CN105860152A - Water-soluble hybrid material loaded with metal nanoparticles and preparing method of water-soluble hybrid material - Google Patents
Water-soluble hybrid material loaded with metal nanoparticles and preparing method of water-soluble hybrid material Download PDFInfo
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Abstract
The invention relates to a water-soluble hybrid material loaded with metal nanoparticles and a preparing method of the water-soluble hybrid material. The hybrid material is prepared from carrier molecules A, stabilizer molecules B and the metal nanoparticles; an aqueous solution of A and an aqueous solution of B are stirred and mixed, the pH value is regulated, a metal ion saline solution and a reducing agent solution are dropwise added in sequence, an aqueous solution of the hybrid material is obtained, stirring is carried out continuously, a precipitator is added, filtering is carried out, precipitate is taken and dried in a vacuum oven, and the hybrid material loaded with the metal nanoparticles is obtained. The metal nanoparticles in the hybrid material loaded with metal nanoparticles are stably and effectively connected to molecular chains of the carrier molecules in an ionic bond and coordinate bond mode, and thus the hybrid material has the advantages that water solubility is good, and the loading quantity of the metal nanoparticles is adjustable. The preparing method of the hybrid material is free of pollution, few impurities are generated in the product, and operation is simple. The prepared hybrid material loaded with the metal nanoparticles has wide application on the aspects such as antibiotic finishing solutions, self-assembly stock solutions and catalyst materials.
Description
Technical field
The present invention relates to hybrid material of a kind of water soluble negative metal-loaded nanoparticles and preparation method thereof, particularly relate to a kind of steady
Fixed hybrid material of water soluble negative metal-loaded nanoparticles and preparation method thereof.
Background technology
The hybrid material of carried metal nano-particle refers to be keyed to by metal nanoparticle by the effect of chemical bond or secondary or physical bond
On carrier molecule, such hybrid material is widely applied to the sides such as catalysis material, self assembly unit, anti-biotic material and fire proofing
Face.
The groups such as hydroxyl, amino or carboxyl in carrier molecule have good chelation to metal nanoparticle, can be effective
Metal nanoparticle in absorption or trapping solution.During particulate nucleation and growth, in order to obtain mono-dispersed nano
Grain, high molecular polymer is used to as the surfactant in nano-particle preparation process, stabilizer and template, thus can
To obtain the nanoparticle of certain grain size distribution and shape.CN101450385A discloses a kind of employing sodium carboxymethyl cellulose
The method preparing nano silver colloid aqueous solution, using silver nitrate aqueous solution as silver presoma in literary composition, water-soluble with sodium carboxymethyl cellulose
Liquid is as dispersion, after silver nitrate aqueous solution is mixed with sodium carboxymethyl cellulose solution, and regulation and control reaction temperature and pH
Value, is prepared for the aqueous solution obtaining being less than the silver colloidal particles of 100 nanometers containing mean diameter.To contain in CN103480859A
The oxidation Curdlan polysaccharide and the silver nitrate solution equal-volume that have carboxyl form mixed liquor, prepare polysaccharide-based Nano silver grain, logical
Cross control oxidation Curdlan polysaccharide concentration, carboxyl-content and silver nitrate concentration, obtain the spherical silver nanoparticle that size is controlled
Son.But traditional method synthesis nano-particle using environmental protection, the wider distribution of particle diameter, the stability of nano-particle is relatively
Difference.
Summary of the invention
It is an object of the invention to prepare, for above-mentioned, the problem that nano-particle exists, it is provided that a kind of water soluble negative metal-loaded nanoparticles
Hybrid material and preparation method thereof, particularly provide a kind of stable water soluble negative metal-loaded nanoparticles hybrid material and
Preparation method.The hybrid material of carried metal nano-particle prepared by the employing present invention has good water solublity, and its aqueous solution is again
Having the stable dissolving of good stability, i.e. hybrid material to disperse in aqueous, this aqueous solution is not have obvious particulate matter
Suspend or the transparent system of precipitation；Metal nanoparticle load capacity in hybrid material is adjustable, metal nanoparticle with ionic bond and
The form stable of coordinate bond is effectively connected on the strand of carrier molecule；The method can also allow metal nanoparticle stable point
It is dispersed in matrix material, the size of Effective Regulation metal particle size.Less input for the instrument and equipment that preparation process uses, operation
Process is the most easy to implement, and the raw material environmental friendliness and pollution-free used in course of reaction, impurity in products is few, it is easy to post processing；
Whole course of reaction is conducive to industrial amplification production.
A kind of hybrid material of the water soluble negative metal-loaded nanoparticles of the present invention, described water soluble negative metal-loaded nanoparticles miscellaneous
In formed material, by ionic bond and coordinate bond keyed jointing between carboxyl, amino and metal nanoparticle；Described carboxyl and amino adhere to separately point
Sub-A and the strand of molecule B；
In described molecule A and described molecule B, carboxyl-content, amino content and hydroxy radical content sum are more than or equal to described molecule A
Carboxyl, amino and hydroxyl hydrophilic group with the 160% of the mole sum of described molecule B, in A and B Compound complex
Being to ensure that the water miscible principal element of Compound complex, it is water miscible minimum that 160% this numerical value is to ensure that Compound complex can have
Numerical value；
Described by ionic bond and the carboxyl of coordinate bond keyed jointing with described big by the amino content sum of ionic bond and coordinate bond keyed jointing
Carboxyl and the 30% of amino mole sum in equal to described molecule A and described molecule B；
Relative molecular weight >=10000 of described molecule A, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C
Form with H；
Relative molecular weight≤5000 of described molecule B, in addition to the O of carboxyl or the N of amino, molecular backbone mainly by C and
H forms；
The general structure of the hybrid material of described water soluble negative metal-loaded nanoparticles is:
Or
Wherein, strand repetitive number m >=0, n > 0；
The mechanism that triangle bonding scheme stable in general structure schematic diagram is formed is as follows :-the COO in molecule A and B-With
-NH3 +Because the attraction of positive and negative charge, produce electrostatic attraction, i.e. form ionic bond；-COO-In hydroxyl oxygen on have lone pair electrons,
Therefore the unoccupied orbital of lone pair electrons entrance metal ion is combined with metal ion generation covalent coordinate, forms coordinate bond；-NH3 +In
Atom N there is also lone pair electrons, lone pair electrons can be provided equally to form coordinate bond with metal ion and be combined.Metal ion is surely
It is reduced into atomic state by reducing agent under fixed triangle bonding, in the process, the triangle bonding shape in general structure schematic diagram
Formula still can stable existence.
In the process, the pH value of reaction system is to-COO in system-、-NH3 +And Mx+Being formed of bonding structure is the biggest
Impact.-NH in molecule A or molecule B2< in the case of 7, formation can be combined by the H proton of excess in solution at pH value
-NH3 +；Along with the rising of pH value, to neutrality or alkalescence, H proton free in solution reduces, it is impossible to form-NH again3 +
Structure.For-the COOH in molecule A and molecule B, at strong acid condition pH value, < when 2, the dissociation of-COOH is subject to
To suppression ,-COO in system-Content less, therefore the complexing power of metal ion is weakened significantly；Along with pH value increases,
It is gradually increased with the complexing power of metal ion, when solution ph reaches 5～7 ,-COO-Tend to metal ion combination degree
Maximum；But when the pH value of system improves again ,-NH can be destroyed again3 +Structure, thus destroy make the triangle of stable system tie
Structure relation.Therefore, in order to form the stable stable triangle bonding scheme as shown in schematic diagram, so must be effective
The pH value of adjustment and control system, and ensure that pH value is in the range of 4～6.
