CN113493568A - High-molecular noble metal nano composite material and preparation method thereof - Google Patents
High-molecular noble metal nano composite material and preparation method thereof Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 119
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 90
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 75
- 239000002243 precursor Substances 0.000 claims abstract description 53
- 239000011259 mixed solution Substances 0.000 claims abstract description 39
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 38
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
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- 238000002156 mixing Methods 0.000 claims abstract description 17
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 34
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- 239000010931 gold Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
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- 239000010970 precious metal Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 21
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- 239000002253 acid Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
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- 239000012279 sodium borohydride Substances 0.000 claims description 13
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- 239000004800 polyvinyl chloride Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002596 lactones Chemical class 0.000 claims description 6
- -1 polyhexamethylene Polymers 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 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 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 3
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- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229940080262 sodium tetrachloroaurate Drugs 0.000 claims description 3
- 229940071240 tetrachloroaurate Drugs 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 13
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- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
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- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
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- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the technical field of nano functional materials, and particularly relates to a preparation method of a high polymer noble metal nano composite material, which comprises the following steps: according to the molar ratio of the noble metal precursor to the high molecular polymer of 1: (1-2) dissolving and dispersing the noble metal precursor and the high molecular polymer in a solvent to obtain a first mixed solution; and under the mixing condition of 20-30 ℃, adding a reducing agent into the first mixed solution for reduction reaction, and separating to obtain the macromolecular noble metal nano composite material. The preparation method of the macromolecular noble metal nano composite material can effectively prevent other impurity molecules from being grafted on the surface of the noble metal nano particles, improves the grafting amount of the macromolecular polymer on the surface of the noble metal nano particles and obtains the monodispersity composite material, and has the advantages of simple preparation process, simple and convenient operation, high preparation efficiency and high product purity.
Description
Technical Field
The invention belongs to the technical field of nano functional materials, and particularly relates to a high-molecular noble metal nano composite material and a preparation method thereof.
Background
In recent years, noble metal nanoparticles having stable chemical properties have great advantages in the fields of medicine, photoelectricity, catalysis, and the like, and have been greatly studied. With the change of the particle size, the shape and the surface-coated compound of the metal nano-particles, the thermodynamic property, the mechanical property and the like of the metal nano-particles are obviously changed. The polymer nano composite material as a novel composite material can exert the surface effect, the quantum effect and the small-size effect of the nano particles, has the advantages of the polymer material, and is particularly attractive in the field of functional materials. At present, the preparation methods of the polymer nano composite materials are various and mainly comprise: in-situ generation of the nano unit in the polymer unit, direct blending of the polymer and the nano unit, in-situ polymerization of the polymer under the nano unit to generate the polymer, simultaneous generation of the polymer unit and the nano unit, and the like. Wherein, the nano-filler is added into the polymer matrix by a proper method, which is a simple and efficient method for preparing the composite material.
At present, the preparation method of the polymer nano composite material comprises the steps of preparing a nano particle dispersion liquid, and then adding a reagent needing to be adsorbed or modified for subsequent steps. Wherein, a layer of molecules is already arranged on the surface of the nano particles to protect the nano particles and prevent the nano particles from agglomerating, so that the nano particles can be stably dispersed in a solution. The adsorbed molecules in this protective layer cannot subsequently be removed completely. In addition, in the method for preparing gold nanoparticles, the two-phase method has the advantages of simple operation, high yield, good monodispersity of the obtained ions and the like, and is most widely used. However, in the two-phase method, a phase transfer catalyst, namely tetraoctylammonium bromide, is required to be used for transferring the gold salt from the aqueous phase to the organic phase, and once the trace amount of surfactant is adsorbed to the surface of the gold nanoparticles, the trace amount of surfactant cannot be completely replaced and removed, so that trace amount of small molecular surfactant remains in the final product. The small molecules have obvious influence on the thermodynamic performance (such as glass transition temperature) of the high polymer and the compatibility of the nano filler and the high polymer matrix.
Disclosure of Invention
The invention aims to provide a preparation method of a high-molecular precious metal nanocomposite, and aims to solve the technical problem that the performance of the composite is influenced because a small-molecular active agent which cannot be removed is easily introduced on the surface of a precious metal nanocomposite in the preparation of the conventional high-molecular precious metal nanocomposite.
