CN105860152B - A kind of hybrid material and preparation method thereof of water soluble negative metal-loaded nanoparticles - Google Patents
A kind of hybrid material and preparation method thereof of water soluble negative metal-loaded nanoparticles Download PDFInfo
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Abstract
The present invention relates to a kind of hybrid materials and preparation method thereof of water soluble negative metal-loaded nanoparticles, the hybrid material is made of carrier molecule A, stable agent molecule B and metal nanoparticle, the aqueous solution of the aqueous solution of A and B is stirred, pH value is adjusted, metal ion salt solution and reducing agent solution are added dropwise successively, obtains the aqueous solution of the hybrid material, lasting stirring, precipitating reagent is added, filtering is the hybrid material of carried metal nano particle after the drying of taking precipitate vacuum drying oven.Metal nanoparticle is effectively connected to the form stable of ionic bond and coordinate bond on the strand of carrier molecule in carried metal nano particle hybrid material, makes it have good water solubility and the adjustable advantage of metal nanoparticle load capacity.The preparation method of the hybrid material is pollution-free, impurity in products is few and easy to operate.The hybrid material 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 and preparation method thereof of water soluble negative metal-loaded nanoparticles, more particularly to
A kind of hybrid material and preparation method thereof of the water soluble negative metal-loaded nanoparticles of stabilization.
Background technology
The hybrid material of carried metal nano particle refers to by the effect of chemical bond or secondary or physical bond by metal nano
Grain is keyed on carrier molecule, such hybrid material is widely applied to catalysis material, self assembly unit, anti-biotic material and fire-retardant
Material etc..
The groups such as hydroxyl, amino or carboxyl in carrier molecule have good chelation, energy to metal nanoparticle
Metal nanoparticle in effective absorption or trapping solution.During particulate nucleation and growth, monodisperse in order to obtain
Nano particle, high molecular polymer is used to as surfactant, stabilizer and the template in nano particle preparation process
Agent, so as to obtain the nano-particle of certain grain size distribution and shape.It is disclosed in CN101450385A a kind of using carboxylic first
The method that base sodium cellulosate prepares nano silver colloid aqueous solution, text in using silver nitrate aqueous solution as silver presoma, with carboxymethyl
Sodium cellulosate aqueous solution is as dispersion, and after silver nitrate aqueous solution is mixed with sodium carboxymethyl cellulose solution, regulation and control are anti-
Temperature and pH value are answered, is prepared for obtaining the aqueous solution of the silver colloidal particles containing average grain diameter less than 100 nanometers.
Mixed liquor is formed with the oxidation Curdlan polysaccharide containing carboxyl and silver nitrate solution in equal volume in CN103480859A, is prepared
Polysaccharide-based Nano silver grain aoxidizes Curdlan polysaccharide concentration, carboxyl-content and silver nitrate concentration by control, obtains particle size
Controllable spherical silver nanoparticles.But it is traditional nano particle is synthesized using environmentally protective method, the wider distribution of grain size,
The stability of nano particle is poor.
Invention content
The purpose of the present invention is be directed to it is above-mentioned prepare nano particle there are the problem of, a kind of water-soluble carried metal is provided and is received
Hybrid material of rice grain and preparation method thereof is especially to provide a kind of hydridization of the water soluble negative metal-loaded nanoparticles of stabilization
Material and preparation method thereof.The hybrid material of the carried metal nano particle prepared using the present invention has good water solubility,
Its aqueous solution is again with good stability, i.e., in aqueous solution, which is not have for the dissolving dispersion that hybrid material is stablized
Apparent particulate matter suspends or the transparent system of precipitation；Metal nanoparticle load capacity in hybrid material is adjustable, metal nano
Particle is effectively connected on the strand of carrier molecule with the form stable of ionic bond and coordinate bond；This method can also allow metal
Nanoparticles stable is dispersed in basis material, the size of Effective Regulation metal particle size.The instrument that preparation process uses
Equipment investment is less, and operating process is simply easy to implement, and the raw material used in reaction process are environmental-friendly and pollution-free, product
Impurity is few, is easy to post-process；Entire reaction process is conducive to industrial amplification production.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles of the present invention, the water-soluble load metal nano
It is bonded by ionic bond and coordinate bond between carboxyl, amino and metal nanoparticle in the hybrid material of grain；The carboxyl and amino
Adhere to the strand of molecule A and molecule B separately；
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
160%, A of the sum of the mole of the sub- A and the molecule B and carboxyl in B Compound complexes, amino and hydroxyl hydrophilic group
Be ensure the water-soluble principal element of Compound complex, 160% this numerical value be ensure Compound complex can have it is water-soluble
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 in the molecule A and molecule B and amino mole；
Relative molecular weight >=10000 of the molecule A, other than the N of the O of carboxyl or amino, molecular backbone is mainly by C
It is formed with H；
Relative molecular weight≤5000 of the molecule B, other than the N of the O of carboxyl or amino, molecular backbone is mainly by C
It is 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 and B-
With-NH3 +Because of the attraction of positive and negative charge, electrostatic attraction is generated, 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 metal ion and form coordinate bond and combined.Metal ion
Atomic state is reduced 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 value of reaction system is to-COO in system-、-NH3 +And Mx+The formation of bonding structure has prodigious
It influences.- NH in molecule A or molecule B2In pH value<In the case of 7, it can be combined to form-NH with excessive H protons in solution3 +；
With the raising of pH value, until under neutral or alkaline condition, the H protons to dissociate in solution are reduced, and cannot re-form-NH3 +Structure.
For-the COOH in molecule A and molecule B, in strong acid condition pH value<When 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 value when improving again, and-NH can be destroyed3 +Structure, to destroy the three-legged structure relationship of stable system of making.Therefore, in order to
The stable triangle bonding scheme stablized as shown in schematic diagram is formed, so the pH value of necessary effective adjustment and control system,
And ensure ranging from the 4~6 of pH value.
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 restored by reducing agent, Mx+The value of middle valence state x be 1~
3, be：Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
As preferred technical solution：
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the molecule B with amino also include hydroxyl
Base or carboxyl；Molecule B with carboxyl also includes hydroxyl or amino.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the carboxyl be located at molecular backbone or
Branch；The amino is located at molecular backbone or branch.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the molecular backbone of the molecule A is also
Including element O, N or S common in organic matter.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the molecular backbone of the molecule B is also
Including element O, N or S common in organic matter.
R in a kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, 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) and amino (- NH2)。
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the load of the metal nanoparticle
Amount is 13~850mg/g.