R1、R2And R3One in respectively following functional group of functional group: cation group, anionic group or polar nonionic
Group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group
For hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
M is metal nanoparticle, by Mx+Metal ion through reducing agent reduction form, Mx+The value of middle valence state x is 1～3,
For: Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
As preferred technical scheme:
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the molecule B of band amino also comprises hydroxyl or carboxylic
Base；Molecule B with carboxyl also comprises hydroxyl or amino.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, described carboxyl is positioned at molecular backbone or side chain；
Described amino is positioned at molecular backbone or side chain.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the molecular backbone of described molecule A also includes
Element O, N or S common in machine thing.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the molecular backbone of described molecule B also includes
Element O, N or S common in machine thing.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, R in described molecule A and molecule B1、R2
And R3One in respectively following functional group of functional group: cation group, anionic group or polar nonionic group；Described
Cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether
Base, amino, amide groups, sulfydryl or halogen；Preferably: anionic group, carboxylic acid group (-COO-)；Polar nonionic base
Group, hydroxyl (-OH) and amino (-NH2)。
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the load capacity of described metal nanoparticle is
13～850mg/g.
Present invention also offers the preparation method of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles, molecule A material will be contained
Aqueous solution and aqueous solution containing molecule B substance, the pH value of regulation reaction system, to 4～6, then depends in mixed liquor
Secondary dropping metal ion salt solution and reductant solution, stir after dropping, obtain carried metal nano-particle hybrid material
Aqueous solution, continuously stirred and add precipitant, sucking filtration, obtain the precipitate of hygrometric state, after the drying precipitate of hygrometric state, i.e. obtain water
The hybrid material of dissolubility carried metal nano-particle；
Intersect containing carboxyl and amino containing molecule A material and the B substance containing molecule, it may be assumed that during containing molecule A material containing carboxyl, containing dividing
Sub-B substance contains amino；Otherwise, during containing molecule A material containing amino, the B substance containing molecule contains carboxyl.
The preparation method of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, by the water containing molecule A material
Solution and the aqueous solution containing molecule B substance, be under the conditions of 20～60 DEG C；Stirring is accompanied by during mixing；Regulation reaction system
PH value use 0.1～0.3mol/L the H of HCl solution, 0.05～0.15mol/L2SO4Solution or the HNO of 0.1～0.3mol/L3
Solution regulates；Stirring after metal ion salt solution dropping, the persistent period is 0.5～1h；Stir after reductant solution dropping
Mixing, the persistent period is 1～2h；Repeatedly rinse precipitate 2～3 times with precipitant, fully remove the deionized water in precipitate；Wet
The drying precipitate of state uses the mode that vacuum drying oven is dried, and baking temperature is 25～30 DEG C, and vacuum is 0.09～-0.1MPa.
The preparation method of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the described A material containing molecule is
Molecule A carboxylic containing molecule A material or molecule A containing amino containing molecule A material；Described molecule A is carboxylic containing dividing
Sub-A material selected from sodium alginate, potassium alginate, sodium carboxymethyl cellulose, potassium carboxymethylcellulose, sodium hydroxyethlcellulose,
Carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyetbyl chitosan sodium, carboxyetbyl chitosan potassium,
One in 2,3-bis-sodium carboxymethyl cellulose, 2,3-bis-potassium carboxymethylcellulose, sodium polyacrylate and polyacrylic acid potassium；Preferably
For sodium alginate, potassium alginate, sodium carboxymethyl cellulose, potassium carboxymethylcellulose, carboxymethyl chitosan sodium, carboxymethyl chitosan
Sugar potassium, sodium polyacrylate and polyacrylic acid potassium, optimum for sodium carboxymethyl cellulose and potassium carboxymethylcellulose；
The described molecule A A material containing molecule containing amino is chitosan, carboxymethyl chitosan or polyacrylamide；Preferably shell
Polysaccharide；
Described containing molecule B substance be molecule B carboxylic containing molecule B substance or molecule B containing amino containing molecule B substance；
Described molecule B carboxylic containing molecule B substance selected from chain length less than the alkyl chain acid of 6 carbon, specially n-butyric acie, just
Valeric acid or n-caproic acid；
Described molecule B being less than the alkyl chain ammonia of 6 carbon, polyetheramine D230 containing molecule B substance selected from chain length, gathering containing amino
Ether amines D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fat
Fat amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, fat
One in amine polyoxyethylene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；
Preferably polyetheramine D230, aliphatic amine polyoxyethylene ether AC-1810, polyetheramine T403 and aliphatic amine polyoxyethylene ether
One in AC-1205, is most preferably polyetheramine D230；Described chain length is n-propylamine, positive fourth less than the alkyl streptamine of 6 carbon
Amine, n-amylamine or n-hexylamine；
Described metal ion salt solution is AgNO3、FeCl2、HAuCl4、Cr2(SO4)3、PtCl2、PdCl2、CuSO4Or Ni (NO3)2
Aqueous solution；
Described reductant solution is sodium borohydride, potassium borohydride, ascorbic acid, sodium triethylborohydride, hydrazine hydrate or formaldehyde；
Described precipitant is ethanol or acetone, preferably ethanol；Described precipitant and the hybrid material of carried metal nano-particle
The volume ratio of aqueous solution be 2～3:1；The preparation side of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above
When method, the described aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, containing molecule A material and containing molecule B
The mol ratio of material is 1:0.3～1；
The described mass percent concentration containing the aqueous solution of molecule A material is 0.5%～3%；
The mass percent concentration of the described aqueous solution containing molecule B substance is 3%～10%；
The concentration of described metal ion salt solution is 0.005～2g/mL；
Described metal cation salt is 0.1～10:1 with the mol ratio containing molecule A material；
Described metal cation salt is 1:0.5～12 with the mol ratio of reducing agent material；
Described precipitant is 2～4:1 with the volume ratio of the aqueous solution of carried metal nano-particle hybrid material；
The mass percent concentration of the aqueous solution of described carried metal nano-particle hybrid material is 0.5%～10.5%；
The load capacity of described metal nanoparticle is 13～850mg/g.
Beneficial effect:
The invention provides a kind of technique simple, the easy-operating preparation side preparing stable carried metal nano-particle hybrid material
Method, the carried metal nano-particle hybrid material that the method prepares has good water solublity, and metal nanoparticle is at carrier
Load capacity on molecule is adjustable.
