +) solution: weighing 4.078g of silver nitrate into a glass bottle, adding 200ml of deionized water into the bottle, and putting the glass bottle containing the solution into an ultrasonic machine for ultrasonic treatment to fully dissolve the solute.
3.529g of sodium citrate (C) are subsequently weighed out 6 H 5 Na 3 O 7 ·2H 2 O, SC) is added into a glass bottle, 200ml of deionized water is added into the bottle, the glass bottle with the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment to fully dissolve the solute, and a 60mM and 200ml sodium citrate solution is prepared.
Finally, 200ml of tannic acid (C) was prepared at 15mM 76 H 52 O 46 TA) solution: weighing 4.082g of tannic acid, adding into a glass bottle, adding 200ml of deionized water into the bottle, and placing the glass bottle with the solution into an ultrasonic machine to carry out ultrasonic treatment to fully dissolve the solute.
2. Primary silver grain synthesis (G0 synthesis):
mixing 40ml of sodium citrate aqueous solution and 40ml of tannic acid aqueous solution to a constant volume of 400ml to obtain a mixed solution, heating the mixed solution in a three-neck round-bottom flask to boil, connecting a condenser on the three-neck flask for reflux, heating the mixed solution by using a heating device with a magnetic stirring function (stirring the mixed solution at 450 r/min), and then dropwise adding 8ml of AgNO at a uniform speed in 64s at a rotating speed of 100r by using a peristaltic pump 3 The solution (as shown in Table 3G 0) was incubated for 60min after the addition was complete.
3. Preparing by superposition:
setting the temperature of the solution to 100 ℃, taking out 160ml of the solution (the taking amount is shown in the table 3G 1) by using a LongPumpYZ 1515X-A type peristaltic pump (the rotating speed is 300r, the time is 18 s), injecting 120ml of deionized water by using a pipette gun, respectively adding 4ml of SC solution and 12ml of TA solution by using the pipette gun after the solution is heated to be stable at 100 ℃, dropwise adding 128s by using the peristaltic pump at 100r and dropwise adding 24ml of AgNO at constant speed 3 Obtaining a first precursor, adjusting the final reaction volume of the first precursor and the volume of the primary silver crystal grain solutionAnd (5) keeping the temperature and reacting for 30min to obtain a silver crystal grain solution prepared by superposing G1 generation, wherein the preparation of the superposition of G1 generation is finished.
4. 160ml of Ag crystal grain solution prepared by G1 generation superposition (the amount is shown in Table 3G 2), injecting deionized water 112ml by using a liquid-transferring gun, after the solution is heated up to 90 ℃, respectively adding 4ml of SC solution and 12ml of TA solution by using the liquid-transferring gun, dropwise adding 32ml of AgNO at constant speed for 120s by using a peristaltic pump at 160r 3 And (3) obtaining a second precursor, adjusting the final reaction volume of the second precursor to be the same as the volume of the silver crystal grain solution prepared by G1 generation superposition, namely 200ml, carrying out heat preservation reaction for 10min to obtain a silver crystal grain solution prepared by G2 generation superposition, and finishing the G2 generation superposition preparation.
5. Taking the silver crystal grain solution prepared by the previous generation superposition as a basic solution prepared by the next generation superposition, carrying out the superposition reaction according to the raw material dosage shown in tables 3G 3-G10 to obtain a silver crystal grain solution prepared by G10 generation superposition, and finishing the preparation of G10 generation superposition;
and after the G10 generation stacking preparation is finished, centrifuging, washing for 2 times with water, washing for 2 times with alcohol, centrifuging and drying at the rotating speed of 5000r each time for 4min to obtain the dry and loose nano silver powder particles.
TABLE 3 superimposed preparation scheme medicine dosage (unit: ml)
Claims (10)
1. A preparation method of nano silver powder with controllable particle size is characterized by comprising the following specific steps:
s1, preparing a primary silver crystal grain solution by using a silver source solution, a sodium citrate solution and a tannic acid solution, and taking part of the primary silver crystal grain solution as a basic solution prepared by G1 generation superposition;
s2, adjusting the temperature of the basic solution to be not lower than 80 ℃, and adding deionized water, a sodium citrate solution, a tannic acid solution and a silver source solution into the basic solution to obtain a silver crystal grain solution prepared by G1 generation superposition;
s3, taking part of the silver crystal grain solution prepared by superposition of the previous generation as a basic solution prepared by superposition of the next generation, and repeating the step S2 to obtain a silver crystal grain solution prepared by the next generation; obtaining final silver crystal grain solution by a generation-by-generation superposition method, and carrying out solid-liquid separation, cleaning and drying on the final silver crystal grain solution to obtain nano silver powder with controllable granularity;
the algebra of the generation-by-generation superposition is more than or equal to 1.
2. The method for preparing the silver nanoparticles with controllable particle size according to claim 1, wherein the step S1 comprises the following steps:
s1.1, mixing and diluting a sodium citrate aqueous solution and a tannic acid aqueous solution in a volume ratio of 1 (1-0.75) by 1.6-15 times, and heating to boil to obtain a mixed solution;
s1.2, dropwise adding a silver source solution accounting for 0.6-6% of the mixed solution into the mixed solution, and after dropwise adding, keeping the temperature for 10-30 min to obtain a primary silver crystal grain solution.
3. The method for preparing the silver nanoparticles with controllable particle size according to claim 2, wherein the silver source solution is added dropwise into the mixed solution at a dropping rate of 100r/min to 160 r/min.
4. The method for preparing silver nanoparticles with controllable particle size according to claim 2, wherein in step S1, the concentration of the aqueous solution of sodium citrate is 40 mM-60 mM, the concentration of the aqueous solution of tannic acid is 5 mM-15 mM, and the concentration of the silver source solution is 40 mM-60 mM.
5. The method for preparing the nano silver powder with the controllable particle size according to any one of claims 1 to 4, wherein in the step S1, the silver source solution is a silver nitrate solution, a silver chloride solution or a silver sulfate solution.
6. The method for preparing the nano silver powder with the controllable particle size according to claim 1, wherein in the step S2, the ratio of the sodium citrate solution to the tannic acid solution is 1 to 3, and the ratio of the tannic acid solution to the silver nitrate solution is 1 (1.3-3.3).
7. The method for preparing the silver nanoparticles with controllable particle size according to claim 1, wherein in step S2, the silver source solution is dripped into the mixed solution containing the base solution, deionized water, sodium citrate solution and tannic acid solution at a dripping speed of 100r/min to 160r/min, and the heat preservation reaction is carried out for 30min to 60min, so as to obtain the silver crystal grain solution prepared by G1 generation superposition.
8. The method for preparing silver nanoparticles with controllable particle size according to claim 1, wherein the base solution temperature is adjusted to 90-100 ℃ in step S2.
9. The method for preparing a silver nanoparticle powder with controllable particle size according to claim 1, wherein the volume of the silver grain solution prepared by stacking the next generation is the same as that of the silver grain solution prepared by stacking the previous generation in the process of preparing the silver nanoparticle powder by stacking.
10. The method for preparing silver nanoparticles with controllable particle size according to claim 1, wherein the amount of the base solution is equal to the total amount of the deionized water, the sodium citrate solution, the tannic acid solution and the silver source solution added during each generation of the silver crystal grain solution.
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