The present invention also provides a kind of preparation methods of the hybrid material of water soluble negative metal-loaded nanoparticles, will contain molecule
The aqueous solution of A substances is mixed with the aqueous solution of the B substance containing molecule, adjusts the pH value of reaction system to 4~6, then to mixed liquor
In metal ion salt solution and reducing agent solution are added dropwise successively, stirred after being added dropwise, obtain carried metal nano particle hydridization
The aqueous solution of material persistently stirs and is added precipitating reagent, filters, and obtains the sediment of hygrometric state, is after the drying precipitate of hygrometric state
Obtain the hybrid material of water soluble negative metal-loaded nanoparticles；
Containing carboxyl and amino, i.e., the substances of A containing molecule intersect with B substance containing molecule：The substances of A containing molecule whens containing carboxyl, contain
Molecule B substance contains amino；Conversely, the substances 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 objects
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；Stirring is accompanied by when mixing；It adjusts anti-
Answer the pH value of system using the HCl solution of 0.1~0.3mol/L, the H of 0.05~0.15mol/L2SO4Solution or 0.1~
The HNO of 0.3mol/L3Solution is adjusted；Metal ion salt solution stirs after being added dropwise, and the duration is 0.5~1h；Reducing agent
Solution stirs after being added dropwise, and the duration is 1~2h；Rinse sediment repeatedly with precipitating reagent 2~3 times, fully removal precipitation
Deionized water in object；The mode that the drying precipitate of hygrometric state is dried using vacuum drying oven, drying temperature are 25~30 DEG C,
Vacuum degree is 0.09~-0.1MPa.
A kind of preparation method of the hybrid material of water soluble negative metal-loaded nanoparticles as described above, the A containing molecule
Substance is the carboxylic substances of A containing molecule of molecule A or the amino-containing substances of A containing molecule of molecule A；The molecule A is carboxylic to be contained
Molecule A substances be selected from sodium alginate, potassium alginate, sodium carboxymethylcellulose, potassium carboxymethylcellulose, sodium hydroxyethlcellulose,
Carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyetbyl chitosan sodium, carboxyetbyl chitosan potassium, 2,
One kind in bis- sodium carboxymethylcelluloses of 3-, bis- potassium carboxymethylcelluloses of 2,3-, Sodium Polyacrylate and polyacrylic acid potassium；Preferably
For sodium alginate, potassium alginate, sodium carboxymethylcellulose, potassium carboxymethylcellulose, carboxymethyl chitosan sodium, carboxymethyl chitosan
Potassium, Sodium Polyacrylate and polyacrylic acid potassium, it is optimal for sodium carboxymethylcellulose and potassium carboxymethylcellulose；
The amino-containing substances of A containing molecule of molecule A are chitosan, carboxymethyl chitosan or polyacrylamide；Preferably
For chitosan；
The B substance containing molecule is the carboxylic B substances containing molecule of molecule B or the amino-containing B substances containing molecule of molecule B；
Alkyl chain acid of the carboxylic B substances containing molecule of molecule B selected from chain length less than 6 carbon, 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, gather
Ether amines D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fatty amine are poly-
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 chain length be less than 6 carbon alkyl streptamine be 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；
The precipitating reagent is ethyl alcohol or acetone, preferably ethyl alcohol；The precipitating reagent is miscellaneous with carried metal nano particle
The volume ratio for changing the aqueous solution of material is 2~3:1；A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above
Preparation method, when the aqueous solution of the substances of A containing molecule is mixed with the aqueous solution of the B substance containing molecule, the substances of A containing molecule with contain
The molar ratio of molecule B substance is 1:0.3~1；
The mass percent concentration of the aqueous solution of the substances 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%；
A concentration of 0.005~2g/mL of the metal ion salt solution；
The molar ratio of the metal cation salt and the substances of A containing molecule is 0.1~10:1；
The molar ratio of the metal cation salt and reducing agent substance is 1:0.5~12；
The volume ratio of the precipitating reagent and the aqueous solution of carried metal nano particle hybrid material is 2~4:1；
The mass percent concentration of the aqueous solution of the carried metal nano particle hybrid material is 0.5%~10.5%；
The load capacity of the metal nanoparticle is 13~850mg/g.
Advantageous effect：
It is easy-operating to prepare stable carried metal nano particle hybrid material the present invention provides a kind of simple for process
Preparation method, the carried metal nano particle hybrid material that this method is prepared have good water solubility, metal nano
Load capacity of the grain on carrier molecule is adjustable.
The hybrid material of water soluble negative carrying metal ion prepared by the present invention has good water solubility, i.e. the hydridization material
Expect that can be stablized is dispersed in water, aqueous solution is the transparent system that no apparent particulate matter suspends or precipitates.With do not add
The aqueous solution of molecule B substance stabilizers is compared, and aqueous solution is with good stability, passes through the pH value of regulation system, shape
At between metal nanoparticle and molecule A and molecule B ionic bond and coordinate bond be bonded, the load that metal nanoparticle can be stablized
In carrier molecule A substances, and disperse in aqueous solution, gold when without adding molecule B substance stabilizers in aqueous solution
Metal nano-particle stability is poor, easily reunites；It can be divided to regulate and control carrier by regulating and controlling the amount of the molecule B substance stabilizers of addition
The amount of portative metal nanoparticle in sub- A substances；The hybrid material obtained can pass through absolute ethyl alcohol either third
Ketone is purified to the fibrous solids of dry state, and convenient for storage, the solid matter after purification can re-dissolve in water again, be configured to water
Solution；The material uses after being re-dubbed solution with water, has the functional effects such as good antibacterial.It is used in the reaction process
Water is nontoxic as reaction dissolvent, environmentally protective；Less input for the instrument and equipment that preparation process itself uses, operating process
Simple easy to implement, experiment condition is mild, is easy to implement large-scale industrial production.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should 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 range.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles of the present invention, water soluble negative metal-loaded nanoparticles
It is bonded by ionic bond and coordinate bond between carboxyl, amino and metal ion in hybrid material, carboxyl and amino adhere to separately molecule A and
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；
The carboxyl bonded by ionic bond and coordinate bond and by the bonded amino content of ionic bond and coordinate bond it
With 30% more than or equal to the sum of carboxyl in the molecule A and the molecule B and amino mole；
Relative molecular weight >=10000 of the molecule A, other than the N of the O of carboxyl or amino, molecular backbone is mainly by C
It is formed with H；
Relative molecular weight≤5000 of the molecule B, other than the N of the O of carboxyl or amino, molecular backbone is mainly by C
It is formed with H；
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 be hydroxyl,
Ether, amino, amide groups, sulfydryl or halogen；
Mx+Value for metal ion, valence state x is 1~3, is：Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the molecule B with amino also include hydroxyl
Base or carboxyl；Molecule B with carboxyl also includes hydroxyl or amino.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the carboxyl be located at molecular backbone or
Branch；The amino is located at molecular backbone or branch.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the molecular backbone of the molecule A is also
Including element O, N or S common in organic matter.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the molecular backbone of the molecule B is also
Including element O, N or S common in organic matter.