The hybrid material of water soluble negative carrying metal ion prepared by the present invention, having good water solublity, i.e. this hybrid material can be steady
Fixed is dispersed in water, and its aqueous solution is not have obvious particulate matter to suspend or the transparent system of precipitation.With without molecule B class
The aqueous solution of material stabilizer is compared, and its aqueous solution has good stability, by the pH value of regulation system, forms metal
Ionic bond and coordinate bond between nano-particle with molecule A and molecule B are bonded, and what metal nanoparticle can be stable is supported on carrier
On molecule A class material, and disperse in aqueous, and without the metal nano in aqueous solution during molecule B class material stabilizer
Granule stability is poor, easily reunites；Carrier molecule A class can be regulated and controled by the amount of the molecule B class material stabilizer that regulation and control are added
The amount of portative metal nanoparticle on material；The hybrid material obtained can be purified to by dehydrated alcohol or acetone
The fibrous solids of dry state, it is simple to storing, the solid matter after purification can be re-dissolved in again in water, be configured to aqueous solution；Should
Material can use after being re-dubbed solution with water, has good antibacterial functional effect such as grade.This course of reaction is adopted and uses water as instead
Answer solvent, nontoxic, environmental protection；Less input for the instrument and equipment that preparation technology itself uses, and operating process is simply prone to
Implementing, experiment condition is gentle, it is simple to realize large-scale industrial production.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art
Can make various changes or modifications the present invention, these equivalent form of values fall within the model that the application appended claims is limited equally
Enclose.
A kind of hybrid material of the water soluble negative metal-loaded nanoparticles of the present invention, the hydridization material of water soluble negative metal-loaded nanoparticles
In material, between carboxyl, amino and metal ion, adhere to molecule A and molecule B separately by ionic bond and coordinate bond keyed jointing, carboxyl and amino
Strand；
In described molecule A and described molecule B, carboxyl-content, amino content and hydroxy radical content sum are more than or equal to described molecule A
With the mole sum of described molecule B 160%；
Described it is more than by ionic bond and the carboxyl of coordinate bond keyed jointing with by the amino content sum of ionic bond and coordinate bond keyed jointing
Carboxyl and the 30% of amino mole sum in described molecule A and described molecule B；
Relative molecular weight >=10000 of described molecule A, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C
Form with H；
Relative molecular weight≤5000 of described molecule B, in addition to the O of carboxyl or the N of amino, molecular backbone mainly by C and
H forms；
The general structure of the hybrid material of water soluble negative metal-loaded nanoparticles is:
Or
Wherein, strand repetitive number m >=0, n > 0；
R1、R2And R3One in respectively following functional group of functional group: cation group, anionic group or polar nonionic
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+For metal ion, the value of valence state x is 1～3, for: Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or
Ni2+。
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the molecule B of band amino also comprises hydroxyl or carboxylic
Base；Molecule B with carboxyl also comprises hydroxyl or amino.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, described carboxyl is positioned at molecular backbone or side chain；
Described amino is positioned at molecular backbone or side chain.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the molecular backbone of described molecule A also includes
Element O, N or S common in machine thing.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the molecular backbone of described molecule B also includes
Element O, N or S common in machine thing.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles as above, the load capacity of described metal nanoparticle is
13～850mg/g.
Embodiment 1
A kind of preparation method of the hybrid material of water solublity loaded Ag nano-particle, under the conditions of 20 DEG C, mass percent is dense
Degree be aqueous solution and the mass percent concentration of the sodium alginate of 0.5% be the aqueous solution of the n-amylamine of 3%, sodium alginate with
The mol ratio of n-amylamine is that the relative molecular weight of 1:0.3, sodium alginate and n-amylamine is respectively 25000 and 87.16, accompanies during mixing
With stirring, with the HCl solution of 0.1mol/L, the pH value of system being adjusted to 4, then dripping concentration in mixed liquor is
The AgNO of 0.005g/mL3Aqueous solution, AgNO3It is 0.1:1 with the mol ratio of sodium alginate, stirs after dropping, when continuing
Between be 0.5h, subsequently dropping borane reducing agent sodium hydride solution, AgNO3It is 1:0.5 with the mol ratio of sodium borohydride, after dropping
The most continuously stirred, the persistent period is 1h, i.e. obtains the aqueous solution of loaded Ag nano-particle hybrid material, and its mass percent is dense
Degree is 0.5%, continuously stirred and add precipitant ethanol, the volume of ethanol and the aqueous solution of loaded Ag nano-particle hybrid material
Ratio is 2:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 2 times, and precipitate is 25 DEG C in temperature, and vacuum is
Under the conditions of 0.09MPa, vacuum drying oven the most i.e. obtains the hybrid material of water solublity loaded Ag nano-particle, in this hybrid material
The load capacity of Ag is 13mg/g.
Embodiment 2
A kind of preparation method of the hybrid material of water solublity load Fe nano-particle, under the conditions of 60 DEG C, mass percent is dense
Degree be aqueous solution and the mass percent concentration of the potassium alginate of 0.6% be the aqueous solution of the n-butylamine of 6%, potassium alginate with
The mol ratio of n-butylamine is that the relative molecular weight of 1:0.7, potassium alginate and n-butylamine is respectively 15000 and 73.14, accompanies during mixing
With stirring, with the HCl solution of 0.15mol/L, the pH value of system being adjusted to 6, then dripping concentration in mixed liquor is 0.2g/mL
FeCl2Aqueous solution, FeCl2Being 2.5:1 with the mol ratio of potassium alginate, stir after dropping, the persistent period is 0.55h,
Dropping reducing agent solution of potassium borohydride, FeCl subsequently2It is 1:1 with the mol ratio of potassium borohydride, the most continuously stirred after dropping,
Persistent period is 2h, i.e. obtains loading the aqueous solution of Fe nano-particle hybrid material, and its mass percent concentration is 1.2%, holds
Continuous stirring also adds precipitant acetone, and precipitant acetone is 4:1 with the volume ratio of the aqueous solution of load Fe nano-particle hybrid material,
Collected by suction precipitate, repeatedly rinses precipitate 3 times with acetone, and precipitate is 30 DEG C in temperature, and vacuum is 0.08MPa bar
Under part, vacuum drying oven the most i.e. obtains the hybrid material of water solublity load Fe nano-particle, the load capacity of Fe in this hybrid material
For 55mg/g.
Embodiment 3
A kind of preparation method of the hybrid material of water solublity load Au nano-particle, under the conditions of 25 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the polyetheramine D400 that mass percent concentration is 4% of the sodium carboxymethyl cellulose of 1%,
Sodium carboxymethyl cellulose is 1:0.5 with the mol ratio of polyetheramine D400, relative with polyetheramine D400 point of sodium carboxymethyl cellulose
Son amount is respectively 19000 and 400, accompanies by stirring, with the HCl solution of 0.2mol/L, the pH value of system is adjusted to 6 during mixing,
Then dripping concentration in mixed liquor is the HAuCl of 0.1g/mL4Aqueous solution, HAuCl4Mol ratio with sodium carboxymethyl cellulose
For 0.5:1, stirring after dropping, the persistent period is 0.6h, subsequently dropping reducing agent ascorbic acid solution, HAuCl4With anti-
The mol ratio of bad hematic acid is 1:2, the most continuously stirred after dropping, and the persistent period is 1.5h, i.e. obtains loading Au nano-particle
The aqueous solution of hybrid material, its mass percent concentration is 1.5%, continuously stirred and add precipitant acetone, precipitant acetone with
The volume ratio of the aqueous solution of load Au nano-particle hybrid material is 3:1, and collected by suction precipitate repeatedly rinses precipitation with acetone
Thing 2 times, precipitate is 26 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load under the conditions of 0.07MPa
The hybrid material of Au nano-particle, in this hybrid material, the load capacity of Au is 60mg/g.