The invention also aims to provide a high-molecular noble metal nano composite material.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a high-molecular noble metal nano composite material comprises the following steps:
according to the molar ratio of the noble metal precursor to the high molecular polymer of 1: (1-2) dissolving and dispersing the noble metal precursor and the high molecular polymer in a solvent to obtain a first mixed solution;
and under the mixing condition of 20-30 ℃, adding a reducing agent into the first mixed solution for reduction reaction, and separating to obtain the macromolecular noble metal nano composite material.
Preferably, the noble metal precursor is selected from: at least one of a gold precursor, a silver precursor, and a platinum precursor.
Preferably, the high molecular polymer is selected from: at least one of polystyrene, polyethylene oxide, polyvinyl chloride, polymethyl methacrylate and polyhexamethylene lactone.
Preferably, the reducing agent is selected from: at least one of sodium borohydride, sodium phosphate, hydrazine hydrate, ascorbic acid, potassium borohydride and sodium citrate.
Preferably, the gold precursor is selected from: at least one of chloroauric acid, sodium tetrachloroaurate and potassium tetrachloroaurate.
Preferably, the silver precursor is selected from: at least one of silver nitrate, silver sulfate and silver acetate.
Preferably, the platinum precursor is selected from: at least one of chloroplatinic acid and sodium chloroplatinate.
Preferably, the solvent comprises the following components in a volume ratio of (1-3): 1 tetrahydrofuran and water.
Preferably, the molar ratio of the reducing agent to the noble metal precursor is (1.2-2): 1.
preferably, the step of adding a reducing agent to the first mixed solution to perform a reduction reaction includes: adding a reducing agent with the concentration of 0.01-0.05 mmol/L into the first mixed solution at the speed of 0.02-2 ml/s based on the volume of 30ml of the first mixed solution, and then reacting for 2-4 hours.
Preferably, the step of separating to obtain the polymer noble metal nanocomposite comprises: adding methanol into the system after the reduction reaction, separating to obtain a crude product, and then adopting a reaction system with a volume ratio of 1: and (40-60) washing the crude product by using a mixed solution of tetrahydrofuran and methanol, and separating to obtain the high-molecular precious metal nanocomposite.
Preferably, the method comprises the following steps: according to the molar ratio of chloroauric acid to polystyrene of 1: (1-2) dissolving and dispersing the chloroauric acid and the polystyrene in a volume ratio of (1-3): 1 to obtain a first mixed solution;
taking the volume of the first mixed solution as a reference, adding a sodium borohydride solution with the concentration of 0.01-0.05 mmol/L into the first mixed solution at the speed of 0.02-2 ml/s under the stirring condition of 20-30 ℃, and reacting for 2-4 hours;
then adding methanol, separating to obtain a crude product, and then adopting a solvent with the volume ratio of 1: (40-60) washing the crude product with a mixed solution of tetrahydrofuran and methanol, and separating to obtain the polystyrene gold nanocomposite.
Correspondingly, the high-molecular precious metal nano composite material is composed of precious metal nano particles and high-molecular polymers grafted on the surfaces of the precious metal nano particles, wherein the grafting density of the high-molecular polymers is 0.8-1.5 high-molecular chain number/nm2The mass percentage of the high molecular polymer is 8-80% based on the total mass of the high molecular noble metal nano composite material as 100%.
Preferably, the particle size of the polymer noble metal nano composite material is 5-20 nm.
Preferably, the noble metal nanoparticles are selected from: at least one of gold nanoparticles, silver nanoparticles, and platinum nanoparticles.
Preferably, the high molecular polymer is selected from: at least one of polystyrene, polyethylene oxide, polyvinyl chloride, polymethyl methacrylate and polyhexamethylene lactone.
