CN105949526B - A kind of hybrid material aqueous solution of carried metal nano particle and preparation method thereof - Google Patents
A kind of hybrid material aqueous solution of carried metal nano particle and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/16—Halogen-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0831—Gold
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/08—Metals
- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0856—Iron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
Abstract
The present invention relates to a kind of hybrid material aqueous solution of carried metal nano particle and preparation method thereof.The hybrid material aqueous solution is dissolved in the solution of water formation for hybrid material, and the hybrid material is made of carrier molecule A, stable agent molecule B and metal nanoparticle.Step is：The aqueous solution of the aqueous solution of A and B is stirred, adjusts the pH of mixed solution, metal ion salt solution and reducing agent solution is added dropwise successively into mixed liquor, stirs, that is, obtains the hybrid material aqueous solution.Metal nanoparticle is effectively connected on the strand of carrier molecule with the form stable of ionic bond and coordinate bond in hybrid material, makes it have good water solubility, the advantages of metal nanoparticle load capacity is adjustable.The preparation method of the hybrid material aqueous solution is pollution-free, impurity in products is few and easy to operate.The hybrid material aqueous solution of the water soluble negative metal-loaded nanoparticles of preparation is widely used in antibiotic finishing solution, self assembly stoste and catalysis material etc..
Description
Technical field
The present invention relates to a kind of hybrid material aqueous solution of carried metal nano particle and preparation method thereof, more particularly to
Hybrid material aqueous solution of water miscible carried metal nano particle a kind of of stabilization and preparation method thereof.
Background technology
The hybrid material of carried metal nano particle refers to metal nano by the effect of chemical bond or secondary or physical bond
Grain is keyed on carrier molecule, such hybrid material is widely applied to metal ion adsorption material, catalysis material, self assembly list
Member, anti-biotic material, fire proofing etc..
The groups such as hydroxyl, amino, carboxyl in carrier molecule have good chelation to metal nanoparticle, can have
Metal nanoparticle in the absorption of effect or trapping solution.It is monodispersed in order to obtain during particulate nucleation and growth
Nano particle, high molecular polymer are used to regard surfactant, stabilizer, template in nano particle preparation process,
So as to obtain the nano-particle of certain grain size distribution and shape.From at present from the point of view of disclosed patent and document, although
There is substantial amounts of research to concentrate in the preparation of nano-Ag particles, but it is traditional using environmentally protective method synthesis nanometer
Particle, the distributing inhomogeneity of particle diameter, the stability of nano particle are poor.As disclosed a kind of use in patent CN101121203A
The method that sodium carboxymethylcellulose prepares nano-Ag particles as reducing agent and protective agent at the same time, still, wherein used carboxylic
Sodium carboxymethylcellulose pyce is not provided with detailed molecular weight, the particle size and form of the nanometer being prepared yet heterogeneity,
Also need to use microwave heating equipment in implementation process, be unfavorable for large industrialized production.In CN103480859A with containing
The oxidation Curdlan polysaccharide and silver nitrate solution of carboxyl form mixed liquor in equal volume, and polysaccharide-based Nano silver grain is prepared, but
It is the particle size and form and heterogeneity for the nano silver product being prepared.And in this two patents, all avoid silver nanoparticle
The problem of stability of particle.Although and for example part solves the problems, such as that nano silver product form is homogeneous in CN101450385A,
It is that reaction condition highest will react that duration is most long to reach 20h to 90 DEG C, seriously affects industrial efficiency.
Unlike above-mentioned patented method, the technical solution reaction condition that patent of the present invention proposes is gentle, is being provided
Process conditions under, stable, monodispersed nano-Ag particles hybrid material can be obtained.And propose and explain nano silver
The bonded mechanism of particle and carrier material, it was demonstrated that the load that nano-Ag particles can be stablized is on a support material, anti-by regulating and controlling
Condition is answered to adjust the load capacity of nano-Ag particles.Less input for the instrument and equipment that whole preparation process uses, operating process
Simple easy to implement, the raw material used in reaction process are environmental-friendly, pollution-free, and impurity in products is few, are easy to post-process；Entirely
Reaction process is conducive to industrial amplification production.
The content of the invention
The purpose of the present invention is for it is above-mentioned prepare nano particle there are the problem of, the present invention provides a kind of carried metal
Hybrid material aqueous solution of nano particle and preparation method thereof, is especially to provide a kind of water miscible carried metal nanometer of stabilization
Hybrid material aqueous solution of particle and preparation method thereof.Wherein, by the pH of regulation system, metal nanoparticle and molecule are formed
Ionic bond and coordinate bond bonding, metal nanoparticle between A and molecule B can be stablized, uniformly be supported on carrier molecule A class things
In matter, and it is scattered in aqueous, metal nanoparticle stability during without adding molecule B class material stabilizers in aqueous solution
Difference, easily reunites；In addition to this it is possible to carrier molecule A classes are regulated and controled by the amount for the molecule B class material stabilizers for regulating and controlling addition
The amount of portative metal nanoparticle on material.
The present invention a kind of carried metal nano particle hybrid material aqueous solution, the carried metal nano particle it is miscellaneous
Change material aqueous solution to be made of the hybrid material and water of carried metal nano particle, the hydridization material of the carried metal nano particle
Bonded by ionic bond and coordinate bond between carboxyl, amino and metal nanoparticle in material, the carboxyl and amino adhere to molecule A separately
With the strand of molecule B；
In the molecule A and the molecule B, the sum of carboxyl-content, amino content and hydroxy radical content are more than or equal to described point
The 160% of the sum of the mole of sub- A and the molecule B, carboxyl, amino and hydroxyl hydrophilic group in A, B Compound complex
Be ensure the water miscible principal element of Compound complex, 160% this numerical value be ensure Compound complex can have it is water miscible
Minimum numerical value.