Embodiment 4
A kind of preparation method of the hybrid material of water solublity load Cr nano-particle, under the conditions of 30 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the polyetheramine D2000 that mass percent concentration is 5% of the potassium carboxymethylcellulose of 1%,
Potassium carboxymethylcellulose is 1:0.5 with the mol ratio of polyetheramine D2000, and potassium carboxymethylcellulose is relative with polyetheramine D2000's
Molecular weight is respectively 26000 and 2000, accompanies by stirring during mixing, is adjusted by the pH value of system with the HCl solution of 0.25mol/L
Joint is to 5, and then dripping concentration in mixed liquor is the Cr of 1g/mL2(SO4)3Aqueous solution, Cr2(SO4)3With carboxymethyl cellulose
The mol ratio of potassium is 0.5:1, stirs after dropping, and the persistent period is 0.65h, subsequently dropping reducing agent sodium triethylborohydride
Solution, Cr2(SO4)3Being 1:3 with the mol ratio of sodium triethylborohydride, the most continuously stirred after dropping, the persistent period is 1h,
I.e. obtaining the aqueous solution of load C r nano-particle hybrid material, its mass percent concentration is 2.9%, and continuously stirred and addition is sunk
Shallow lake agent ethanol, precipitant ethanol is 4:1 with the volume ratio of the aqueous solution of the hybrid material of load C r nano-particle, and collected by suction sinks
Shallow lake thing, repeatedly rinses precipitate 2 times with ethanol, and precipitate is 27 DEG C in temperature, and vacuum is vacuum baking under the conditions of 0.06MPa
Case the most i.e. obtains the hybrid material of water solublity load Cr nano-particle, and in this hybrid material, the load capacity of Cr is 850mg/g.
Embodiment 5
The preparation method of the hybrid material of a kind of water solublity supporting Pt nano-particle, under the conditions of 50 DEG C, by mass percent concentration
It is the aqueous solution of the polyetheramine D4000 that aqueous solution and mass percent concentration are 8% of the sodium hydroxyethlcellulose of 1.5%,
Sodium hydroxyethlcellulose is 1:0.8 with the mol ratio of polyetheramine D4000, and sodium hydroxyethlcellulose is relative with polyetheramine D4000's
Molecular weight is respectively 310000 and 4000, accompanies by stirring during mixing, is adjusted by the pH value of system with the HCl solution of 0.3mol/L
Joint is to 4, and then dripping concentration in mixed liquor is the PtCl of 0.5g/mL2Aqueous solution, PtCl2With sodium hydroxyethlcellulose mole
Ratio is 5:1, stirs after dropping, and the persistent period is 0.7h, subsequently dropping reducing agent hydrazine hydrate solution, PtCl2With hydrazine hydrate
Mol ratio be 1:4, the most continuously stirred after dropping, the persistent period is 2h, i.e. obtains supporting Pt nano-particle hybrid material
Aqueous solution, its mass percent concentration is 6.3%, continuously stirred and add precipitant acetone, precipitant acetone and supporting Pt
The volume ratio of the aqueous solution of the hybrid material of nano-particle is 3:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 3 times,
Precipitate is 28 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity supporting Pt nanometer under the conditions of 0.05MPa
The hybrid material of granule, in this hybrid material, the load capacity of Pt is 99mg/g.
Embodiment 6
A kind of preparation method of the hybrid material of water solublity load Pd nano-particle, under the conditions of 60 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the polyetheramine T403 that mass percent concentration is 6% of the carboxyethyl cellulose potassium of 2%,
Carboxyethyl cellulose potassium is 1:0.8 with the mol ratio of polyetheramine T403, carboxyethyl cellulose potassium and the average molecular of polyetheramine T403
Amount is respectively 35200 and 400, accompanies by stirring, with the H of 0.05mol/L during mixing2SO4The pH value of system is adjusted to by solution
6, then dripping concentration in mixed liquor is the PdCl of 0.03g/mL2Aqueous solution, PdCl2Mol ratio with carboxyethyl cellulose potassium
For 8:1, stirring after dropping, the persistent period is 0.75h, subsequently dropping reducing agent formalin, PdCl2With formaldehyde mole
Ratio is 1:5, and the most continuously stirred after dropping, the persistent period is 2h, i.e. obtains the water-soluble of load P d nano-particle hybrid material
Liquid, its mass percent concentration is 2.0%, continuously stirred and add precipitant acetone, precipitant acetone and load P d nanometer
The volume ratio of the aqueous solution of the hybrid material of grain is 2:1, and collected by suction precipitate repeatedly rinses precipitate 3 times with acetone, precipitation
Thing is 30 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load Pd nano-particle under the conditions of 0.04MPa
Hybrid material, in this hybrid material, the load capacity of Pd is 100mg/g.
Embodiment 7
A kind of preparation method of the hybrid material of water solublity loaded Cu nano-particle, under the conditions of 28 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the polyetheramine T3000 that mass percent concentration is 9% of the carboxymethyl chitosan sodium of 1.7%,
Carboxymethyl chitosan sodium is 1:0.7 with the mol ratio of polyetheramine T3000, relative with polyetheramine T3000 point of carboxymethyl chitosan sodium
Son amount is respectively 340000 and 3000, accompanies by stirring, with the H of 0.07mol/L during mixing2SO4The pH value of system is adjusted by solution
Joint is to 6, and then dripping concentration in mixed liquor is the CuSO of 1.6g/mL4Aqueous solution, CuSO4With carboxymethyl chitosan sodium
Mol ratio is 0.5:1, stirs after dropping, and the persistent period is 0.8h, subsequently dropping borane reducing agent sodium hydride solution, CuSO4
Being 1:6 with the mol ratio of sodium borohydride, the most continuously stirred after dropping, the persistent period is 1h, i.e. obtains loaded Cu nanometer
The aqueous solution of grain hybrid material, its mass percent concentration is 5.5%, continuously stirred and add precipitant ethanol, precipitant ethanol
Being 3:1 with the volume ratio of the aqueous solution of loaded Cu nano-particle hybrid material, collected by suction precipitate, it is heavy repeatedly to rinse with ethanol
Shallow lake thing 2 times, precipitate is 30 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water soluble negative under the conditions of 0.03MPa
Carrying the hybrid material of Cu nano-particle, in this hybrid material, the load capacity of Cu is 112mg/g.