The invention provides a preparation method of a high-molecular noble metal nano composite material, which comprises the following steps of according to the molar ratio of a noble metal precursor to a high-molecular polymer being 1: (1-2), dissolving and dispersing the noble metal precursor and the high molecular polymer in a solvent, adding a reducing agent into the first mixed solution for reduction reaction under the mixing condition of 20-30 ℃, and separating to obtain the high molecular noble metal nanocomposite. According to the invention, through an oxidation-reduction method, a reducing agent is used for reducing a noble metal precursor to form noble metal nano particles, and simultaneously, a high molecular polymer is grafted to the surfaces of the generated noble metal nano particles, so that the composite material with the high molecular polymer grafted on the surfaces of the noble metal nano particles is obtained. The preparation method provided by the invention can effectively prevent other impurity molecules from being grafted on the surface of the noble metal nanoparticles, improves the grafting amount of the high polymer on the surface of the noble metal nanoparticles and obtains the monodispersity composite material, and has the advantages of simple preparation process, simple and convenient operation, high preparation efficiency and high product purity.
The macromolecular noble metal nano composite material provided by the invention is composed of noble metal nanoparticles and a macromolecular polymer grafted on the surfaces of the noble metal nanoparticles, wherein the macromolecular polymer has high grafting density, and the grafting density is 0.8-1.5 macromolecular chain number/nm2The mass percentage of the high molecular polymer is 8-80% based on the total mass of the high molecular noble metal nano composite material as 100%. In the high-molecular precious metal nano composite material, except for the grafted high-molecular polymer, other surface active molecules are not grafted on the surface of the precious metal nano particles, so that the high-molecular precious metal nano composite material is excellent and stable in performance.
Drawings
FIG. 1 is a topographical view of composites of examples 1, 3, 5 and 7 of the present invention.
FIG. 2 is a schematic diagram of a process for preparing a polystyrene gold nanoparticle composite material according to an embodiment of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of a high-molecular noble metal nano composite material, which comprises the following steps:
s10, according to the molar ratio of the noble metal precursor to the high molecular polymer of 1: (1-2) dissolving and dispersing the noble metal precursor and the high molecular polymer in a solvent to obtain a first mixed solution;
s20, under the mixing condition of 20-30 ℃, adding a reducing agent into the first mixed solution for reduction reaction, and separating to obtain the high-molecular noble metal nano composite material.
The preparation method of the high molecular noble metal nano composite material provided by the embodiment of the invention comprises the following steps of according to the molar ratio of a noble metal precursor to a high molecular polymer of 1: (1-2), dissolving and dispersing the noble metal precursor and the high molecular polymer in a solvent, adding a reducing agent into the first mixed solution for reduction reaction under the mixing condition of 20-30 ℃, and separating to obtain the high molecular noble metal nanocomposite. According to the embodiment of the invention, a reducing agent is used for reducing a noble metal precursor to form noble metal nano particles by an oxidation-reduction method, and simultaneously, a high molecular polymer is grafted to the surfaces of the generated noble metal nano particles, so that the composite material with the high molecular polymer grafted on the surfaces of the noble metal nano particles is obtained. The preparation method provided by the embodiment of the invention can effectively prevent other impurity molecules from being grafted on the surface of the noble metal nanoparticles, improves the grafting amount of the high polymer on the surface of the noble metal nanoparticles and obtains the monodispersity composite material, and has the advantages of simple preparation process, simple and convenient operation, high preparation efficiency and high product purity.
Specifically, in step S10, the noble metal precursor and the high molecular polymer are mixed in such an amount that the molar ratio of the noble metal precursor to the high molecular polymer is 1: (1-2) dissolving and dispersing the noble metal precursor and the high molecular polymer in a solvent to obtain a first mixed solution. According to the embodiment of the invention, the molar ratio of the noble metal precursor to the high molecular polymer is 1: (1-2), the high molecular polymer is dissolved and dispersed in a solvent, the molar ratio ensures that the high molecular polymer is fully grafted on the surface of the noble metal nanoparticle, the high molecular noble metal nanocomposite with excellent performance is fully obtained, unoccupied dangling bonds on the surface of the noble metal are avoided, and the influence of other micromolecule surfactants introduced on the surface of the noble metal nanoparticle on the performance of the composite material in the subsequent treatment process or the application process is avoided.