The carboxyl bonded by ionic bond and coordinate bond and the amino bonded by ionic bond and coordinate bond contain
30% of the sum of amount more than or equal to the sum of carboxyl-content in the molecule A and molecule B and amino mole；
Relative molecular weight >=10000 of the molecule A, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C
Formed with H；
Relative molecular weight≤5000 of the molecule B, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C
Formed with H；
The general structure of the hybrid material of the water soluble negative metal-loaded nanoparticles is：
Or
Wherein, strand repetitive unit number m >=0, n>0；
The mechanism that the triangle bonding scheme stablized in general structure schematic diagram is formed is as follows：- COO in molecule A, B-
With-NH3 +Because the attraction of positive and negative charge, electrostatic attraction is produced, that is, forms ionic bond；-COO-In hydroxyl oxygen on have orphan to electricity
Son, therefore lone pair electrons enter the unoccupied orbital of metal ion and metal ion occurs covalent coordinate and combined, and form coordinate bond；-NH3 +
In N atoms there is also lone pair electrons, be equally capable of providing lone pair electrons and form coordinate bond with metal ion and combined.Metal ion
Atomic state is reduced into by reducing agent under stable triangle bonding, in the process, the triangle in general structure schematic diagram
Bonding scheme can be still stabilized.
In the process, the pH of reaction system is to-COO in system-、-NH3 +And Mx+The formation of bonding structure has very big shadow
Ring.- NH in molecule A or molecule B2In the case of pH value ＜ 7 ,-NH can be combined to form with H protons excessive in solution3 +；With
The rise of pH value, to neutral or alkaline condition, the H protons to dissociate in solution are reduced, it is impossible to re-form-NH3 +Structure.
For-the COOH in molecule A and molecule B, in strong acid condition pH ＜ 2, the dissociation of-COOH is suppressed, in system-
COO-Content it is less, therefore the complexing power of metal ion is weakened significantly；As pH value increases, the complexing with metal ion
Ability gradually increases, when solution ph reaches 5~7 ,-COO-Tend to be maximum with metal ion combination degree；But work as system
PH when improving again, and-NH can be destroyed3 +Structure, so as to destroy the three-legged structure relation for making stable system.Therefore, for shape
Into the triangle bonding scheme of the stable stabilization as shown in schematic diagram, so the pH of necessary effective adjustment and control system, and protect
The scope for demonstrate,proving pH is 4~6.
R1、R2And R3Functional group is respectively one kind in following functional group：Cation group, anionic group or polarity are non-
Ionic group；The cation group is tertiary amine base or quaternary ammonium group；The anionic group is carboxylic acid group；The polar nonionic
Group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
M is metal nanoparticle, by Mx+Metal ion by reducing agent reduction form, Mx+The value of middle valence state x for 1~
3, be：Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
As preferable technical solution：
A kind of hybrid material aqueous solution of carried metal nano particle as described above, the molecule B with amino also include hydroxyl
Base or carboxyl, the molecule B with carboxyl also include hydroxyl or amino.
A kind of hybrid material aqueous solution of carried metal nano particle as described above, the carboxyl be located at molecular backbone or
Side chain, the amino are located at molecular backbone or side chain.
A kind of hybrid material aqueous solution of carried metal nano particle as described above, the molecular backbone of the molecule A is also
Including element O, N or S.
A kind of hybrid material aqueous solution of carried metal nano particle as described above, the molecular backbone of the molecule B is also
Including element O, N or S.
A kind of hybrid material aqueous solution of carried metal nano particle as described above, R in the molecule A and molecule B1、R2
And R3Functional group is respectively one kind in following functional group：Cation group, anionic group or polar nonionic group；It is described
Cation group is tertiary amine base or quaternary ammonium group；The anionic group is carboxylic acid group；The polar nonionic group is hydroxyl, ether
Base, amino, amide groups, sulfydryl or halogen.Preferably：Anionic group, carboxylic acid group (- COO-)；Polar nonionic group, hydroxyl
Base (- OH), amino (- NH2)。
Present invention also offers a kind of preparation method of the hybrid material aqueous solution of carried metal nano particle, molecule will be contained
The aqueous solution of A materials is mixed with the aqueous solution of the B substance containing molecule, the pH to 4~6 of reaction system is adjusted, then into mixed liquor
Metal ion salt solution, reducing agent solution are added dropwise successively, is stirred after being added dropwise, obtains carried metal nano particle hybrid material
Aqueous solution；
The materials of A containing molecule and B substance containing molecule are intersected containing carboxyl and amino, i.e.,：The materials of A containing molecule whens containing carboxyl, contain
Molecule B substance contains amino；Conversely, the materials of A containing molecule whens containing amino, B substance containing molecule contain carboxyl.
A kind of preparation method of the hybrid material of water soluble negative metal-loaded nanoparticles as described above, will contain molecule A things
The aqueous solution of matter is mixed with the aqueous solution of the B substance containing molecule, is under the conditions of 20~60 DEG C, when mixing accompanies by stirring；Adjust anti-
The pH of system is answered to use HCl solution, the H of 0.05~0.15mol/L of 0.1~0.3mol/L2SO4Solution or 0.1~0.3mol/L
HNO3Solution is adjusted；Metal ion salt solution stirs after being added dropwise, and the duration is 0.5~1h；Reducing agent solution is added dropwise
After stir, the duration is 1~2h.