A kind of hybrid material of water soluble negative metal-loaded nanoparticles as described above, the load of the metal nanoparticle
Amount is 13~850mg/g.
Embodiment 1
A kind of preparation method of the hybrid material of water solubility loaded Ag nano particle, under the conditions of 20 DEG C, by quality percentage
The aqueous solution for the sodium alginate that specific concentration is 0.5% is mixed with the aqueous solution for the n-amylamine that mass percent concentration is 3%, seaweed
The molar ratio of sour sodium and n-amylamine is 1:0.3, the relative molecular weight of sodium alginate and n-amylamine is respectively 25000 and 87.16, is mixed
Stirring is accompanied by when conjunction, and the pH value of system is adjusted to 4 with the HCl solution of 0.1mol/L, is then added dropwise into mixed liquor a concentration of
The AgNO of 0.005g/mL3Aqueous solution, AgNO3Molar ratio with sodium alginate is 0.1:1, it is stirred after being added dropwise, the duration
For 0.5h, reducing agent sodium borohydride solution, AgNO is then added dropwise3Molar ratio with sodium borohydride is 1:0.5, after being added dropwise again
Lasting stirring, duration are 1h to get to the aqueous solution of loaded Ag nano particle hybrid material, and mass percent concentration is
0.5%, precipitating reagent ethyl alcohol is persistently stirred and is added, the volume ratio of ethyl alcohol and the aqueous solution of loaded Ag nano particle hybrid material is
2:1, collected by suction sediment rinses sediment with ethyl alcohol 2 times repeatedly, and sediment is 25 DEG C in temperature, vacuum degree 0.09MPa
Under the conditions of obtain the hybrid material that water soluble negative carries Ag nano particles after vacuum drying oven drying, the load of Ag in the hybrid material
Amount is 13mg/g.
Embodiment 2
A kind of preparation method of the hybrid material of water-soluble load Fe nano particles, under the conditions of 60 DEG C, by quality percentage
The aqueous solution for the potassium alginate that specific concentration is 0.6% is mixed with the aqueous solution for the n-butylamine that mass percent concentration is 6%, seaweed
The molar ratio of sour potassium and n-butylamine is 1:0.7, the relative molecular weight of potassium alginate and n-butylamine is respectively 15000 and 73.14, is mixed
Stirring is accompanied by when conjunction, and the pH value of system is adjusted to 6 with the HCl solution of 0.15mol/L, is then added dropwise into mixed liquor a concentration of
The FeCl of 0.2g/mL2Aqueous solution, FeCl2Molar ratio with potassium alginate is 2.5:1, it is stirred after being added dropwise, the duration is
Reducing agent solution of potassium borohydride, FeCl is then added dropwise in 0.55h2Molar ratio with potassium borohydride is 1:1, it is held again after being added dropwise
Continuous stirring, duration are 2h to get to the aqueous solution of load Fe nano particle hybrid materials, and mass percent concentration is
1.2%, persistently stir and be added precipitating reagent acetone, the body of precipitating reagent acetone and the aqueous solution of load Fe nano particle hybrid materials
Product is than being 4:1, collected by suction sediment rinses sediment with acetone 3 times repeatedly, and sediment is 30 DEG C in temperature, and vacuum degree is
It is to obtain the hybrid material of water soluble negative load Fe nano particles after vacuum drying oven drying under the conditions of 0.08MPa, in the hybrid material
The load capacity of Fe is 55mg/g.
Embodiment 3
A kind of preparation method of the hybrid material of water-soluble load Au nano particles, under the conditions of 25 DEG C, by quality percentage
The aqueous solution for the polyetheramine D400 that the aqueous solution for the sodium carboxymethylcellulose that specific concentration is 1% is 4% with mass percent concentration
The molar ratio of mixing, sodium carboxymethylcellulose and polyetheramine D400 are 1:0.5, the phase of sodium carboxymethylcellulose and polyetheramine D400
It is respectively 19000 and 400 to molecular weight, when mixing accompanies by stirring, is arrived the pH value adjusting of system with the HCl solution of 0.2mol/L
6, the HAuCl of a concentration of 0.1g/mL is then added dropwise into mixed liquor4Aqueous solution, HAuCl4With the molar ratio of sodium carboxymethylcellulose
It is 0.5:1, it is stirred after being added dropwise, duration 0.6h, reducing agent ascorbic acid solution, HAuCl is then added dropwise4With it is anti-bad
The molar ratio of hematic acid is 1:2, it is persistently stirred again after being added dropwise, the duration is 1.5h to get miscellaneous to load Au nano particles
Change the aqueous solution of material, mass percent concentration 1.5% persistently stirs and is added precipitating reagent acetone, precipitating reagent acetone and
The volume ratio for loading the aqueous solution of Au nano particle hybrid materials is 3:1, collected by suction sediment rinses precipitation with acetone repeatedly
Object 2 times, sediment are 26 DEG C in temperature, obtain water soluble negative load under the conditions of vacuum degree is 0.07MPa after vacuum drying oven drying
The hybrid material of Au nano particles, the load capacity of Au is 60mg/g in the hybrid material.
Embodiment 4
A kind of preparation method of the hybrid material of water-soluble load Cr nano particles, under the conditions of 30 DEG C, by quality percentage
The aqueous solution for the polyetheramine D2000 that the aqueous solution for the potassium carboxymethylcellulose that specific concentration is 1% is 5% with mass percent concentration
The molar ratio of mixing, potassium carboxymethylcellulose and polyetheramine D2000 are 1:0.5, potassium carboxymethylcellulose and polyetheramine D2000's
Relative molecular weight is respectively 26000 and 2000, and when mixing accompanies by stirring, with the HCl solution of 0.25mol/L by the pH value tune of system
It saves to 5, the Cr of a concentration of 1g/mL is then added dropwise into mixed liquor2(SO4)3Aqueous solution, Cr2(SO4)3With potassium carboxymethylcellulose
Molar ratio be 0.5:1, it is stirred after being added dropwise, duration 0.65h, it is molten that reducing agent sodium triethylborohydride is then added dropwise
Liquid, Cr2(SO4)3Molar ratio with sodium triethylborohydride is 1:3, it is persistently stirred again after being added dropwise, duration 1h, i.e.,
The aqueous solution of load C r nano particle hybrid materials is obtained, mass percent concentration 2.9% persistently stirs and precipitation is added
The volume ratio of agent ethyl alcohol, precipitating reagent ethyl alcohol and the aqueous solution of the hybrid material of load C r nano particles is 4:1, collected by suction precipitation
Object, sediment is rinsed with ethyl alcohol 2 times repeatedly, and sediment is 27 DEG C in temperature, and vacuum drying oven is dry under the conditions of vacuum degree is 0.06MPa
It is to obtain the hybrid material of water soluble negative load Cr nano particles after dry, the load capacity of Cr is 850mg/g in the hybrid material.