In some embodiments, the noble metal precursor is selected from: at least one of a gold precursor, a silver precursor, and a platinum precursor. In some embodiments, the gold precursor is selected from: at least one of chloroauric acid, sodium tetrachloroaurate and potassium tetrachloroaurate. In some embodiments, the silver precursor is selected from: at least one of silver nitrate, silver sulfate and silver acetate. In some embodiments, the platinum precursor is selected from: at least one of chloroplatinic acid and sodium chloroplatinate. The noble metal precursor of the embodiment of the present invention includes, but is not limited to, any of the substances given in the above embodiments, and the noble metal precursor can be reduced to form the noble metal nanoparticles under the action of the reducing agent, and has the characteristics of the noble metal nanoparticles.
In some embodiments, the high molecular weight polymer is selected from: at least one of polystyrene, polyethylene oxide, polyvinyl chloride, polymethyl methacrylate and polyhexamethylene lactone. According to the embodiment of the invention, at least one high molecular polymer of polystyrene, polyethylene oxide, polyvinyl chloride, polymethyl methacrylate and polycaprolactone is grafted on the surface of the noble metal nanoparticles, so that the high molecular noble metal nanocomposite not only can exert the surface effect, the quantum effect and the small-size effect of the noble metal nanoparticles, but also has the advantages of the high molecular material.
In some embodiments, the noble metal precursor and the high molecular polymer are dissolved and dispersed in a solvent comprising (1-3): 1 in a solvent of tetrahydrofuran and water. The embodiment of the invention adopts the following components in volume ratio (1-3): 1 as a solvent, wherein the tetrahydrofuran and the water can be mutually dissolved to form a single phase, a phase transfer agent is not needed, so that the subsequent reaction among the noble metal precursor, the high molecular polymer and the reducing agent is directly carried out in the single phase, the subsequent treatment is simple and convenient, and other small molecular surfactants are prevented from being introduced on the surface of the noble metal nano particles. In addition, the volume ratio of tetrahydrofuran to water is (1-3): 1 fully ensures the solubility and the dispersibility of the noble metal precursor and the high molecular polymer in a solvent, and is beneficial to the subsequent reduction reaction to generate the monodisperse high molecular noble metal nano composite material with small and uniform particle size.
Specifically, in step S20, a reducing agent is added to the first mixed solution under the mixing condition of 20 to 30 ℃ to perform a reduction reaction, and the polymer noble metal nanocomposite is obtained by separation. In the embodiment of the invention, under the room-temperature mixing condition of 20-30 ℃, the reducing agent is added into the first mixed solution, the noble metal precursor in the system is uniformly reduced, and the high molecular polymer is grafted on the surface of the noble metal nano-particles while the noble metal nano-particles are generated, so that the high molecular noble metal nano-composite material with a single dispersion phase is formed. The mixing condition can be stirring and other conditions, which not only effectively avoids the reduction to form the agglomeration of the noble metal nanoparticles to form large particles, but also is beneficial to the full contact of the generated noble metal nanoparticles and the high molecular polymer, so that the noble metal nanoparticles are fully grafted on the surfaces of the noble metal nanoparticles, the agglomeration of the noble metal nanoparticles is further prevented, and meanwhile, the monodisperse high molecular noble metal nanocomposite with small and uniform particle size is obtained.
In some embodiments, the reducing agent is selected from: at least one of sodium borohydride, sodium phosphate, hydrazine hydrate, ascorbic acid, potassium borohydride and sodium citrate, and the reducing agents can effectively reduce the noble metal precursor to generate the noble metal nano-particles with uniform particle size.
In some embodiments, the molar ratio of the reducing agent to the noble metal precursor is (1.2-2): 1. the embodiment of the invention adopts the reducing agent with a slightly higher molar ratio than the noble metal precursor for reduction, so that the noble metal precursor in the system can be fully ensured to react into the noble metal simple substance.
In some embodiments, the step of adding a reducing agent to the first mixed solution to perform a reduction reaction includes: adding a reducing agent with the concentration of 0.01-0.05 mmol/L into the first mixed solution at the speed of 0.02-2 ml/s based on the volume of 30ml of the first mixed solution, and then reacting for 2-4 hours. According to the embodiment of the invention, the reduction rate of the noble metal precursor is regulated and controlled by controlling the concentration, the addition rate and the like of the reducing agent, so that the noble metal nanoparticles are prevented from being agglomerated to form large particles due to the excessively fast or uneven reduction and the like of the noble metal precursor, and the monodisperse high-molecular noble metal nanocomposite with small and uniform particle size can be obtained.