Embodiment 8
A kind of preparation method of the hybrid material of water solublity load Ni nano-particle, under the conditions of 40 DEG C, mass percent is dense
Degree is the aqueous solution of the carboxymethyl chitosan potassium of 1.5% and the aliphatic amine polyoxyethylene ether AC-1210 that mass percent concentration is 7%
Aqueous solution, the mol ratio of carboxymethyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1210 is 1:0.6, carboxymethyl chitosan
The relative molecular weight of sugar potassium and aliphatic amine polyoxyethylene ether AC-1210 is respectively 200000 and 1200, accompanies by stirring during mixing,
With the H of 0.1mol/L2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is 0.01g/mL's
Ni(NO3)2Aqueous solution, Ni (NO3)2Being 3:1 with the mol ratio of carboxymethyl chitosan potassium, stir after dropping, the persistent period is
0.85h, subsequently dropping reducing agent solution of potassium borohydride, Ni (NO3)2It is 1:7 with the mol ratio of potassium borohydride, after dropping again
Continuously stirred, the persistent period is 2h, i.e. obtains loading the aqueous solution of Ni nano-particle hybrid material, its mass percent concentration
It is 3.1%, continuously stirred and add precipitant acetone, the aqueous solution of precipitant acetone and the hybrid material of load Ni nano-particle
Volume ratio be 2:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 2 times, precipitate is 26 DEG C in temperature, very
Reciprocal of duty cycle is the hybrid material that vacuum drying oven the most i.e. obtains water solublity load Ni nano-particle under the conditions of 0.02MPa, this hydridization material
In material, the load capacity of Ni is 263mg/g.
Embodiment 9
A kind of preparation method of the hybrid material of water solublity loaded Ag nano-particle, under the conditions of 50 DEG C, mass percent is dense
Degree is the aqueous solution of the carboxyetbyl chitosan sodium of 0.5% and the aliphatic amine polyoxyethylene ether AC-1810 that mass percent concentration is 5%
Aqueous solution, the mol ratio of carboxyetbyl chitosan sodium and aliphatic amine polyoxyethylene ether AC-1810 is 1:0.8, and carboxyethyl shell gathers
The relative molecular weight of sugar sodium and aliphatic amine polyoxyethylene ether AC-1810 is respectively 21000 and 1800, accompanies by stirring during mixing, uses
The H of 0.12mol/L2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is 0.05g/mL's
AgNO3Aqueous solution, AgNO3Being 0.8:1 with the mol ratio of carboxyetbyl chitosan sodium, stir after dropping, the persistent period is
0.9h, subsequently dropping reducing agent ascorbic acid solution, AgNO3It is 1:8 with the mol ratio of ascorbic acid, continues again after dropping
Stirring, the persistent period is 1h, i.e. obtains the aqueous solution of loaded Ag nano-particle hybrid material, and its mass percent concentration is 2.2%,
Continuously stirred and add precipitant ethanol, the volume ratio of precipitant ethanol and the aqueous solution of the hybrid material of loaded Ag nano-particle
For 2:1, collected by suction precipitate, repeatedly rinsing precipitate with ethanol 3 times, precipitate is 29 DEG C in temperature, and vacuum is 0.01MPa
Under the conditions of vacuum drying oven the most i.e. obtain the hybrid material of water solublity loaded Ag nano-particle, the load of Ag in this hybrid material
Amount is 384mg/g.
Embodiment 10
A kind of preparation method of the hybrid material of water solublity load Fe nano-particle, under the conditions of 20 DEG C, mass percent is dense
Degree is the aqueous solution of the carboxyetbyl chitosan potassium of 2.5% and the aliphatic amine polyoxyethylene ether AC-1812 that mass percent concentration is 5%
Aqueous solution, the mol ratio of carboxyetbyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1812 is 1:0.6, and carboxyethyl shell gathers
The relative molecular weight of sugar potassium and aliphatic amine polyoxyethylene ether AC-1812 is respectively 165000 and 1900, accompanies by stirring during mixing,
With the H of 0.15mol/L2SO4The pH value of system is adjusted to 4 by solution, and then dripping concentration in mixed liquor is 0.16g/mL
FeCl2Aqueous solution, FeCl2Being 0.6:1 with the mol ratio of carboxyetbyl chitosan potassium, stir after dropping, the persistent period is
0.55h, subsequently dropping reducing agent sodium triethylborohydride solution, FeCl2It is 1:9 with the mol ratio of sodium triethylborohydride, dropping
After the most continuously stirred, the persistent period is 1.5h, i.e. obtain load Fe nano-particle hybrid material aqueous solution, its quality hundred
Proportion by subtraction concentration is 4.2%, continuously stirred and add precipitant acetone, precipitant acetone and load Fe nano-particle hybrid material
The volume ratio of aqueous solution is 2:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 2 times, and precipitate is 30 DEG C in temperature,
Vacuum is the hybrid material that vacuum drying oven the most i.e. obtains water solublity load Fe nano-particle under the conditions of 0.09MPa, this hydridization
In material, the load capacity of Fe is 419mg/g.
Embodiment 11
A kind of preparation method of the hybrid material of water solublity load Au nano-particle, under the conditions of 40 DEG C, mass percent is dense
Degree be aqueous solution and the mass percent concentration of 2,3-bis-sodium carboxymethyl cellulose of 2.8% be the aliphatic amine polyoxyethylene ether of 6%
The aqueous solution of AC-1815,2,3-bis-sodium carboxymethyl cellulose with the mol ratio of aliphatic amine polyoxyethylene ether AC-1815 are
1:0.8, the relative molecular weight of 2,3-bis-sodium carboxymethyl cellulose and aliphatic amine polyoxyethylene ether AC-1815 is respectively 40000 and 900,
Stirring is accompanied by, with the HNO of 0.1mol/L during mixing3The pH value of system is adjusted to 6 by solution, then drips dense in mixed liquor
Degree is the HAuCl of 0.18g/mL4Aqueous solution, HAuCl4With 2, the mol ratio of 3-bis-sodium carboxymethyl cellulose is 3:1, drips
Stirring after Biing, the persistent period is 0.5h, subsequently dropping reducing agent hydrazine hydrate solution, HAuCl4It is 1:10 with the mol ratio of hydrazine hydrate,
After dropping the most continuously stirred, the persistent period is 2h, i.e. obtain load Au nano-particle hybrid material aqueous solution, its matter
Amount percent concentration is 3%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Au nano-particle hybrid material
The volume ratio of aqueous solution be 4:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate in temperature is
26 DEG C, vacuum is the hybrid material that vacuum drying oven the most i.e. obtains water solublity load Au nano-particle under the conditions of-0.1MPa,
In this hybrid material, the load capacity of Au is 523mg/g.
Embodiment 12
A kind of preparation method of the hybrid material of water solublity load Cr nano-particle, under the conditions of 30 DEG C, mass percent is dense
Degree be aqueous solution and the mass percent concentration of 2,3-bis-potassium carboxymethylcellulose of 0.9% be the aliphatic amine polyoxyethylene ether of 8%
The aqueous solution of AC-1205,2,3-bis-potassium carboxymethylcelluloses are 1:1 with the mol ratio of aliphatic amine polyoxyethylene ether AC-1205,
The relative molecular weight of 2,3-bis-potassium carboxymethylcelluloses and aliphatic amine polyoxyethylene ether AC-1205 is respectively 250000 and 1200, mixed
Stirring is accompanied by, with the HNO of 0.15mol/L during conjunction3The pH value of system is adjusted to 5 by solution, then drips dense in mixed liquor
Degree is the Cr of 0.006g/mL2(SO4)3Aqueous solution, Cr2(SO4)3With 2, the mol ratio of 3-bis-potassium carboxymethylcellulose is 0.6:1, drips
Stirring after adding, the persistent period is 1h, subsequently dropping reducing agent formalin, Cr2(SO4)3It is 1:11 with the mol ratio of formaldehyde,
After dropping the most continuously stirred, the persistent period is 1h, i.e. obtains the aqueous solution of load C r nano-particle hybrid material, its matter
Amount percent concentration is 2.8%, continuously stirred and add precipitant ethanol, the hydridization of precipitant ethanol and load C r nano-particle
The volume ratio of the aqueous solution of material is 2:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 3 times, and precipitate is in temperature
Being 25 DEG C, vacuum is the hydridization material that vacuum drying oven the most i.e. obtains water solublity load Cr nano-particle under the conditions of-0.09MPa
Material, in this hybrid material, the load capacity of Cr is 589mg/g.