Embodiment 5
A kind of preparation method of the hybrid material of water solubility supporting Pt nano particle, under the conditions of 50 DEG C, by quality percentage
The polyetheramine D4000's that the aqueous solution for the sodium hydroxyethlcellulose that specific concentration is 1.5% is 8% with mass percent concentration is water-soluble
Liquid mixes, and the molar ratio of sodium hydroxyethlcellulose and polyetheramine D4000 are 1:0.8, sodium hydroxyethlcellulose and polyetheramine D4000
Relative molecular weight be respectively 310000 and 4000, when mixing, accompanies by stirring, with the HCl solution of 0.3mol/L by the pH value of system
It adjusts to 4, the PtCl of a concentration of 0.5g/mL is then added dropwise into mixed liquor2Aqueous solution, PtCl2With rubbing for sodium hydroxyethlcellulose
You are than being 5:1, it is stirred after being added dropwise, duration 0.7h, reducing agent hydrazine hydrate solution, PtCl is then added dropwise2With hydration
The molar ratio of hydrazine is 1:4, it is persistently stirred again after being added dropwise, the duration is 2h to get to supporting Pt nano particle hydridization material
The aqueous solution of material, mass percent concentration 6.3% persistently stir and are added precipitating reagent acetone, precipitating reagent acetone and load
The volume ratio of the aqueous solution of the hybrid material of Pt nano particles is 3:1, collected by suction sediment rinses sediment repeatedly with acetone
3 times, sediment is 28 DEG C in temperature, and obtaining water soluble negative after vacuum drying oven drying under the conditions of vacuum degree is 0.05MPa carries Pt
The hybrid material of nano particle, the load capacity of Pt is 99mg/g in the hybrid material.
Embodiment 6
A kind of preparation method of the hybrid material of water-soluble load Pd nano particles, under the conditions of 60 DEG C, by quality percentage
The aqueous solution for the polyetheramine T403 that the aqueous solution for the carboxyethyl cellulose potassium that specific concentration is 2% is 6% with mass percent concentration
The molar ratio of mixing, carboxyethyl cellulose potassium and polyetheramine T403 are 1:0.8, the phase of carboxyethyl cellulose potassium and polyetheramine T403
It is respectively 35200 and 400 to molecular weight, when mixing accompanies by stirring, with the H of 0.05mol/L2SO4Solution adjusts the pH value of system
To 6, the PdCl of a concentration of 0.03g/mL is then added dropwise into mixed liquor2Aqueous solution, PdCl2With mole of carboxyethyl cellulose potassium
Than being 8:1, it is stirred after being added dropwise, duration 0.75h, reducing agent formalin, PdCl is then added dropwise2With rubbing for formaldehyde
You are than being 1:5, persistently stirred again after being added dropwise, the duration be 2h to get to load Pd nano particle hybrid materials water
Solution, mass percent concentration 2.0% persistently stir and are added Pd nanometers of precipitating reagent acetone, precipitating reagent acetone and load
The volume ratio of the aqueous solution of the hybrid material of particle is 2:1, collected by suction sediment rinses sediment with acetone 3 times repeatedly, sinks
Starch is 30 DEG C in temperature, and obtaining water soluble negative after vacuum drying oven drying under the conditions of vacuum degree is 0.04MPa carries Pd nanometers
The hybrid material of grain, the load capacity of Pd is 100mg/g in the hybrid material.
Embodiment 7
A kind of preparation method of the hybrid material of water solubility loaded Cu nano particle, under the conditions of 28 DEG C, by quality percentage
The polyetheramine T3000's that the aqueous solution for the carboxymethyl chitosan sodium that specific concentration is 1.7% is 9% with mass percent concentration is water-soluble
Liquid mixes, and the molar ratio of carboxymethyl chitosan sodium and polyetheramine T3000 are 1:0.7, carboxymethyl chitosan sodium and polyetheramine T3000
Relative molecular weight be respectively 340000 and 3000, when mixing, accompanies by stirring, with the H of 0.07mol/L2SO4Solution is by the pH of system
Value is adjusted to 6, and the CuSO of a concentration of 1.6g/mL is then added dropwise into mixed liquor4Aqueous solution, CuSO4With carboxymethyl chitosan sodium
Molar ratio is 0.5:1, it is stirred after being added dropwise, duration 0.8h, reducing agent sodium borohydride solution, CuSO is then added dropwise4
Molar ratio with sodium borohydride is 1:6, it is persistently stirred again after being added dropwise, the duration is 1h to get to loaded Cu nanometer
The aqueous solution of grain hybrid material, mass percent concentration 5.5% persistently stir and are added precipitating reagent ethyl alcohol, precipitating reagent second
The volume ratio of alcohol and the aqueous solution of loaded Cu nano particle hybrid material is 3:1, collected by suction sediment is rinsed repeatedly with ethyl alcohol
Sediment 2 times, sediment are 30 DEG C in temperature, and water solubility is obtained after vacuum drying oven drying under the conditions of vacuum degree is 0.03MPa
The hybrid material of loaded Cu nano particle, the load capacity of Cu is 112mg/g in the hybrid material.
Embodiment 8
A kind of preparation method of the hybrid material of water-soluble load Ni nano particles, under the conditions of 40 DEG C, by quality percentage
The aliphatic amine polyoxyethylene ether that the aqueous solution for the carboxymethyl chitosan potassium that specific concentration is 1.5% is 7% with mass percent concentration
The aqueous solution of AC-1210 mixes, and the molar ratio of carboxymethyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1210 are 1:0.6, carboxylic
Methyl chitosan potassium and the relative molecular weight of aliphatic amine polyoxyethylene ether AC-1210 are respectively 200000 and 1200, companion when mixing
With stirring, with the H of 0.1mol/L2SO4Solution adjusts the pH value of system to 6, and a concentration of 0.01g/ is then added dropwise into mixed liquor
Ni (the NO of mL3)2Aqueous solution, Ni (NO3)2Molar ratio with carboxymethyl chitosan potassium is 3:1, it is stirred after being added dropwise, when continuing
Between be 0.85h, then be added dropwise reducing agent solution of potassium borohydride, Ni (NO3)2Molar ratio with potassium borohydride is 1:7, it is added dropwise
It persistently stirs again afterwards, the duration is 2h to get to the aqueous solution of load Ni nano particle hybrid materials, and mass percent is dense
Degree is 3.1%, persistently stirs and be added precipitating reagent acetone, and precipitating reagent acetone is water-soluble with the hybrid material of load Ni nano particles
The volume ratio of liquid is 2:1, collected by suction sediment rinses sediment with acetone 2 times repeatedly, and sediment is 26 DEG C in temperature, very
The hybrid material that water soluble negative carries Ni nano particles, the hydridization are obtained under the conditions of reciprocal of duty cycle is 0.02MPa after vacuum drying oven drying
The load capacity of Ni is 263mg/g in material.