In some embodiments, the step of isolating the polymeric noble metal nanocomposite comprises: adding methanol into the system after the reduction reaction, separating to obtain a crude product, and then adopting a reaction system with a volume ratio of 1: and (40-60) washing the crude product by using a mixed solution of tetrahydrofuran and methanol, and separating to obtain the high-molecular precious metal nanocomposite. The embodiment of the invention adopts a crude product in a system after methanol settling reduction reaction, and then adopts a methanol-methanol mixed solution with a volume ratio of 1: and (40-60) washing and extracting the crude product by using a mixed solution of tetrahydrofuran and methanol, and removing redundant unreacted impurity components and the like to obtain the high-molecular precious metal nano composite material.
In some embodiments, as shown in fig. 2, the method for preparing the polymer-precious metal nanocomposite comprises the following steps:
s11, according to the molar ratio of chloroauric acid to polystyrene of 1: (1-2) dissolving and dispersing the chloroauric acid and the polystyrene in a volume ratio of (1-3): 1 to obtain a first mixed solution;
s21, taking the volume of the first mixed solution as a reference, adding a sodium borohydride solution with the concentration of 0.01-0.05 mmol/L into the first mixed solution at the speed of 0.02-2 ml/s under the stirring condition of 20-30 ℃, and reacting for 2-4 hours;
s31, then adding methanol, separating to obtain a crude product, and then adopting a method with a volume ratio of 1: (40-60) washing the crude product with a mixed solution of tetrahydrofuran and methanol, and separating to obtain the polystyrene gold nanocomposite.
Correspondingly, the embodiment of the invention also provides a high-molecular precious metal nano composite material, which consists of precious metal nano particles and a high-molecular polymer grafted on the surfaces of the precious metal nano particles, wherein the grafting density of the high-molecular polymer is 0.8-1.5 high-molecular chain number/nm2The mass percentage of the high molecular polymer is 8-80% based on the total mass of the high molecular noble metal nano composite material as 100%.
The high-molecular precious metal nano composite material provided by the embodiment of the invention consists of precious metal nano particles and a high-molecular polymer grafted on the surfaces of the precious metal nano particles, wherein the high-molecular polymer has high grafting density, and the grafting density is 0.8-1.5 high molecular chain number/nm2The mass percentage of the high molecular polymer is 8-80% based on the total mass of the high molecular noble metal nano composite material as 100%. In the macromolecular noble metal nano composite material of the invention,besides the high molecular polymer, other surface active molecules are not grafted on the surfaces of the noble metal nanoparticles, so that the performance is excellent and stable.
The polymer precious metal nanocomposite provided by the embodiment of the invention can be prepared by any one of the methods described above.
In some embodiments, the polymer noble metal nanocomposite material has a particle size of 5 to 20 nm. The polymer precious metal nanocomposite provided by the embodiment of the invention has a small and uniform particle size of 5-20 nm. The smaller the particle size of the polymer noble metal nano composite material, the higher the polymer grafting degree, the better the modification effect on noble metal nano particles, and the more stable the performance of the composite material; the larger the particle size of the polymer noble metal nanocomposite, the more the surface is limited.
In some embodiments, the noble metal nanoparticles are selected from: at least one of gold nanoparticles, silver nanoparticles, and platinum nanoparticles.
In some embodiments, the high molecular weight polymer is selected from: at least one of polystyrene, polyethylene oxide, polyvinyl chloride, polymethyl methacrylate and polyhexamethylene lactone.
The features of the above embodiments of the present invention are discussed in detail in the foregoing, and are not described in detail herein.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the advanced performance of the polymer-noble metal nanocomposite material and the preparation method thereof according to the embodiment of the present invention remarkably manifest, the above technical solution is exemplified by a plurality of embodiments.
Example 1
A polystyrene gold nano composite material is prepared by the following steps:
(1) 50mmol of polystyrene are dissolved in 20ml of tetrahydrofuran and mixed with 20.9mg of chloroauric acid in 10ml of water and stirred at room temperature until uniform mixing occurs.