Embodiment 13
The preparation method of the hybrid material of a kind of water solublity supporting Pt nano-particle, under the conditions of 60 DEG C, by mass percent concentration
It is the aqueous solution of the polyetheramine T5000 that aqueous solution and mass percent concentration are 10% of the carboxymethyl chitosan sodium of 3%,
Carboxymethyl chitosan sodium is 1:1 with the mol ratio of polyetheramine T5000, relative with polyetheramine T5000 point of carboxymethyl chitosan sodium
Son amount is respectively 340000 and 5000, accompanies by stirring, with the HNO of 0.2mol/L during mixing3The pH value of system is regulated by solution
To 4, then dripping concentration in mixed liquor is the PtCl of 2g/mL2Aqueous solution, PtCl2Mol ratio with carboxymethyl chitosan sodium
For 10:1, stirring after dropping, the persistent period is 0.6h, subsequently dropping borane reducing agent sodium hydride solution, PtCl2With hydroboration
The mol ratio of sodium is 1:12, the most continuously stirred after dropping, and the persistent period is 2h, i.e. obtains supporting Pt nano-particle hydridization material
The aqueous solution of material, its mass percent concentration is 8.3%, continuously stirred and add precipitant ethanol, precipitant ethanol and supporting Pt
The volume ratio of the aqueous solution of the hybrid material of nano-particle is 2:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 3 times,
Precipitate is 30 DEG C in temperature, and vacuum the most i.e. obtains water solublity supporting Pt nanometer for vacuum drying oven under the conditions of-0.08MPa
The hybrid material of granule, in this hybrid material, the load capacity of Pt is 612mg/g.
Embodiment 14
A kind of preparation method of the hybrid material of water solublity load Pd nano-particle, under the conditions of 40 DEG C, mass percent is dense
Degree is the aqueous solution water with the aliphatic amine polyoxyethylene ether AC-1215 that mass percent concentration is 3% of the polyacrylic acid potassium of 1.2%
Solution mixes, and polyacrylic acid potassium is 1:0.5, polyacrylic acid potassium and fatty amine with the mol ratio of aliphatic amine polyoxyethylene ether AC-1215
The relative molecular weight of polyoxyethylene ether AC-1215 is respectively 20000 and 800, accompanies by stirring during mixing, with 0.25mol/L's
HNO3The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is the PdCl of 0.12g/mL2Aqueous solution,
PdCl2Being 2:1 with the mol ratio of polyacrylic acid potassium, stir after dropping, the persistent period is 0.65h, drips borane reducing agent subsequently
Hydrofining solution, PdCl2Being 1:2.5 with the mol ratio of potassium borohydride, the most continuously stirred after dropping, the persistent period is 1h,
I.e. obtaining the aqueous solution of load P d nano-particle hybrid material, its mass percent concentration is 2.9%, and continuously stirred and addition is sunk
Shallow lake agent acetone, precipitant acetone is 2:1 with the volume ratio of the aqueous solution of load P d nano-particle hybrid material, and collected by suction precipitates
Thing, repeatedly rinses precipitate 2 times with acetone, and precipitate is 26 DEG C in temperature, and vacuum is vacuum drying oven under the conditions of-0.1MPa
The dried hybrid material i.e. obtaining water solublity load Pd nano-particle, in this hybrid material, the load capacity of Pd is 648mg/g.
Embodiment 15
A kind of preparation method of the hybrid material of water solublity loaded Cu nano-particle, under the conditions of 30 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the n-butyric acie that mass percent concentration is 7% of the chitosan of 1.6%, chitosan and positive fourth
The relative molecular weight that mol ratio is 1:0.9, chitosan and n-butyric acie of acid is respectively 240000 and 88.1, accompanies by stirring during mixing,
With the HNO of 0.3mol/L3The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is 0.8g/mL's
CuSO4Aqueous solution, CuSO4Being 6:1 with the mol ratio of chitosan, stir after dropping, the persistent period is 0.7h, drips subsequently
Add reducing agent ascorbic acid solution, CuSO4It is 1:3.5 with the mol ratio of ascorbic acid, the most continuously stirred after dropping, continue
Time is 1h, i.e. obtains the aqueous solution of loaded Cu nano-particle hybrid material, and its mass percent concentration is 10.5%, continues
Stirring and add precipitant ethanol, precipitant ethanol is 3:1 with the volume ratio of the aqueous solution of loaded Cu nano-particle hybrid material,
Collected by suction precipitate, repeatedly rinses precipitate 3 times with ethanol, and precipitate is 28 DEG C in temperature, and vacuum is 0.09MPa bar
Under part, vacuum drying oven the most i.e. obtains the hybrid material of water solublity loaded Cu nano-particle, the load capacity of Cu in this hybrid material
For 13mg/g.
Embodiment 16
A kind of preparation method of the hybrid material of water solublity load Ni nano-particle, under the conditions of 20 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the positive valeric acid that mass percent concentration is 6% of the carboxymethyl chitosan of 2.4%, carboxymethyl
Chitosan is 1:0.4 with the mol ratio of positive valeric acid, and the relative molecular weight of carboxymethyl chitosan and positive valeric acid is respectively 10000 Hes
102.13, accompany by stirring during mixing, with the HCl solution of 0.1mol/L, the pH value of system is adjusted to 6, then in mixed liquor
Dropping concentration is the Ni (NO of 0.06g/mL3)2Aqueous solution, Ni (NO3)2It is 0.8:1 with the mol ratio of carboxymethyl chitosan, dropping
After stir, the persistent period is 0.75h, subsequently dropping borane reducing agent sodium hydride solution, Ni (NO3)2With sodium borohydride mole
Ratio is 1:4.5, and the most continuously stirred after dropping, the persistent period is 2h, i.e. obtains loading the water of Ni nano-particle hybrid material
Solution, its mass percent concentration is 2.5%, continuously stirred and add precipitant acetone, precipitant acetone and load Ni nanometer
The volume ratio of the aqueous solution of granule hybrid material is 3:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 2 times, precipitation
Thing is 29 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load Ni nano-particle under the conditions of-0.1MPa
Hybrid material, in this hybrid material, the load capacity of Ni is 419mg/g.