Embodiment 9
A kind of preparation method of the hybrid material of water solubility loaded Ag nano particle, under the conditions of 50 DEG C, by quality percentage
The aliphatic amine polyoxyethylene ether that the aqueous solution for the carboxyetbyl chitosan sodium that specific concentration is 0.5% is 5% with mass percent concentration
The aqueous solution of AC-1810 mixes, and the molar ratio of carboxyetbyl chitosan sodium and aliphatic amine polyoxyethylene ether AC-1810 are 1:0.8, carboxylic
The relative molecular weight of ethyl chitosan sodium and aliphatic amine polyoxyethylene ether AC-1810 are respectively 21000 and 1800, and when mixing accompanies by
Stirring, with the H of 0.12mol/L2SO4Solution adjusts the pH value of system to 6, and a concentration of 0.05g/ is then added dropwise into mixed liquor
The AgNO of mL3Aqueous solution, AgNO3Molar ratio with carboxyetbyl chitosan sodium is 0.8:1, it is stirred after being added dropwise, the duration is
Reducing agent ascorbic acid solution, AgNO is then added dropwise in 0.9h3Molar ratio with ascorbic acid is 1:8, continue again after being added dropwise
Stirring, duration are 1h to get to the aqueous solution of loaded Ag nano particle hybrid material, and mass percent concentration is
2.2%, persistently stir and be added precipitating reagent ethyl alcohol, precipitating reagent ethyl alcohol and the aqueous solution of the hybrid material of loaded Ag nano particle
Volume ratio is 2:1, collected by suction sediment rinses sediment with ethyl alcohol 3 times repeatedly, and sediment is 29 DEG C in temperature, vacuum degree
To obtain the hybrid material that water soluble negative carries Ag nano particles, the hybrid material after vacuum drying oven drying under the conditions of 0.01MPa
The load capacity of middle Ag is 384mg/g.
Embodiment 10
A kind of preparation method of the hybrid material of water-soluble load Fe nano particles, under the conditions of 20 DEG C, by quality percentage
The aliphatic amine polyoxyethylene ether that the aqueous solution for the carboxyetbyl chitosan potassium that specific concentration is 2.5% is 5% with mass percent concentration
The aqueous solution of AC-1812 mixes, and the molar ratio of carboxyetbyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1812 are 1:0.6, carboxylic
Ethyl chitosan potassium and the relative molecular weight of aliphatic amine polyoxyethylene ether AC-1812 are respectively 165000 and 1900, companion when mixing
With stirring, with the H of 0.15mol/L2SO4Solution adjusts the pH value of system to 4, is then added dropwise into mixed liquor a concentration of
The FeCl of 0.16g/mL2Aqueous solution, FeCl2Molar ratio with carboxyetbyl chitosan potassium is 0.6:1, it stirs, continues after being added dropwise
Time is 0.55h, and reducing agent sodium triethylborohydride solution, FeCl is then added dropwise2Molar ratio with sodium triethylborohydride is
1:9, persistently stirred again after being added dropwise, the duration be 1.5h to get to load Fe nano particle hybrid materials aqueous solution,
Its mass percent concentration is 4.2%, persistently stirs and be added precipitating reagent acetone, and precipitating reagent acetone and load Fe nano particles are miscellaneous
The volume ratio for changing the aqueous solution of material is 2:1, collected by suction sediment rinses sediment with acetone 2 times repeatedly, and sediment is in temperature
Degree is 30 DEG C, obtains the hydridization that water soluble negative carries Fe nano particles under the conditions of vacuum degree is 0.09MPa after vacuum drying oven drying
Material, the load capacity of Fe is 419mg/g in the hybrid material.
Embodiment 11
A kind of preparation method of the hybrid material of water-soluble load Au nano particles, under the conditions of 40 DEG C, by quality percentage
The fatty amine polyoxy that the aqueous solution for bis- sodium carboxymethylcelluloses of 2,3- that specific concentration is 2.8% is 6% with mass percent concentration
The aqueous solution of vinethene AC-1815 mixes, mole of 2,3- bis- sodium carboxymethylcelluloses and aliphatic amine polyoxyethylene ether AC-1815
Than being 1:The relative molecular weight of 0.8,2,3- bis- sodium carboxymethylcellulose and aliphatic amine polyoxyethylene ether AC-1815 is respectively
40000 and 900, when mixing, accompanies by stirring, with the HNO of 0.1mol/L3Solution adjusts the pH value of system to 6, then to mixing
The HAuCl of a concentration of 0.18g/mL is added dropwise in liquid4Aqueous solution, HAuCl4Molar ratio with bis- sodium carboxymethylcelluloses of 2,3- is 3:
1, it is stirred after being added dropwise, duration 0.5h, reducing agent hydrazine hydrate solution, HAuCl is then added dropwise4With mole of hydrazine hydrate
Than being 1:10, persistently stirred again after being added dropwise, the duration be 2h to get to load Au nano particle hybrid materials it is water-soluble
Liquid, mass percent concentration 3% persistently stir and are added precipitating reagent ethyl alcohol, precipitating reagent ethyl alcohol and load Au nano particles
The volume ratio of the aqueous solution of hybrid material is 4:1, collected by suction sediment rinses sediment with ethyl alcohol 2 times repeatedly, and sediment exists
Temperature is 26 DEG C, and obtaining water soluble negative after vacuum drying oven drying under the conditions of vacuum degree is -0.1MPa carries the miscellaneous of Au nano particles
Change material, the load capacity of Au is 523mg/g in the hybrid material.
Embodiment 12
A kind of preparation method of the hybrid material of water-soluble load Cr nano particles, under the conditions of 30 DEG C, by quality percentage
The fatty amine polyoxy that the aqueous solution for bis- potassium carboxymethylcelluloses of 2,3- that specific concentration is 0.9% is 8% with mass percent concentration
The aqueous solution of vinethene AC-1205 mixes, mole of 2,3- bis- potassium carboxymethylcelluloses and aliphatic amine polyoxyethylene ether AC-1205
Than being 1:The relative molecular weight of 1,2,3- bis- potassium carboxymethylcellulose and aliphatic amine polyoxyethylene ether AC-1205 are respectively 250000
With 1200, when mixing, accompanies by stirring, with the HNO of 0.15mol/L3Solution adjusts the pH value of system to 5, then into mixed liquor
The Cr of a concentration of 0.006g/mL is added dropwise2(SO4)3Aqueous solution, Cr2(SO4)3Molar ratio with bis- potassium carboxymethylcelluloses of 2,3- is
0.6:1, it is stirred after being added dropwise, duration 1h, reducing agent formalin, Cr is then added dropwise2(SO4)3With mole of formaldehyde
Than being 1:11, it is persistently stirred again after being added dropwise, the duration is 1h to get to the water-soluble of load C r nano particle hybrid materials
Liquid, mass percent concentration 2.8% persistently stir and are added precipitating reagent ethyl alcohol, precipitating reagent ethyl alcohol and load C r nanometers
The volume ratio of the aqueous solution of the hybrid material of grain is 2:1, collected by suction sediment rinses sediment with ethyl alcohol 3 times repeatedly, precipitation
Object is 25 DEG C in temperature, and obtaining water soluble negative after vacuum drying oven drying under the conditions of vacuum degree is -0.09MPa carries Cr nano particles
Hybrid material, the load capacity of Cr is 589mg/g in the hybrid material.