A kind of preparation method of the hybrid material aqueous solution of carried metal nano particle as described above, the A containing molecule
Material is the carboxylic materials of A containing molecule of molecule A or the amino-containing materials of A containing molecule of molecule A；The B substance containing molecule is point
The carboxylic B substance containing molecule of sub- B or the amino-containing B substances containing molecule of molecule B；
The carboxylic materials of A containing molecule of molecule A are selected from sodium alginate, potassium alginate, sodium carboxymethylcellulose, carboxylic first
Base cellulose potassium, sodium hydroxyethlcellulose, carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyethyl
Chitosan sodium, carboxyetbyl chitosan potassium, bis- sodium carboxymethylcelluloses of 2,3-, bis- potassium carboxymethylcelluloses of 2,3-, Sodium Polyacrylate
With one kind in polyacrylic acid potassium；Preferably sodium alginate, potassium alginate, sodium carboxymethylcellulose, potassium carboxymethylcellulose,
Carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, Sodium Polyacrylate, polyacrylic acid potassium, it is optimal for sodium carboxymethylcellulose, carboxylic
Methylcellulose potassium；
The amino-containing materials of A containing molecule of molecule A are chitosan, carboxymethyl chitosan or polyacrylamide；Preferably
For chitosan；
The carboxylic B substances containing molecule of molecule B are selected from the alkyl chain acid that chain length is less than 6 carbon, be specially n-butyric acie,
Positive valeric acid or n-caproic acid；
The amino-containing B substances containing molecule of molecule B are selected from chain length and are less than the alkyl chain ammonia of 6 carbon, polyetheramine D230, poly-
Ether amines D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fatty amine gather
Ethylene oxide ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, fatty amine polyoxy second
One kind in alkene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；Preferably
One in polyetheramine D230, aliphatic amine polyoxyethylene ether AC-1810, polyetheramine T403 and aliphatic amine polyoxyethylene ether AC-1205
Kind, it is most preferably polyetheramine D230；The alkyl streptamine that the chain length is less than 6 carbon is n-propylamine, n-butylamine, n-amylamine or just oneself
Amine；
The metal ion salt solution is AgNO3、FeCl2、HAuCl4、Cr2(SO4)3、PtCl2、PdCl2、CuSO4Or Ni
(NO3)2Aqueous solution；
The reducing agent solution is sodium borohydride, potassium borohydride, ascorbic acid, sodium triethylborohydride, hydrazine hydrate or first
Aldehyde solution.
A kind of preparation method of the hybrid material aqueous solution of carried metal nano particle as described above, the A containing molecule
When the aqueous solution of material is mixed with the aqueous solution of the B substance containing molecule, the molar ratio of the materials of A containing molecule and the B substance containing molecule is 1:
0.3~1；
The mass percent concentration of the aqueous solution of the materials of A containing molecule is 0.5%~3%；
The mass percent concentration of the aqueous solution of the B substance containing molecule is 3%~10%；
The concentration of the metal ion salt solution is 0.005~2g/mL；
The molar ratio of the metal cation salt and the materials of A containing molecule is 0.1~10:1；
The concentration of the solution of the reducing agent is 0.01~0.1g/mL；
The molar ratio of the metal cation salt and reducing agent material is 1:0.5~12；
The mass percent concentration of the hybrid material aqueous solution of the carried metal nano particle is 0.5%~10.5%.
Beneficial effect：
The hybrid material of the carried metal nano particle prepared using the present invention has good water solubility, its aqueous solution tool
There is good stability, i.e., the dissolving that hybrid material is stablized disperses in aqueous, which does not have obvious particulate matter to hang
Float or precipitate, the metal nanoparticle load capacity in hybrid material is adjustable, and metal nanoparticle has with the form stable of ionic bond
Effect is connected on the strand of carrier molecule；Less input for the instrument and equipment that preparation process uses, and operating process is simply easy to
Implement, the raw material used in reaction process are environmental-friendly, pollution-free, and impurity in products is few, is easy to post-process；Whole reaction process
Be conducive to industrial amplification production.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed scope.
A kind of hybrid material aqueous solution of carried metal nano particle of the present invention, the hydridization material of carried metal nano particle
Material aqueous solution is made of the hybrid material and water of carried metal nano particle, in the hybrid material of carried metal nano particle, carboxylic
Bonded by ionic bond and coordinate bond between base, amino and metal nanoparticle, carboxyl and amino adhere to dividing for molecule A and molecule B separately
Subchain；
In molecule A and the molecule B, the sum of carboxyl-content, amino content and hydroxy radical content be more than or equal to the molecule A and
The 160% of the sum of the mole of the molecule B；
By the bonded carboxyl of ionic bond and coordinate bond and the amino content bonded by ionic bond and coordinate bond it
With 30% more than or equal to the sum of carboxyl-content in the molecule A and the molecule B and amino mole；
Relative molecular weight >=10000 of molecule A, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C and H
Composition；
Relative molecular weight≤5000 of molecule B, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C and H groups
Into；
The general structure of the hybrid material of water soluble negative metal-loaded nanoparticles is：
Or
Wherein, strand repetitive unit number m >=0, n>0；
R1、R2And R3Functional group is respectively one kind in following functional group：Cation group, anionic group or polarity are non-
Ionic group；Cation group is tertiary amine base or quaternary ammonium group；Anionic group is carboxylic acid group；Polar nonionic group for hydroxyl,
Ether, amino, amide groups, sulfydryl or halogen；
M is metal nanoparticle, by Mx+Metal ion by reducing agent reduction form, Mx+The value of middle valence state x for 1~
3, be：Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
Embodiment 1
A kind of preparation method of the hybrid material aqueous solution of loaded Ag nano particle, under the conditions of 20 DEG C, by quality percentage
The amino-containing chitosan aqueous solution that specific concentration is 0.5% and the carboxylic n-butyric acie that mass percent concentration is 3% are water-soluble
Liquid presses mixing, wherein, the relative molecular weight of chitosan is 240000, and the molecular weight of n-butyric acie is 88.1, chitosan and n-butyric acie
Molar ratio be 1:0.3, accompany by stirring；The pH value of reaction system is adjusted to 4 using the HCl solution of 0.1mol/L, then to mixed
Close the AgNO for being added dropwise that concentration is 0.005g/mL in liquid3Solution, wherein AgNO3Molar ratio with chitosan is 0.1:1, it is added dropwise
0.5h is persistently stirred afterwards；It is 0.048g/mL sodium borohydride aqueous solutions that concentration, which is added dropwise, wherein AgNO3With rubbing for sodium borohydride
You are than being 1:0.5, continue to stir 1h after being added dropwise, obtain the loaded Ag nano particle that mass percent concentration is 0.5%
Hybrid material aqueous solution.