(2) Adding 10ml of sodium borohydride solution while violently stirring, controlling the dropping speed to be 10ml/5s, continuously stirring and reacting for 3 hours at room temperature after the solution changes color, adding 500ml of methanol after the reaction is completed, and standing for a period of time to enable the nano particles to settle at the bottom of the reaction container.
(3) And pouring out the supernatant, taking the bottom nanoparticles, adding 10ml of tetrahydrofuran solution, and performing ultrasonic treatment to uniformly disperse the nanoparticles. Adding 500ml of methanol solution to settle the nano particles, centrifugally separating, taking the bottom nano particles, repeatedly washing, washing off the residual unreacted substances, and drying the obtained black solid in vacuum.
Example 2
A polystyrene gold nano composite material is prepared by the following steps:
(1) 50mmol of polystyrene are dissolved in 20ml of tetrahydrofuran and mixed with 12.54mg of chloroauric acid in 10ml of water and stirred at room temperature until uniform mixing takes place.
(2) Adding 10ml of sodium borohydride solution while violently stirring, controlling the dropping speed to be 10ml/5s, continuously stirring and reacting for 3 hours at room temperature after the solution changes color, adding 500ml of methanol after the reaction is completed, and standing for a period of time to enable the nano particles to settle at the bottom of the reaction container.
(3) And pouring out the supernatant, taking the bottom nanoparticles, adding 10ml of tetrahydrofuran solution, and performing ultrasonic treatment to uniformly disperse the nanoparticles. Adding 500ml of methanol solution to settle the nano particles, centrifugally separating, taking the bottom nano particles, repeatedly washing, washing off the residual unreacted substances, and drying the obtained black solid in vacuum.
Example 3
A polystyrene gold nano composite material is prepared by the following steps:
(1) 50mmol of polystyrene are dissolved in 20ml of tetrahydrofuran and mixed with 20.9mg of chloroauric acid in 10ml of water and stirred at room temperature until uniform mixing occurs.
(2) Adding 10ml of sodium borohydride solution while violently stirring, controlling the dropping speed to be 10ml/5min, continuously stirring and reacting for 3h at room temperature after the solution changes color, adding 500ml of methanol after the reaction is completed, and standing for a period of time to enable the nano particles to settle at the bottom of the reaction container.
(3) And pouring out the supernatant, taking the bottom nanoparticles, adding 10ml of tetrahydrofuran solution, and performing ultrasonic treatment to uniformly disperse the nanoparticles. Adding 500ml of methanol solution to settle the nano particles, centrifugally separating, taking the bottom nano particles, repeatedly washing, washing off redundant unreacted substances, and drying the obtained black solid in vacuum to obtain the polystyrene gold nano composite material.
Example 4
A polystyrene gold nano composite material is prepared by the following steps:
(1) 100mmol of polystyrene was dissolved in 20ml of tetrahydrofuran, mixed with 20.9mg of chloroauric acid in 10ml of water and stirred at room temperature until uniform mixing.
(2) Adding 10ml of sodium borohydride solution while violently stirring, controlling the dropping speed to be 10ml/5s, continuously stirring and reacting for 3 hours at room temperature after the solution changes color, adding 500ml of methanol after the reaction is completed, and standing for a period of time to enable the nano particles to settle at the bottom of the reaction container.
(3) And pouring out the supernatant, taking the bottom nanoparticles, adding 10ml of tetrahydrofuran solution, and performing ultrasonic treatment to uniformly disperse the nanoparticles. Adding 500ml of methanol solution to settle the nano particles, centrifugally separating, taking the bottom nano particles, repeatedly washing, washing off redundant unreacted substances, and drying the obtained black solid in vacuum to obtain the polystyrene gold nano composite material.
Example 5
A polystyrene gold nano composite material is prepared by the following steps:
(1) 100mmol of polystyrene was dissolved in 20ml of tetrahydrofuran, mixed with 12.54mg of chloroauric acid in 10ml of water and stirred at room temperature until uniform mixing.
(2) Adding 10ml of sodium borohydride solution while violently stirring, controlling the dropping speed to be 10ml/5min, continuously stirring and reacting at room temperature after the solution changes color, adding 500ml of methanol when the reaction is completed for 3h, and standing for a period of time to enable the nano particles to settle at the bottom of the reaction container.