Embodiment 13
A kind of preparation method of the hybrid material of water solubility supporting Pt nano particle, under the conditions of 60 DEG C, by quality percentage
The polyetheramine T5000's that the aqueous solution for the carboxymethyl chitosan sodium that specific concentration is 3% is 10% with mass percent concentration is water-soluble
Liquid mixes, and the molar ratio of carboxymethyl chitosan sodium and polyetheramine T5000 are 1:1, carboxymethyl chitosan sodium and polyetheramine T5000's
Relative molecular weight is respectively 340000 and 5000, and when mixing accompanies by stirring, with the HNO of 0.2mol/L3Solution is by the pH value of system
It adjusts to 4, the PtCl of a concentration of 2g/mL is then added dropwise into mixed liquor2Aqueous solution, PtCl2With mole of carboxymethyl chitosan sodium
Than being 10:1, it is stirred after being added dropwise, duration 0.6h, reducing agent sodium borohydride solution, PtCl is then added dropwise2With boron hydrogen
The molar ratio for changing sodium is 1:12, it is persistently stirred again after being added dropwise, the duration is 2h to get to supporting Pt nano particle hydridization
The aqueous solution of material, mass percent concentration 8.3% persistently stir and are added precipitating reagent ethyl alcohol, precipitating reagent ethyl alcohol with it is negative
The volume ratio for carrying the aqueous solution of the hybrid material of Pt nano particles is 2:1, collected by suction sediment rinses precipitation with ethyl alcohol repeatedly
Object 3 times, sediment are 30 DEG C in temperature, obtain water soluble negative load under the conditions of vacuum degree is -0.08MPa after vacuum drying oven drying
The hybrid material of Pt nano particles, the load capacity of Pt is 612mg/g in the hybrid material.
Embodiment 14
A kind of preparation method of the hybrid material of water-soluble load Pd nano particles, under the conditions of 40 DEG C, by quality percentage
The aliphatic amine polyoxyethylene ether AC- that the aqueous solution for the polyacrylic acid potassium that specific concentration is 1.2% is 3% with mass percent concentration
The molar ratio of 1215 aqueous solution mixing, polyacrylic acid potassium and aliphatic amine polyoxyethylene ether AC-1215 are 1:0.5, polyacrylic acid
Potassium and the relative molecular weight of aliphatic amine polyoxyethylene ether AC-1215 are respectively 20000 and 800, and when mixing accompanies by stirring, uses
The HNO of 0.25mol/L3Solution adjusts the pH value of system to 5, and the PdCl of a concentration of 0.12g/mL is then added dropwise into mixed liquor2
Aqueous solution, PdCl2Molar ratio with polyacrylic acid potassium is 2:1, it stirs after being added dropwise, duration 0.65h, is then added dropwise
Reducing agent solution of potassium borohydride, PdCl2Molar ratio with potassium borohydride is 1:2.5, it is persistently stirred again after being added dropwise, when continuing
Between be 1h to get to the aqueous solution of load Pd nano particle hybrid materials, mass percent concentration 2.9%, lasting stirring
And precipitating reagent acetone is added, the volume ratio of precipitating reagent acetone and the aqueous solution of load Pd nano particle hybrid materials is 2:1, it filters
Sediment is collected, rinses sediment repeatedly with acetone 2 times, sediment is 26 DEG C in temperature, and vacuum degree is true under the conditions of being -0.1MPa
It is to obtain the hybrid material of water soluble negative load Pd nano particles after empty oven drying, the load capacity of Pd is in the hybrid material
648mg/g。
Embodiment 15
A kind of preparation method of the hybrid material of water solubility loaded Cu nano particle, under the conditions of 30 DEG C, by quality percentage
The aqueous solution for the chitosan that specific concentration is 1.6% is mixed with the aqueous solution for the n-butyric acie that mass percent concentration is 7%, chitosan
Molar ratio with n-butyric acie is 1:0.9, the relative molecular weight of chitosan and n-butyric acie is respectively 240000 and 88.1, companion when mixing
With stirring, with the HNO of 0.3mol/L3Solution adjusts the pH value of system to 5, and a concentration of 0.8g/ is then added dropwise into mixed liquor
The CuSO of mL4Aqueous solution, CuSO4Molar ratio with chitosan is 6:1, it is stirred after being added dropwise, duration 0.7h, then
Reducing agent ascorbic acid solution, CuSO is added dropwise4Molar ratio with ascorbic acid is 1:3.5, it persistently stirs, holds again after being added dropwise
The continuous time is 1h to get to the aqueous solution of loaded Cu nano particle hybrid material, mass percent concentration 10.5%, persistently
Stir and be added precipitating reagent ethyl alcohol, the volume ratio of precipitating reagent ethyl alcohol and the aqueous solution of loaded Cu nano particle hybrid material is 3:1,
Collected by suction sediment, sediment is rinsed with ethyl alcohol 3 times repeatedly, and sediment is 28 DEG C in temperature, and vacuum degree is 0.09MPa conditions
It is to obtain the hybrid material of water soluble negative load Cu nano particles after lower vacuum drying oven drying, the load capacity of Cu is in the hybrid material
13mg/g。
Embodiment 16
A kind of preparation method of the hybrid material of water-soluble load Ni nano particles, under the conditions of 20 DEG C, by quality percentage
The aqueous solution for the carboxymethyl chitosan that specific concentration is 2.4% is mixed with the aqueous solution for the positive valeric acid that mass percent concentration is 6%,
The molar ratio of carboxymethyl chitosan and positive valeric acid is 1:0.4, the relative molecular weight of carboxymethyl chitosan and positive valeric acid is respectively
10000 and 102.13, when mixing, accompanies by stirring, is adjusted the pH value of system to 6 with the HCl solution of 0.1mol/L, then to mixed
Close the Ni (NO that a concentration of 0.06g/mL is added dropwise in liquid3)2Aqueous solution, Ni (NO3)2Molar ratio with carboxymethyl chitosan is 0.8:
1, it is stirred after being added dropwise, duration 0.75h, reducing agent sodium borohydride solution, Ni (NO is then added dropwise3)2With sodium borohydride
Molar ratio be 1:4.5, persistently stirred again after being added dropwise, the duration be 2h to get to load Ni nano particle hydridization materials
The aqueous solution of material, mass percent concentration 2.5% persistently stir and are added precipitating reagent acetone, precipitating reagent acetone and load
The volume ratio of the aqueous solution of Ni nano particle hybrid materials is 3:1, collected by suction sediment rinses sediment 2 with acetone repeatedly
Secondary, sediment is 29 DEG C in temperature, and obtaining water soluble negative load Ni after vacuum drying oven drying under the conditions of vacuum degree is -0.1MPa receives
The hybrid material of rice grain, the load capacity of Ni is 419mg/g in the hybrid material.