Embodiment 2
A kind of preparation method of the hybrid material aqueous solution of load Fe nano particles, under the conditions of 60 DEG C, by quality percentage
The carboxylic positive valeric acid that the amino-containing carboxymethyl chitosan sugar aqueous solution that specific concentration is 3% is 10% with mass percent concentration
Aqueous solution mixes, wherein, the relative molecular weight of carboxymethyl chitosan is 10000, and the molecular weight of positive valeric acid is 102.13, carboxymethyl
The molar ratio of chitosan and positive valeric acid is 1:1, accompany by stirring；Using the H of 0.15mol/L2SO4Solution adjusts the pH of reaction system
Then the FeCl that concentration is 2g/mL is added dropwise to 6 in value into mixed liquor2Solution, wherein FeCl2With the molar ratio of carboxymethyl chitosan
For 10:1,1h is persistently stirred after being added dropwise；It is 0.01g/mL potassium borohydride aqueous solutions that concentration, which is added dropwise, wherein FeCl2With
The molar ratio of potassium borohydride is 1:12, continue to stir 2h after being added dropwise, obtain the load that mass percent concentration is 10.5%
The hybrid material aqueous solution of Fe nano particles.
Embodiment 3
A kind of preparation method of the hybrid material aqueous solution of load Au nano particles, under the conditions of 30 DEG C, by quality percentage
The carboxylic n-caproic acid water that the amino-containing polyacrylamide solution that specific concentration is 1% is 4% with mass percent concentration
Solution mixes, wherein, the relative molecular weight of polyacrylamide is 1 × 106, the molecular weight of n-caproic acid is 115.15, polyacrylamide
The molar ratio of amine and n-caproic acid is 1:0.4, accompany by stirring；Using the HNO of 0.3mol/L3Solution adjust reaction system pH value to
5, the HAuCl that concentration is 0.008g/mL is then added dropwise into mixed liquor4Solution, wherein HAuCl4With the molar ratio of polyacrylamide
For 0.5:1,0.6h is persistently stirred after being added dropwise；It is 0.032g/mL aqueous ascorbic acids that concentration, which is added dropwise, wherein
HAuCl4Molar ratio with ascorbic acid is 1:0.8, continue to stir 1.1h after being added dropwise, obtaining mass percent concentration is
The hybrid material aqueous solution of 0.9% load Au nano particles.
Embodiment 4
A kind of preparation method of the hybrid material aqueous solution of load C r nano particles, under the conditions of 40 DEG C, by quality percentage
The carboxylic sodium alginate aqueous solution that specific concentration is 2% and the amino-containing n-propylamine that mass percent concentration is 5% are water-soluble
Liquid mixes, wherein, the relative molecular weight of sodium alginate is 25000, and the molecular weight of n-propylamine is 59.11, sodium alginate and positive third
The molar ratio of amine is 1:0.5, accompany by stirring；The pH value of reaction system is adjusted to 4.5 using the HCl solution of 0.3mol/L, then
The Cr that concentration is 0.1g/mL is added dropwise into mixed liquor2(SO4)3Solution, wherein Cr2(SO4)3Molar ratio with sodium alginate is
0.9:1,0.8h is persistently stirred after being added dropwise；It is 0.06g/mL sodium triethylborohydride aqueous solutions that concentration, which is added dropwise, Cr2
(SO4)3Molar ratio with sodium triethylborohydride is 1:1.2, continue to stir 1.3h after being added dropwise, it is dense to obtain mass percent
Spend the hybrid material aqueous solution of the load C r nano particles for 2.1%.
Embodiment 5
A kind of preparation method of the hybrid material aqueous solution of supporting Pt nano particle, under the conditions of 45 DEG C, by quality percentage
Carboxylic sodium carboxymethyl cellulose solution that specific concentration is 1.8% and mass percent concentration be 7% it is amino-containing just
Amylamine aqueous solution mixes, wherein, the relative molecular weight of sodium carboxymethylcellulose is 19000, and the molecular weight of n-amylamine is 87.16,
The molar ratio of sodium carboxymethylcellulose and n-amylamine is 1:0.7, accompany by stirring；Using the HNO of 0.1mol/L3Solution adjusts reaction
Then the PtCl that concentration is 1.9g/mL is added dropwise to 4.8 in the pH value of system into mixed liquor2Solution, is persistently stirred after being added dropwise
0.9h, wherein, PtCl2Molar ratio with sodium carboxymethylcellulose is 2.6:1；It is 0.07g/mL hydrazine hydrate water that concentration, which is added dropwise,
Solution, PtCl2Molar ratio with hydrazine hydrate is 1:2, continue to stir 1.9h after being added dropwise, obtaining mass percent concentration is
The hybrid material aqueous solution of 9.6% supporting Pt nano particle.
Embodiment 6
A kind of preparation method of the hybrid material aqueous solution of load Pd nano particles, under the conditions of 50 DEG C, by quality percentage
The amino-containing n-butylamine water that the carboxylic potassium alginate aqueous solution that specific concentration is 1.6% is 6% with mass percent concentration
Solution mixes, wherein, the relative molecular weight of potassium alginate is 15000, and the molecular weight of n-butylamine is 73.14, potassium alginate with just
The molar ratio of butylamine is 1:0.6, accompany by stirring；Using the H of 0.05mol/L2SO4Solution adjusts the pH value of reaction system to 5.2,
Then the PdCl that concentration is 0.8g/mL is added dropwise into mixed liquor2Solution, persistently stirs 0.8h, wherein PdCl after being added dropwise2With
The molar ratio of potassium alginate is 1.9:1；It is 0.018g/mL formalins that concentration, which is added dropwise, PdCl2With the molar ratio of formaldehyde
For 1:5, continue to stir 1.5h after being added dropwise, obtain the hydridization for the load Pd nano particles that mass percent concentration is 4.5%
Material aqueous solution.
Embodiment 7
A kind of preparation method of the hybrid material aqueous solution of loaded Cu nano particle, under the conditions of 56 DEG C, by quality percentage
Carboxylic potassium carboxymethylcellulose aqueous solution that specific concentration is 2% and mass percent concentration be 8% it is amino-containing just oneself
Amine aqueous solution mixes, wherein, the relative molecular weight of potassium carboxymethylcellulose is 26000, and the molecular weight of n-hexylamine is 101.19, carboxylic
The molar ratio of methylcellulose potassium and n-hexylamine is 1:0.5, accompany by stirring；Using the HNO of 0.1mol/L3Solution adjusts reactant
Then the CuSO that concentration is 1.5g/mL is added dropwise to 4.9 in the pH value of system into mixed liquor4Solution, is persistently stirred after being added dropwise
0.78h, wherein CuSO4Molar ratio with potassium carboxymethylcellulose is 3.6:1；It is 0.08g/mL sodium borohydrides that concentration, which is added dropwise,
Aqueous solution, wherein CuSO4Molar ratio with sodium borohydride is 1:8.5, continue to stir 1.45h after being added dropwise, obtain quality hundred
Divide the hybrid material aqueous solution for the loaded Cu nano particle that specific concentration is 10%.