Embodiment 17
A kind of preparation method of the hybrid material of water solublity loaded Ag nano-particle, under the conditions of 25 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the n-caproic acid that mass percent concentration is 5% of the polyacrylamide of 0.8%, polyacrylamide
Amine is respectively 1 × 10 with the relative molecular weight that mol ratio is 1:0.7, polyacrylamide and n-caproic acid of n-caproic acid6With 115.15, mixed
Accompany by stirring during conjunction, with the HCl solution of 0.3mol/L, the pH value of system is adjusted to 4, in mixed liquor, then drip concentration
AgNO for 0.08g/mL3Aqueous solution, AgNO3It is 3.5:1 with the mol ratio of polyacrylamide, stirs after dropping, hold
The continuous time is 0.8h, subsequently dropping reducing agent sodium triethylborohydride solution, AgNO3With the mol ratio of sodium triethylborohydride it is
1:5.5, the most continuously stirred after dropping, the persistent period is 2h, i.e. obtains the aqueous solution of loaded Ag nano-particle hybrid material,
Its mass percent concentration is 0.5%, continuously stirred and add precipitant acetone, and precipitant acetone is miscellaneous with loaded Ag nano-particle
The volume ratio of the aqueous solution of formed material is 3:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 3 times, and precipitate is in temperature
Degree is 29 DEG C, and vacuum is the hydridization that vacuum drying oven the most i.e. obtains water solublity loaded Ag nano-particle under the conditions of 0.09MPa
Material, in this hybrid material, the load capacity of Ag is 763mg/g.
Embodiment 18
A kind of preparation method of the hybrid material of water solublity load Fe nano-particle, under the conditions of 50 DEG C, mass percent is dense
Degree be aqueous solution and the mass percent concentration of the sodium alginate of 2.6% be the aqueous solution of the n-hexylamine of 5%, sodium alginate with
The mol ratio of n-hexylamine is that the relative molecular weight of 1:0.5, sodium alginate and n-hexylamine is respectively 25000 and 101.19, accompanies during mixing
With stirring, with the H of 0.05mol/L2SO4The pH value of system is adjusted to 6 by solution, then drips concentration in mixed liquor and is
The FeCl of 0.5g/mL2Aqueous solution, FeCl2Being 5:1 with the mol ratio containing sodium alginate, stir after dropping, the persistent period is
0.85h, subsequently dropping reducing agent hydrazine hydrate solution, FeCl2It is 1:6.5 with the mol ratio of hydrazine hydrate, the most persistently stirs after dropping
Mixing, the persistent period is 1h, i.e. obtains loading the aqueous solution of Fe nano-particle hybrid material, and its mass percent concentration is 7.3%,
Continuously stirred and add precipitant ethanol, precipitant ethanol with the volume ratio of the aqueous solution of load Fe nano-particle hybrid material is
2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate is 27 DEG C in temperature, and vacuum is 0.09MPa
Under the conditions of vacuum drying oven the most i.e. obtain water solublity load Fe nano-particle hybrid material, the load of Fe in this hybrid material
Amount is 692mg/g.
Embodiment 19
A kind of preparation method of the hybrid material of water solublity load Au nano-particle, under the conditions of 60 DEG C, mass percent is dense
Degree be aqueous solution and the mass percent concentration of the potassium alginate of 1.4% be the aqueous solution of the n-propylamine of 3%, potassium alginate with
The mol ratio of n-propylamine is that the relative molecular weight of 1:0.3, potassium alginate and n-propylamine is respectively 15000 and 59.11, accompanies during mixing
With stirring, with the H of 0.15mol/L2SO4The pH value of system is adjusted to 5 by solution, then drips concentration in mixed liquor and is
The HAuCl of 0.15g/mL4Aqueous solution, HAuCl4Aqueous solution is 0.6:1 with the mol ratio of potassium alginate, stirs after dropping,
Persistent period is 0.9h, subsequently dropping reducing agent formalin, HAuCl4It is 1:7.5 with the mol ratio of formaldehyde, after dropping
The most continuously stirred, the persistent period is 1h, i.e. obtains loading the aqueous solution of Au nano-particle hybrid material, and its mass percent is dense
Degree is 2.1%, continuously stirred and add precipitant ethanol, and precipitant ethanol is water-soluble with the hybrid material of load Au nano-particle
The volume ratio of liquid is 2:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 3 times, and precipitate is 26 DEG C in temperature,
Vacuum is the hybrid material that vacuum drying oven the most i.e. obtains water solublity load Au nano-particle under the conditions of-0.1MPa, this hydridization
In material, the load capacity of Au is 782mg/g.
Embodiment 20
A kind of preparation method of the hybrid material of water solublity load Cr nano-particle, under the conditions of 20 DEG C, mass percent is dense
Degree is the aqueous solution aqueous solution with the polyetheramine D230 that mass percent concentration is 4% of the sodium polyacrylate of 2.9%, poly-third
Olefin(e) acid sodium is 1:0.6 with the mol ratio of polyetheramine D230, and the relative molecular weight of sodium polyacrylate and polyetheramine D230 is respectively
30000 and 230, accompany by stirring during mixing, with the HNO of 0.3mol/L3The pH value of system is adjusted to 6 by solution, then to
Dripping concentration in mixed liquor is the Cr of 0.5g/mL2(SO4)3Aqueous solution, Cr2(SO4)3It is 3:1 with the mol ratio of sodium polyacrylate,
Stirring after dropping, the persistent period is 1h, subsequently dropping reducing agent solution of potassium borohydride, Cr2(SO4)3With rubbing of potassium borohydride
That ratio is 1:8.5, and the most continuously stirred after dropping, the persistent period is 2h, i.e. obtains load C r nano-particle hybrid material
Aqueous solution, its mass percent concentration is 10.5%, continuously stirred and add precipitant ethanol, and precipitant ethanol is received with load C r
The volume ratio of the aqueous solution of rice grain hybrid material is 4:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 3 times, heavy
Shallow lake thing is 25 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Cr nano-particle for vacuum drying oven under the conditions of-0.1MPa
Hybrid material, in this hybrid material, the load capacity of Cr is 850mg/g.
Claims (10)
1. a hybrid material for water soluble negative metal-loaded nanoparticles, is characterized in that: described water soluble negative metal-loaded nanoparticles
In hybrid material, by ionic bond and coordinate bond keyed jointing between carboxyl, amino and metal ion；Described carboxyl and amino adhere to separately point
Sub-A and the strand of molecule B；
In described molecule A and described molecule B, carboxyl-content, amino content and hydroxy radical content sum are more than or equal to described point
The 160% of the mole sum of sub-A and described molecule B；
Described by ionic bond and the carboxyl of coordinate bond keyed jointing and the described amino content by ionic bond and coordinate bond keyed jointing it
With more than or equal to carboxyl and the 30% of amino mole sum in described molecule A and described molecule B；
Relative molecular weight >=10000 of described molecule A, in addition to the O of carboxyl or the N of amino, molecular backbone mainly by
C and H forms；
Relative molecular weight≤5000 of described molecule B, in addition to the O of carboxyl or the N of amino, molecular backbone is mainly by C
Form with H；
The general structure of the hybrid material of described water soluble negative metal-loaded nanoparticles is:
Or
Wherein, strand repetitive number m >=0, n > 0；
R1、R2And R3Functional group is respectively the one in following functional group: cation group, anionic group or polarity are non-
Ionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polarity non-from
Subbase group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
M is metal nanoparticle, by Mx+Metal ion through reducing agent reduction form, Mx+The value of middle valence state x is 1～3,
For: Ag+、Fe2+、Au3+、Cr3+、Pt2+、Pd2+、Cu2+Or Ni2+。
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 1, it is characterised in that band amino
Molecule B also comprises hydroxyl or carboxyl；Molecule B with carboxyl also comprises hydroxyl or amino.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 1, it is characterised in that described carboxyl
It is positioned at molecular backbone or side chain；Described amino is positioned at molecular backbone or side chain.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 1, it is characterised in that described molecule
The molecular backbone of A also includes element O, N or S.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 1, it is characterised in that described molecule
The molecular backbone of B also includes element O, N or S.
The hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 1, it is characterised in that described metal
The load capacity of nano-particle is 13～850mg/g.
7. the preparation method of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles as according to any one of claim 1～6, its
Feature is: by the aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, the pH value of regulation reaction system
To 4～6, in mixed liquor, then drip metal ion salt solution, stir after dropping, drip reductant solution subsequently,
After dropping the most continuously stirred, i.e. obtain the aqueous solution of carried metal nano-particle hybrid material, continuously stirred and add heavy
Shallow lake agent, is collected by filtration precipitate, i.e. obtains the hybrid material of water soluble negative metal-loaded nanoparticles after drying precipitate；
Intersect containing carboxyl and amino containing molecule A material and the B substance containing molecule, it may be assumed that during containing molecule A material containing carboxyl,
The B substance containing molecule contains amino；Otherwise, during containing molecule A material containing amino, the B substance containing molecule contains carboxyl.
The preparation method of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 7, its feature exists
In, by the aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, it is under the conditions of 20～60 DEG C；Mixed
Stirring is accompanied by during conjunction；The pH value of regulation reaction system uses HCl solution, 0.05～the 0.15mol/L's of 0.1～0.3mol/L
H2SO4Solution or the HNO of 0.1～0.3mol/L3Solution regulates；Stir after metal ion salt solution dropping, when continuing
Between be 0.5～1h；Stirring after reductant solution dropping, the persistent period is 1～2h；Drying precipitate uses vacuum drying oven
It is dried.
The preparation method of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 7, it is characterised in that
The described A material containing molecule be molecule A carboxylic containing molecule A material or molecule A containing amino containing molecule A material；Institute
State molecule A carboxylic fine selected from sodium alginate, potassium alginate, sodium carboxymethyl cellulose, carboxymethyl containing molecule A material
Dimension element potassium, sodium hydroxyethlcellulose, carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyethyl
Chitosan sodium, carboxyetbyl chitosan potassium, 2,3-bis-sodium carboxymethyl cellulose, 2,3-bis-potassium carboxymethylcellulose, sodium polyacrylate
With the one in polyacrylic acid potassium；
The described molecule A A material containing molecule containing amino is chitosan, carboxymethyl chitosan or polyacrylamide；
Described containing molecule B substance be molecule B carboxylic containing molecule B substance or molecule B containing amino containing molecule B substance；
Described molecule B carboxylic containing molecule B substance selected from chain length less than 6 carbon alkyl chain acid, specially n-butyric acie,
Positive valeric acid or n-caproic acid；
Described molecule B containing amino containing molecule B substance selected from chain length less than the alkyl chain ammonia of 6 carbon, polyetheramine D230,
Polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000,
Aliphatic amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815,
Aliphatic amine polyoxyethylene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215
In one；Described chain length is n-propylamine, n-butylamine, n-amylamine or n-hexylamine less than the alkyl streptamine of 6 carbon；
Described metal ion salt solution is AgNO3、FeCl2、HAuCl4、Cr2(SO4)3、PtCl2、PdCl2、CuSO4
Or Ni (NO3)2Aqueous solution；
Described reductant solution is sodium borohydride, potassium borohydride, ascorbic acid, sodium triethylborohydride, hydrazine hydrate or formaldehyde；
Described precipitant is ethanol or acetone.
The preparation method of the hybrid material of a kind of water soluble negative metal-loaded nanoparticles the most according to claim 7, its feature exists
In, when the described aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, divide with containing containing molecule A material
The mol ratio of sub-B substance is 1:0.3～1；
The described mass percent concentration containing the aqueous solution of molecule A material is 0.5%～3%；
The mass percent concentration of the described aqueous solution containing molecule B substance is 3%～10%；
The concentration of described metal ion salt solution is 0.005～2g/mL；
Described metal cation salt is 0.1～10:1 with the mol ratio containing molecule A material；
Described metal cation salt is 1:0.5～12 with the mol ratio of reducing agent material；
The mass percent concentration of the aqueous solution of described carried metal nano-particle hybrid material is 0.5%～10.5%；
Described precipitant is 2～4:1 with the volume ratio of the aqueous solution of carried metal nano-particle hybrid material；
The temperature of described drying precipitate is 25～30 DEG C, and vacuum is 0.09～-0.1MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107099164A (en) * | 2017-03-24 | 2017-08-29 | 深圳大学 | A kind of nano metal particles resin composite materials and preparation method thereof |
| CN109735062A (en) * | 2018-12-13 | 2019-05-10 | 上海东华镜月资产经营有限公司 | Master batch and preparation method thereof containing cross hybridization porous material |
| CN109908869A (en) * | 2017-12-13 | 2019-06-21 | 宁波市河清源技术转移服务有限公司 | A kind of preparation method of water softening nano adsorption material |
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| WO2023024661A1 (en) * | 2022-04-20 | 2023-03-02 | 山东海科创新研究院有限公司 | Antibacterial agent, and antibacterial polysulfone composite material and preparation method therefor |
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| 花蓓蓓: ""有机/无机杂化可溶型纳米银及其功能材料的构筑与应用开拓"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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| CN107099164A (en) * | 2017-03-24 | 2017-08-29 | 深圳大学 | A kind of nano metal particles resin composite materials and preparation method thereof |
| CN109908869A (en) * | 2017-12-13 | 2019-06-21 | 宁波市河清源技术转移服务有限公司 | A kind of preparation method of water softening nano adsorption material |
| CN109735062A (en) * | 2018-12-13 | 2019-05-10 | 上海东华镜月资产经营有限公司 | Master batch and preparation method thereof containing cross hybridization porous material |
| CN109735062B (en) * | 2018-12-13 | 2021-01-01 | 上海东华镜月资产经营有限公司 | Master batch containing cross hybrid porous material and preparation method thereof |
| CN114397448A (en) * | 2021-04-01 | 2022-04-26 | 苏州育德扬生物技术有限公司 | Preparation of sugar functionalized nanoparticles and application of sugar functionalized nanoparticles in influenza virus detection |
| CN114397448B (en) * | 2021-04-01 | 2024-01-19 | 苏州育德扬生物技术有限公司 | Preparation of sugar functionalized nano particles and application of sugar functionalized nano particles in influenza virus detection |
| WO2023024661A1 (en) * | 2022-04-20 | 2023-03-02 | 山东海科创新研究院有限公司 | Antibacterial agent, and antibacterial polysulfone composite material and preparation method therefor |
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