(3) And pouring out the supernatant, taking the bottom nanoparticles, adding 10ml of tetrahydrofuran solution, and performing ultrasonic treatment to uniformly disperse the nanoparticles. Adding 500ml of methanol solution to settle the nano particles, centrifugally separating, taking the bottom nano particles, repeatedly washing, washing off redundant unreacted substances, and drying the obtained black solid in vacuum to obtain the polystyrene gold nano composite material.
Example 6
A polystyrene gold nano composite material is prepared by the following steps:
(1) 100mmol of polystyrene was dissolved in 40ml of tetrahydrofuran, mixed with 20ml of an aqueous solution of 20.9mg of chloroauric acid, and stirred at room temperature until uniform mixing occurred.
(2) Adding a sodium borohydride solution while violently stirring, controlling the dropping speed to be 10ml/5min, then continuously stirring at room temperature for reaction, adding 500ml of methanol when the reaction is completed for 3h, and standing for a period of time to enable the nanoparticles to settle at the bottom of the reaction container.
(3) And pouring out the supernatant, taking the bottom nanoparticles, adding 10ml of tetrahydrofuran solution, and performing ultrasonic treatment to uniformly disperse the nanoparticles. Adding 500ml of methanol solution to settle the nano particles, centrifugally separating, taking the bottom nano particles, repeatedly washing, washing off redundant unreacted substances, and drying the obtained black solid in vacuum to obtain the polystyrene gold nano composite material.
Example 7
A polystyrene gold nano composite material is prepared by the following steps:
(1) 50mmol of polystyrene are dissolved in 400ml of tetrahydrofuran and mixed with 12.54mg of chloroauric acid in 20ml of water and stirred at room temperature until uniform mixing takes place.
(2) Adding 10ml of sodium borohydride solution while violently stirring, controlling the dropping speed to be 10ml/5s, continuously stirring and reacting for 3 hours at room temperature after the solution changes color, adding 500ml of methanol after the reaction is completed, and standing for a period of time to enable the nano particles to settle at the bottom of the reaction container.
(3) And pouring out the supernatant, taking the bottom nanoparticles, adding 10ml of tetrahydrofuran solution, and performing ultrasonic treatment to uniformly disperse the nanoparticles. Adding 500ml of methanol solution to settle the nano particles, centrifugally separating, taking the bottom nano particles, repeatedly washing, washing off redundant unreacted substances, and drying the obtained black solid in vacuum to obtain the polystyrene gold nano composite material.
Furthermore, in order to verify the advancement of the gold polystyrene nanocomposite prepared in embodiments 1 to 7 of the present invention, performance tests were performed in the embodiments of the present invention.
Test example 1
The test example of the present invention observed the morphology of the gold-polystyrene nanocomposites prepared in examples 1, 3, 5 and 7, as shown in the scanning electron microscope of fig. 1, wherein (a) is the morphology of the gold-polystyrene nanocomposite prepared in example 1, with a particle size of 8.1 ± 0.8 nm; (b) is a morphology chart of the gold polystyrene nanocomposite prepared in example 3, with a particle size of 12.5 ± 1.8 nm; (c) is a morphology chart of the gold polystyrene nanocomposite prepared in example 5, with a particle size of 7.7 ± 0.7 nm; (d) is a morphology map of the gold polystyrene nanocomposite prepared in example 7, with a particle size of 10.4 ± 1.4 nm. Therefore, the particle size of the polystyrene gold nanocomposite prepared by the embodiment of the invention is 5-20 nm, and the polystyrene gold nanocomposite is small in particle size and uniform.
Test example 2
The example of the present invention detects the grafting condition of polystyrene in the gold-polystyrene nanocomposite prepared in examples 1, 3, 5 and 7, and the test results are shown in table 1 below:
TABLE 1
As can be seen from the above tests, the polystyrene gold nanocomposite prepared in the examples of the present invention has high graft density of polystyrene, and the particle size of the composite is small and uniform.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the polymer noble metal nano composite material is characterized by comprising the following steps:
according to the molar ratio of the noble metal precursor to the high molecular polymer of 1: (1-2) dissolving and dispersing the noble metal precursor and the high molecular polymer in a solvent to obtain a first mixed solution;
and under the mixing condition of 20-30 ℃, adding a reducing agent into the first mixed solution for reduction reaction, and separating to obtain the macromolecular noble metal nano composite material.