Embodiment 8
A kind of preparation method of the hybrid material aqueous solution of load Ni nano particles, under the conditions of 42 DEG C, by quality percentage
Carboxylic sodium hydroxyethlcellulose aqueous solution that specific concentration is 2.3% and mass percent concentration be 9% it is amino-containing poly-
Ether amines D230 aqueous solutions mix, wherein, the relative molecular weight of sodium hydroxyethlcellulose is 310000, the molecular weight of polyetheramine D230
For 230, the molar ratio of sodium hydroxyethlcellulose and polyetheramine D230 are 1:0.8, accompany by stirring；It is molten using the HCl of 0.19mol/L
Liquid adjusts the pH value of reaction system to 4.59, and the Ni (NO that concentration is 1.6g/mL are then added dropwise into mixed liquor3)2Solution, wherein
Ni(NO3)2Molar ratio with sodium hydroxyethlcellulose is 4.3:1,0.82h is persistently stirred after being added dropwise；Concentration, which is added dropwise, is
0.1g/mL potassium borohydride aqueous solutions, wherein Ni (NO3)2Molar ratio with potassium borohydride is 1:9.8, continue to stir after being added dropwise
1.52h, obtains the hybrid material aqueous solution for the load Ni nano particles that mass percent concentration is 10%.
Embodiment 9
A kind of preparation method of the hybrid material aqueous solution of supporting Pt nano particle, under the conditions of 46 DEG C, by quality percentage
The carboxylic carboxyethyl cellulose aqueous solutions of potassium that specific concentration is 2.56% and mass percent concentration be 8.3% it is amino-containing
Polyetheramine D400 aqueous solutions mix, wherein, the relative molecular weight of carboxyethyl cellulose potassium is 35200, the molecule of polyetheramine D400
Measure as 400, the molar ratio of carboxyethyl cellulose potassium and polyetheramine D400 are 1:0.68, accompany by stirring；Using 0.05mol/L's
H2SO4Solution adjusts the pH value of reaction system to 4.3, and the PtCl that concentration is 1.8g/mL is then added dropwise into mixed liquor2Solution, its
Middle PtCl2Molar ratio with carboxyethyl cellulose potassium is 5.3:1,0.92h is persistently stirred after being added dropwise；Concentration, which is added dropwise, is
0.09g/mL aqueous ascorbic acids, wherein PtCl2Molar ratio with ascorbic acid is 1:2.2, continue to stir after being added dropwise
1.25h, obtains the hybrid material aqueous solution for the supporting Pt nano particle that mass percent concentration is 8%.
Embodiment 10
A kind of preparation method of the hybrid material aqueous solution of load Ni nano particles, under the conditions of 52 DEG C, by quality percentage
The carboxylic carboxymethyl chitosan sodium water solution that specific concentration is 2.4% and mass percent concentration be 9.2% it is amino-containing
Polyetheramine D2000 aqueous solutions mix, wherein, the relative molecular weight of carboxymethyl chitosan sodium is 340000, point of polyetheramine D2000
Son amount is 2000, and the molar ratio of carboxymethyl chitosan sodium and polyetheramine D2000 are 1:0.7, accompany by stirring；Using 0.1mol/L's
HNO3Solution adjusts the pH value of reaction system to 5.1, and the Ni (NO that concentration is 0.6g/mL are then added dropwise into mixed liquor3)2It is molten
Liquid, wherein Ni (NO3)2Molar ratio with carboxymethyl chitosan sodium is 5.3:1,0.87h is persistently stirred after being added dropwise；Dropwise plus
It is 0.072g/mL sodium triethylborohydride aqueous solutions to enter concentration, wherein Ni (NO3)2Molar ratio with sodium triethylborohydride is 1:
2.4, continue to stir 1.62h after being added dropwise, obtain the hybrid material for the load Ni nano particles that mass percent concentration is 7%
Aqueous solution.
Embodiment 11
A kind of preparation method of the hybrid material aqueous solution of load Fe nano particles, under the conditions of 55 DEG C, by quality percentage
The carboxylic carboxymethyl chitosan aqueous solutions of potassium that specific concentration is 1.3% and mass percent concentration be 3.9% it is amino-containing
Polyetheramine D4000 aqueous solutions mix, wherein, the relative molecular weight of carboxymethyl chitosan potassium is 200000, point of polyetheramine D4000
Son amount is 4000, and the molar ratio of carboxymethyl chitosan potassium and polyetheramine D4000 are 1:0.36, accompany by stirring；Using 0.19mol/L
HCl solution adjust reaction system pH value to 5.36, the FeCl that concentration is 0.89g/mL is then added dropwise into mixed liquor2It is molten
Liquid, wherein FeCl2Molar ratio with carboxymethyl chitosan potassium is 6.3:1,0.86h is persistently stirred after being added dropwise；It is added dropwise
Concentration is 0.068g/mL hydrazine hydrate aqueous solutions, wherein FeCl2Molar ratio with hydrazine hydrate is 1:2, continue to stir after being added dropwise
1.92h, obtains the hybrid material aqueous solution for the load Fe nano particles that mass percent concentration is 4%.Time is 1.5h, to obtain the final product
To the load Fe nano particle hybrid material aqueous solutions that mass percent concentration is 9.0%.