Embodiment 17
A kind of preparation method of the hybrid material of water solubility loaded Ag nano particle, under the conditions of 25 DEG C, by quality percentage
The aqueous solution for the polyacrylamide that specific concentration is 0.8% is mixed with the aqueous solution for the n-caproic acid that mass percent concentration is 5%, is gathered
The molar ratio of acrylamide and n-caproic acid is 1:0.7, the relative molecular weight of polyacrylamide and n-caproic acid is respectively 1 × 106With
115.15, when mixing, accompanies by stirring, is adjusted the pH value of system to 4 with the HCl solution of 0.3mol/L, is then dripped into mixed liquor
Add the AgNO of a concentration of 0.08g/mL3Aqueous solution, AgNO3Molar ratio with polyacrylamide is 3.5:1, it is stirred after being added dropwise,
Duration is 0.8h, and reducing agent sodium triethylborohydride solution, AgNO is then added dropwise3With the molar ratio of sodium triethylborohydride
It is 1:5.5, it is persistently stirred again after being added dropwise, the duration is 2h to get to the water-soluble of loaded Ag nano particle hybrid material
Liquid, mass percent concentration 0.5% persistently stir and are added precipitating reagent acetone, precipitating reagent acetone and loaded Ag nanometer
The volume ratio of the aqueous solution of grain hybrid material is 3:1, collected by suction sediment rinses sediment with acetone 3 times repeatedly, sediment
It it is 29 DEG C in temperature, obtaining water soluble negative after vacuum drying oven drying under the conditions of vacuum degree is 0.09MPa carries Ag nano particles
Hybrid material, the load capacity of Ag is 763mg/g in the hybrid material.
Embodiment 18
A kind of preparation method of the hybrid material of water-soluble load Fe nano particles, under the conditions of 50 DEG C, by quality percentage
The aqueous solution for the sodium alginate that specific concentration is 2.6% is mixed with the aqueous solution for the n-hexylamine that mass percent concentration is 5%, seaweed
The molar ratio of sour sodium and n-hexylamine is 1:0.5, the relative molecular weight of sodium alginate and n-hexylamine is respectively 25000 and 101.19,
Stirring is accompanied by when mixing, with the H of 0.05mol/L2SO4Solution adjusts the pH value of system to 6, is then added dropwise into mixed liquor dense
Degree is the FeCl of 0.5g/mL2Aqueous solution, FeCl2It is 5 with the molar ratio containing sodium alginate:1, it is stirred after being added dropwise, when continuing
Between be 0.85h, then be added dropwise reducing agent hydrazine hydrate solution, FeCl2Molar ratio with hydrazine hydrate is 1:6.5, after being added dropwise again
Lasting stirring, duration are 1h to get to the aqueous solution of load Fe nano particle hybrid materials, and mass percent concentration is
7.3%, persistently stir and be added precipitating reagent ethyl alcohol, the body of precipitating reagent ethyl alcohol and the aqueous solution of load Fe nano particle hybrid materials
Product is than being 2:1, collected by suction sediment rinses sediment with ethyl alcohol 2 times repeatedly, and sediment is 27 DEG C in temperature, and vacuum degree is
It is to obtain the hybrid material of water soluble negative load Fe nano particles after vacuum drying oven drying under the conditions of 0.09MPa, in the hybrid material
The load capacity of Fe is 692mg/g.
Embodiment 19
A kind of preparation method of the hybrid material of water-soluble load Au nano particles, under the conditions of 60 DEG C, by quality percentage
The aqueous solution for the potassium alginate that specific concentration is 1.4% is mixed with the aqueous solution for the n-propylamine that mass percent concentration is 3%, seaweed
The molar ratio of sour potassium and n-propylamine is 1:0.3, the relative molecular weight of potassium alginate and n-propylamine is respectively 15000 and 59.11, is mixed
Stirring is accompanied by when conjunction, with the H of 0.15mol/L2SO4Solution adjusts the pH value of system to 5, and concentration is then added dropwise into mixed liquor
For the HAuCl of 0.15g/mL4Aqueous solution, HAuCl4The molar ratio of aqueous solution and potassium alginate is 0.6:1, it is stirred after being added dropwise,
Duration is 0.9h, and reducing agent formalin, HAuCl is then added dropwise4Molar ratio with formaldehyde is 1:7.5, after being added dropwise
Persistently stir again, the duration be 1h to get to load Au nano particle hybrid materials aqueous solution, mass percent concentration
It is 2.1%, persistently stirs and be added precipitating reagent ethyl alcohol, the aqueous solution of precipitating reagent ethyl alcohol and the hybrid material of load Au nano particles
Volume ratio be 2:1, collected by suction sediment rinses sediment with ethyl alcohol 3 times repeatedly, and sediment is 26 DEG C in temperature, vacuum
The hybrid material that water soluble negative carries Au nano particles, the hydridization material are obtained under the conditions of degree is -0.1MPa after vacuum drying oven drying
The load capacity of Au is 782mg/g in material.