2. The method of claim 1, wherein the noble metal precursor is selected from the group consisting of: at least one of a gold precursor, a silver precursor, and a platinum precursor; and/or the presence of a gas in the gas,
the high molecular polymer is selected from: at least one of polystyrene, polyethylene oxide, polyvinyl chloride, polymethyl methacrylate and polyhexamethylene lactone; and/or the presence of a gas in the gas,
the reducing agent is selected from: at least one of sodium borohydride, sodium phosphate, hydrazine hydrate, ascorbic acid, potassium borohydride and sodium citrate.
3. The method of preparing a polymeric noble metal nanocomposite material according to claim 2, wherein the gold precursor is selected from the group consisting of: at least one of chloroauric acid, sodium tetrachloroaurate and potassium tetrachloroaurate; and/or the presence of a gas in the gas,
the silver precursor is selected from: at least one of silver nitrate, silver sulfate and silver acetate; and/or the presence of a gas in the gas,
the platinum precursor is selected from: at least one of chloroplatinic acid and sodium chloroplatinate.
4. The method for preparing a polymeric noble metal nanocomposite material according to any one of claims 1 to 3, wherein the solvent comprises, by volume ratio (1 to 3): 1 tetrahydrofuran and water; and/or the presence of a gas in the gas,
the molar ratio of the reducing agent to the noble metal precursor is (1.2-2): 1.
5. the method of preparing a polymeric noble metal nanocomposite according to claim 4, wherein the step of adding a reducing agent to the first mixed solution to perform a reduction reaction includes: adding a reducing agent with the concentration of 0.01-0.05 mmol/L into the first mixed solution at the speed of 0.02-2 ml/s based on the volume of 30ml of the first mixed solution, and then reacting for 2-4 hours.
6. The method of claim 1 or 5, wherein the step of separating the polymer noble metal nanocomposite comprises: adding methanol into the system after the reduction reaction, separating to obtain a crude product, and then adopting a reaction system with a volume ratio of 1: and (40-60) washing the crude product by using a mixed solution of tetrahydrofuran and methanol, and separating to obtain the high-molecular precious metal nanocomposite.
7. The method of preparing a polymeric noble metal nanocomposite material according to claim 6, comprising the steps of:
according to the molar ratio of chloroauric acid to polystyrene of 1: (1-2) dissolving and dispersing the chloroauric acid and the polystyrene in a volume ratio of (1-3): 1 to obtain a first mixed solution;
taking the volume of the first mixed solution as a reference, adding a sodium borohydride solution with the concentration of 0.01-0.05 mmol/L into the first mixed solution at the speed of 0.02-2 ml/s under the stirring condition of 20-30 ℃, and reacting for 2-4 hours;
then adding methanol, separating to obtain a crude product, and then adopting a solvent with the volume ratio of 1: (40-60) washing the crude product with a mixed solution of tetrahydrofuran and methanol, and separating to obtain the polystyrene gold nanocomposite.
8. The macromolecular precious metal nanocomposite is characterized by comprising precious metal nanoparticles and a macromolecular polymer grafted on the surfaces of the precious metal nanoparticles, wherein the grafting density of the macromolecular polymer is 0.8-1.5 macromolecular chain number/nm2The mass percentage of the high molecular polymer is 8-80% based on the total mass of the high molecular noble metal nano composite material as 100%.
9. The polymeric noble metal nanocomposite material according to claim 8, wherein the polymeric noble metal nanocomposite material has a particle size of 5 to 20 nm.
10. A polymeric noble metal nanocomposite according to claim 8 or 9, wherein the noble metal nanoparticles are selected from the group consisting of: at least one of gold nanoparticles, silver nanoparticles, and platinum nanoparticles; and/or the presence of a gas in the gas,
the high molecular polymer is selected from: at least one of polystyrene, polyethylene oxide, polyvinyl chloride, polymethyl methacrylate and polyhexamethylene lactone.
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