Embodiment 12
A kind of preparation method of the hybrid material aqueous solution of load Ni nano particles, under the conditions of 36 DEG C, by quality percentage
The carboxylic carboxyetbyl chitosan sodium water solution that specific concentration is 2.34% and mass percent concentration be 4.6% it is amino-containing
Polyetheramine T403 aqueous solutions mix, wherein, the relative molecular weight of carboxyetbyl chitosan sodium is 21000, the molecule of polyetheramine T403
Measure as 400, the molar ratio of carboxyetbyl chitosan sodium and polyetheramine T403 are 1:0.58, accompany by stirring；Using 0.08mol/L's
H2SO4Solution adjusts the pH value of reaction system to 5.3, and the Ni (NO that concentration is 1.7g/mL are then added dropwise into mixed liquor3)2It is molten
Liquid, wherein Ni (NO3)2Molar ratio with carboxyetbyl chitosan sodium is 4.3:1,0.84h is persistently stirred after being added dropwise；Dropwise plus
It is 0.05g/mL formalins, wherein Ni (NO to enter concentration3)2Molar ratio with formaldehyde is 1:9, continue to stir after being added dropwise
1.32h, obtains the hybrid material aqueous solution for the load Ni nano particles that mass percent concentration is 5%.
Embodiment 13
A kind of preparation method of the hybrid material aqueous solution of load Au nano particles, under the conditions of 50 DEG C, by quality percentage
The carboxylic carboxyetbyl chitosan aqueous solutions of potassium that specific concentration is 2.3% and mass percent concentration be 8.2% it is amino-containing
Polyetheramine T3000 aqueous solutions mix, wherein, the relative molecular weight of carboxyetbyl chitosan potassium is 165000, point of polyetheramine T3000
Son amount is 3000, and the molar ratio of carboxyetbyl chitosan potassium and polyetheramine T3000 are 1:0.4, accompany by stirring；Using 0.19mol/L
HCl solution adjust reaction system pH value to 4.6, the HAuCl that concentration is 0.009g/mL is then added dropwise into mixed liquor4It is molten
Liquid, wherein HAuCl4Molar ratio with carboxyetbyl chitosan potassium is 9.3:1,0.72h is persistently stirred after being added dropwise；It is added dropwise
Concentration is 0.04g/mL sodium borohydride aqueous solutions, wherein HAuCl4Molar ratio with sodium borohydride is 1:1.9, it is added dropwise follow-up
Continuous stirring 1.72h, obtains the hybrid material aqueous solution for the load Au nano particles that mass percent concentration is 7%.
Embodiment 14
A kind of preparation method of the hybrid material aqueous solution of load C r nano particles, under the conditions of 56 DEG C, by quality percentage
Bis- sodium carboxymethyl cellulose solutions of carboxylic 2,3- that specific concentration is 1.3% and mass percent concentration are 5% to contain ammonia
The polyetheramine T5000 aqueous solutions mixing of base, wherein, the relative molecular weight of 2,3- bis- sodium carboxymethylcelluloses is 40000, polyetheramine
The molecular weight of T5000 is that the molar ratio of 5000,2,3- bis- sodium carboxymethylcelluloses and polyetheramine T5000 is 1:0.5, accompany by and stir
Mix；Using the HNO of 0.29mol/L3Solution adjusts the pH value of reaction system to 4.5, and it is 1g/ that concentration is then added dropwise into mixed liquor
The Cr of mL2(SO4)3Solution, wherein Cr2(SO4)3Molar ratio with bis- sodium carboxymethylcelluloses of 2,3- is 6.3:1, after being added dropwise
Persistently stir 0.62h；It is 0.03g/mL potassium borohydride aqueous solutions that concentration, which is added dropwise, wherein Cr2(SO4)3With rubbing for potassium borohydride
You are than being 1:8, continue to stir 1.42h after being added dropwise, obtain the miscellaneous of the load C r nano particles that mass percent concentration is 7%
Change material aqueous solution.
Embodiment 15
A kind of preparation method of the hybrid material aqueous solution of load Au nano particles, under the conditions of 42 DEG C, by quality percentage
Bis- carboxymethyl cellulose aqueous solutions of potassium of carboxylic 2,3- that specific concentration is 2.3% and mass percent concentration are 6% to contain ammonia
The aliphatic amine polyoxyethylene ether AC-1810 aqueous solutions mixing of base, wherein, the relative molecular weight of 2,3- bis- potassium carboxymethylcelluloses is
The molecular weight of 250000, aliphatic amine polyoxyethylene ether AC-1810 are 1800,2,3- bis- potassium carboxymethylcelluloses and fatty amine polyoxy
The molar ratio of vinethene AC-1810 is 1:0.5, accompany by stirring；Using the H of 0.09mol/L2SO4Solution adjusts the pH of reaction system
Then the HAuCl that concentration is 1.7g/mL is added dropwise to 5 in value into mixed liquor4Solution, wherein HAuCl4With bis- carboxymethyl celluloses of 2,3-
The molar ratio of plain potassium is 7.3:1,0.82h is persistently stirred after being added dropwise；It is 0.02g/mL Vitamin C sour waters that concentration, which is added dropwise,
Solution, wherein HAuCl4Molar ratio with ascorbic acid is 1:7.8, continue to stir 1.52h after being added dropwise, obtain quality percentage
Specific concentration is the hybrid material aqueous solution of 2% load Au nano particles.
Embodiment 16
A kind of preparation method of the hybrid material aqueous solution of loaded Ag nano particle, under the conditions of 35 DEG C, by quality percentage
The amino-containing fatty amine that the carboxylic aqueous sodium polyacrylate that specific concentration is 2.3% is 9% with mass percent concentration
Polyoxyethylene ether AC-1812 aqueous solutions mix, wherein, the relative molecular weight of Sodium Polyacrylate is 30000, aliphatic amine polyoxyethylene
The molecular weight of ether AC-1812 is 1900, and the molar ratio of Sodium Polyacrylate and aliphatic amine polyoxyethylene ether AC-1812 are 1:0.9, companion
With stirring；Using the H of 0.13mol/L2SO4Solution adjusts the pH value of reaction system to 5.3, and concentration is then added dropwise into mixed liquor
For the AgNO of 1.6g/mL3Solution, wherein AgNO3Molar ratio with Sodium Polyacrylate is 4:1, persistently stirred after being added dropwise
0.8h；It is 0.066g/mL sodium triethylborohydride aqueous solutions that concentration, which is added dropwise, wherein AgNO3With sodium triethylborohydride
Molar ratio is 1:1.5, continue to stir 1.3h after being added dropwise, obtain the loaded Ag nano particle that mass percent concentration is 2%
Hybrid material aqueous solution.