Embodiment 20
A kind of preparation method of the hybrid material of water-soluble load Cr nano particles, under the conditions of 20 DEG C, by quality percentage
The aqueous solution for the polyetheramine D230 that the aqueous solution for the Sodium Polyacrylate that specific concentration is 2.9% is 4% with mass percent concentration is mixed
It closes, the molar ratio of Sodium Polyacrylate and polyetheramine D230 are 1:0.6, the relative molecular weight point of Sodium Polyacrylate and polyetheramine D230
Not Wei 30000 and 230, when mixing, accompanies by stirring, with the HNO of 0.3mol/L3Solution adjusts the pH value of system to 6, then to
The Cr of a concentration of 0.5g/mL is added dropwise in mixed liquor2(SO4)3Aqueous solution, Cr2(SO4)3Molar ratio with Sodium Polyacrylate is 3:1,
It is stirred after being added dropwise, duration 1h, reducing agent solution of potassium borohydride, Cr is then added dropwise2(SO4)3With rubbing for potassium borohydride
You are than being 1:8.5, it is persistently stirred again after being added dropwise, the duration is 2h to get to load C r nano particle hybrid materials
Aqueous solution, mass percent concentration 10.5% persistently stir and are added precipitating reagent ethyl alcohol, and precipitating reagent ethyl alcohol is received with load C r
The volume ratio of the aqueous solution of rice grain hybrid material is 4:1, collected by suction sediment rinses sediment with ethyl alcohol 3 times repeatedly, sinks
Starch is 25 DEG C in temperature, and obtaining water soluble negative after vacuum drying oven drying under the conditions of vacuum degree is -0.1MPa carries Cr nanometers
The hybrid material of grain, the load capacity of Cr is 850mg/g in the hybrid material.
Claims (10)
1. a kind of hybrid material of water soluble negative metal-loaded nanoparticles, it is characterized in that：The water-soluble load metal nano
It is bonded by ionic bond and coordinate bond between carboxyl, amino and metal nanoparticle in the hybrid material of grain；The carboxyl and amino
Adhere to the strand of molecule A and molecule B separately；
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 in the molecule A and the molecule B and amino mole；
Relative molecular weight >=10000 of the molecule A, other than the N of the O of carboxyl or amino, molecular backbone is mainly by C and H
Composition；
Relative molecular weight≤5000 of the molecule B, other than the N of the O of carboxyl or amino, molecular backbone is mainly by C and H groups
At；
The general structure of the hybrid material of the water soluble negative metal-loaded nanoparticles is：
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 restored by reducing agent, Mx+The value of middle valence state x is 1~3, is：
Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
2. a kind of hybrid material of water soluble negative metal-loaded nanoparticles according to claim 1, which is characterized in that band ammonia
The molecule B of base also includes hydroxyl or carboxyl；Molecule B with carboxyl also includes hydroxyl or amino.
3. a kind of hybrid material of water soluble negative metal-loaded nanoparticles according to claim 1, which is characterized in that described
Carboxyl is located at molecular backbone or branch；The amino is located at molecular backbone or branch.
4. a kind of hybrid material of water soluble negative metal-loaded nanoparticles according to claim 1, which is characterized in that described
The molecular backbone of molecule A further includes element O, N or S.
5. a kind of hybrid material of water soluble negative metal-loaded nanoparticles according to claim 1, which is characterized in that described
The molecular backbone of molecule B further includes element O, N or S.
6. a kind of hybrid material of water soluble negative metal-loaded nanoparticles according to claim 1, which is characterized in that described
The load capacity of metal nanoparticle is 13~850mg/g.
7. such as a kind of preparation of the hybrid material of water soluble negative metal-loaded nanoparticles according to any one of claims 1 to 6
Method, it is characterized in that：The aqueous solution of the substances of A containing molecule is mixed with the aqueous solution of the B substance containing molecule, adjusts the pH of reaction system
Then metal ion salt solution is added dropwise into mixed liquor, is stirred after being added dropwise, reducing agent solution is then added dropwise to 4~6 for value,
Lasting stirring is heavy to get to the aqueous solution of carried metal nano particle hybrid material, persistently stirring and being added again after being added dropwise
Shallow lake agent is collected by filtration sediment, the hybrid material of water soluble negative metal-loaded nanoparticles is obtained after drying precipitate；
Containing carboxyl and amino, i.e., the substances of A containing molecule intersect with B substance containing molecule：The substances of A containing molecule whens containing carboxyl, B containing molecule
Substance contains amino；Conversely, the substances of A containing molecule whens containing amino, B substance containing molecule contain carboxyl.
8. a kind of preparation method of the hybrid material of water soluble negative metal-loaded nanoparticles according to claim 7, special
Sign is, the aqueous solution of the substances of A containing molecule is mixed with the aqueous solution of the B substance containing molecule, is under the conditions of 20~60 DEG C；Mixing
When accompany by stirring；The pH value of reaction system is adjusted using the HCl solution of 0.1~0.3mol/L, the H of 0.05~0.15mol/L2SO4
The HNO of solution or 0.1~0.3mol/L3Solution is adjusted；Metal ion salt solution stirs after being added dropwise, the duration 0.5
~1h；Reducing agent solution stirs after being added dropwise, and the duration is 1~2h；Drying precipitate is dried using vacuum drying oven.
9. a kind of preparation method of the hybrid material of water soluble negative metal-loaded nanoparticles according to claim 7, special
Sign is that the substances of A containing molecule are the carboxylic substances of A containing molecule of molecule A or the amino-containing substances of A containing molecule of molecule A；Institute
It states the carboxylic substances of A containing molecule of molecule A and is selected from sodium alginate, potassium alginate, sodium carboxymethylcellulose, carboxymethyl cellulose
Potassium, sodium hydroxyethlcellulose, carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyetbyl chitosan
Sodium, carboxyetbyl chitosan potassium, bis- sodium carboxymethylcelluloses of 2,3-, bis- potassium carboxymethylcelluloses of 2,3-, Sodium Polyacrylate and poly- third
One kind in olefin(e) acid potassium；
The amino-containing substances of A containing molecule of molecule A are chitosan, carboxymethyl chitosan or polyacrylamide；
The B substance containing molecule is the carboxylic B substances containing molecule of molecule B or the amino-containing B substances containing molecule of molecule B；
The carboxylic B substances containing molecule of molecule B are selected from the alkyl chain acid that chain length is less than 6 carbon, 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 polyetheramine that chain length is less than 6 carbon
D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fatty amine polyoxy second
Alkene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether
One kind in AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；The chain length is less than
The alkyl streptamine of 6 carbon is 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；
The precipitating reagent is ethyl alcohol or acetone.
10. a kind of preparation method of the hybrid material of water soluble negative metal-loaded nanoparticles according to claim 7, special
Sign is, when the aqueous solution of the substances of A containing molecule is mixed with the aqueous solution of the B substance containing molecule, the substances of A containing molecule with contain molecule
The molar ratio of B substance is 1:0.3~1；
The mass percent concentration of the aqueous solution of the substances 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%；
A concentration of 0.005~2g/mL of the metal ion salt solution；
The molar ratio of the metal cation salt and the substances of A containing molecule is 0.1~10:1；
The molar ratio of the metal cation salt and reducing agent substance is 1:0.5~12；
The mass percent concentration of the aqueous solution of the carried metal nano particle hybrid material is 0.5%~10.5%；
The volume ratio of the precipitating reagent and the aqueous solution of carried metal nano particle hybrid material is 2~4:1；
The temperature of the drying precipitate is 25~30 DEG C, and vacuum degree is 0.09~-0.1MPa.
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