Embodiment 17
A kind of preparation method of the hybrid material aqueous solution of loaded Cu nano particle, under the conditions of 55 DEG C, by quality percentage
The amino-containing fatty amine that the carboxylic polyacrylic acid aqueous solutions of potassium that specific concentration is 1.6% is 8% with mass percent concentration
Polyoxyethylene ether AC-1815 aqueous solutions mix, wherein, the relative molecular weight of polyacrylic acid potassium is 20000, aliphatic amine polyoxyethylene
The molecular weight of ether AC-1815 is 900, and the molar ratio of polyacrylic acid potassium and aliphatic amine polyoxyethylene ether AC-1815 are 1:0.6, companion
With stirring；Using the HNO of 0.18mol/L3Solution adjusts the pH value of reaction system to 4.7, and concentration is then added dropwise into mixed liquor
For the CuSO of 0.2g/mL4Solution, wherein CuSO4Molar ratio with polyacrylic acid potassium is 5:1, persistently stirred after being added dropwise
0.6h；It is 0.056g/mL hydrazine hydrate aqueous solutions that concentration, which is added dropwise, wherein CuSO4Molar ratio with hydrazine hydrate is 1:1, it is added dropwise
After continue stir 1.8h, obtain mass percent concentration be 1% loaded Cu nano particle hybrid material aqueous solution.
Embodiment 18
A kind of preparation method of the hybrid material aqueous solution of supporting Pt nano particle, under the conditions of 40 DEG C, by quality percentage
The amino-containing fatty amine polyoxy that the carboxylic sodium alginate aqueous solution that specific concentration is 2% is 5% with mass percent concentration
Vinethene AC-1205 aqueous solutions mix, wherein, the relative molecular weight of sodium alginate is 25000, aliphatic amine polyoxyethylene ether AC-
1205 molecular weight is 1200, and the molar ratio of sodium alginate and aliphatic amine polyoxyethylene ether AC-1205 are 1:0.5, accompany by stirring；
The pH value of reaction system is adjusted to 4.5 using the HCl solution of 0.25mol/L, it is 0.1g/mL that concentration is then added dropwise into mixed liquor
PtCl2Solution, wherein PtCl2Molar ratio with sodium alginate is 0.9:1,0.8h is persistently stirred after being added dropwise；It is added dropwise
Concentration is 0.095g/mL formalins, wherein PtCl2Molar ratio with formaldehyde is 1:1.2, continue to stir after being added dropwise
1.3h, obtains the hybrid material aqueous solution for the supporting Pt nano particle that mass percent concentration is 5%.
Embodiment 19
One kind load PdCl2The preparation method of the hybrid material aqueous solution of nano particle, under the conditions of 50 DEG C, by quality hundred
Divide the amino-containing fatty amine that the carboxylic potassium alginate aqueous solution that specific concentration is 1.6% is 5% with mass percent concentration
Polyoxyethylene ether AC-1210 aqueous solutions mix, wherein, the relative molecular weight of potassium alginate is 15000, aliphatic amine polyoxyethylene ether
The molecular weight of AC-1210 is 1200, and the molar ratio of potassium alginate and aliphatic amine polyoxyethylene ether AC-1210 are 1:0.6, accompany by and stir
Mix；Using the H of 0.13mol/L2SO4Solution adjusts the pH value of reaction system to 5.2, and concentration is then added dropwise into mixed liquor is
The PdCl of 0.8g/mL2Solution, wherein PdCl2Molar ratio with potassium alginate is 1.9:1,0.8h is persistently stirred after being added dropwise；
It is 0.087g/mL sodium borohydride aqueous solutions that concentration, which is added dropwise, wherein, PdCl2Molar ratio with sodium borohydride is 1:1.5, drop
Add and continue to stir 1.6h after finishing, obtain the load PdCl that mass percent concentration is 10%2The hybrid material water of nano particle
Solution.
Embodiment 20
A kind of preparation method of the hybrid material aqueous solution of load Fe nano particles, under the conditions of 45 DEG C, by quality percentage
The amino-containing fat that the carboxylic sodium carboxymethyl cellulose solution that specific concentration is 1.8% is 7% with mass percent concentration
Fat amine polyoxyethylene ether AC-1215 aqueous solutions mix, wherein, the relative molecular weight of sodium carboxymethylcellulose is 19000, fatty amine
The molecular weight of polyoxyethylene ether AC-1215 is 800, mole of sodium carboxymethylcellulose and aliphatic amine polyoxyethylene ether AC-1215
Than for 1:0.7, accompany by stirring；Using the H of 0.11mol/L2SO4Solution adjusts the pH value of reaction system to 4.8, then to mixing
The FeCl that concentration is 1.9g/mL is added dropwise in liquid2Solution, wherein FeCl2Molar ratio with sodium carboxymethylcellulose is 2.6:1, it is added dropwise
After persistently stir 0.9h；It is 0.025g/mL aqueous ascorbic acids that concentration, which is added dropwise, wherein FeCl2With ascorbic acid
Molar ratio be 1:2, continue to stir 1.9h after being added dropwise, obtain load Fe nanometers that mass percent concentration is 9.6%
The hybrid material aqueous solution of grain.
Claims (10)
1. a kind of hybrid material aqueous solution of carried metal nano particle, it is characterized in that：The carried metal nano particle it is miscellaneous
Change material aqueous solution to be made of the hybrid material and water of carried metal nano particle, the hydridization material of the carried metal nano particle
Bonded by ionic bond and coordinate bond between carboxyl, amino and metal nanoparticle in material, the carboxyl and amino adhere to molecule A separately
With the strand of molecule B；
In the molecule A and the molecule B, the sum of carboxyl-content, amino content and hydroxy radical content be more than or equal to the molecule A and
The 160% of the sum of the mole of the molecule B；
The carboxyl bonded by ionic bond and coordinate bond and the amino content bonded by ionic bond and coordinate bond it
With 30% more than or equal to the sum of carboxyl-content in the molecule A and the molecule B and amino mole；
Relative molecular weight >=10000 of the molecule A, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C and H
Composition；
Relative molecular weight≤5000 of the molecule B, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C and H groups
Into；
The general structure of the hybrid material of the water soluble negative metal-loaded nanoparticles is：
Or
Wherein, strand repetitive unit number m >=0, n>0；
R1、R2And R3Functional group is respectively one kind in following functional group：Cation group, anionic group or polar nonionic
Group；The cation group is tertiary amine base or quaternary ammonium group；The anionic group is carboxylic acid group；The polar nonionic group
For hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
M is metal nanoparticle, by Mx+Metal ion by reducing agent reduction form, Mx+The value of middle valence state x is 1~3, is：
Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
A kind of 2. hybrid material aqueous solution of carried metal nano particle according to claim 1, it is characterised in that band ammonia
The molecule B of base also includes hydroxyl or carboxyl, and the molecule B with carboxyl also includes hydroxyl or amino.
3. the hybrid material aqueous solution of a kind of carried metal nano particle according to claim 1, it is characterised in that described
Carboxyl is located at molecular backbone or side chain, and the amino is located at molecular backbone or side chain.
4. the hybrid material aqueous solution of a kind of carried metal nano particle according to claim 1, it is characterised in that described
The molecular backbone of molecule A further includes element O, N or S.
5. the hybrid material aqueous solution of a kind of carried metal nano particle according to claim 1, it is characterised in that described
The molecular backbone of molecule B further includes element O, N or S.
6. the hybrid material aqueous solution of a kind of carried metal nano particle according to claim 1, it is characterised in that described
The mass percent concentration of the hybrid material aqueous solution of carried metal nano particle is 0.5%~10.5%.
7. such as a kind of preparation of the hybrid material aqueous solution of carried metal nano particle according to any one of claims 1 to 6
Method, it is characterized in that：The aqueous solution of the materials of A containing molecule is mixed with the aqueous solution of the B substance containing molecule, adjusts the pH of reaction system
To 4~6, metal ion salt solution is then added dropwise into mixed liquor, continues to stir after being added dropwise, it is molten that reducing agent is then added dropwise
Liquid, is persistently stirred again after being added dropwise, that is, obtains the aqueous solution of carried metal nano particle hybrid material；
The materials of A containing molecule and B substance containing molecule are intersected containing carboxyl and amino, i.e.,：The materials of A containing molecule whens containing carboxyl, B containing molecule
Material contains amino；Conversely, the materials of A containing molecule whens containing amino, B substance containing molecule contain carboxyl.
8. a kind of preparation method of the hybrid material aqueous solution of carried metal nano particle according to claim 7, it is special
Sign is that the aqueous solution by the materials of A containing molecule is mixed with the aqueous solution of the B substance containing molecule, be under the conditions of 20~60 DEG C,
Stirring is accompanied by during mixing；The pH for adjusting reaction system uses HCl solution, the 0.05~0.15mol/L of 0.1~0.3mol/L
H2SO4The HNO of solution or 0.1~0.3mol/L3Solution is adjusted；The metal ion salt solution continues to stir after being added dropwise,
Time is 0.5~1h；The reducing agent solution persistently stirs after being added dropwise, and the duration is 1~2h.
9. a kind of preparation method of the hybrid material aqueous solution of carried metal nano particle according to claim 7, it is special
Sign is that the materials of A containing molecule are the carboxylic materials of A containing molecule of molecule A or the amino-containing materials of A containing molecule of molecule A；Institute
It is the carboxylic B substances containing molecule of molecule B or the amino-containing B substances containing molecule of molecule B to state B substance containing molecule；
It is fine that the carboxylic materials of A containing molecule of molecule A are selected from sodium alginate, potassium alginate, sodium carboxymethylcellulose, carboxymethyl
The plain potassium of dimension, sodium hydroxyethlcellulose, carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyethyl shell gather
Sugared sodium, carboxyetbyl chitosan potassium, bis- sodium carboxymethylcelluloses of 2,3-, bis- potassium carboxymethylcelluloses of 2,3-, Sodium Polyacrylate and poly-
One kind in potassium acrylate；
The amino-containing materials of A containing molecule of molecule A are chitosan, carboxymethyl chitosan or polyacrylamide；
The carboxylic B substances containing molecule of molecule B are selected from the alkyl chain acid that chain length is less than 6 carbon, are specially n-butyric acie, positive penta
Acid or n-caproic acid；
The amino-containing B substances containing molecule of molecule B are selected from alkyl streptamine, polyetheramine D230, the polyethers that chain length is less than 6 carbon
Amine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fatty amine polyoxy
Vinethene AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene
One kind in ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；The chain length is small
In the alkyl streptamine of 6 carbon be n-propylamine, n-butylamine, n-amylamine or n-hexylamine；
The metal ion salt solution is AgNO3、FeCl2、HAuCl4、Cr2(SO4)3、PtCl2、PdCl2、CuSO4Or Ni (NO3)2
Aqueous solution；
The reducing agent solution is sodium borohydride, potassium borohydride, ascorbic acid, sodium triethylborohydride, hydrazine hydrate or formaldehyde are molten
Liquid.
10. a kind of preparation method of the hybrid material aqueous solution of carried metal nano particle according to claim 7, it is special
Sign is, when the aqueous solution of the materials of A containing molecule is mixed with the aqueous solution of the B substance containing molecule, the materials of A containing molecule are with containing molecule
The molar ratio of B substance is 1:0.3~1；
The mass percent concentration of the aqueous solution of the materials of A containing molecule is 0.5%~3%；
The mass percent concentration of the aqueous solution of the B substance containing molecule is 3%~10%；
The concentration of the metal ion salt solution is 0.005~2g/mL；
The molar ratio of the metal cation salt and the materials of A containing molecule is 0.1~10:1；
The concentration of the solution of the reducing agent is 0.01~0.1g/mL；
The molar ratio of the metal cation salt and reducing agent material is 1:0.5~12；
The mass percent concentration of the hybrid material aqueous solution of the carried metal nano particle is 0.5%~10.5%.
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