CN102493265A - Method for preparing metal nano particle and cellulose fiber composite material - Google Patents
Method for preparing metal nano particle and cellulose fiber composite material Download PDFInfo
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Abstract
The invention discloses a method for preparing a metal nano particle and cellulose fiber composite material. The method comprises the following steps of: performing dissociation on pulp, and dispersing in deionized water by a fiber dissociator to prepare fiber slurry; adding a solvent into the fiber slurry, stirring and heating to 40 to 100 DEG C, dripping a metal salt solution, and reacting for 1 to 3 hours after dripping; and aging and filtering after reaction, and eluting and drying to obtain the metal nano particle and cellulose fiber composite material. By adopting the method, the in-situ synthesis of the metal nano particle and cellulose fiber composite material is realized, a process for preparing the metal nano particle and cellulose fiber composite material is greatly simplified, the defects that the nano particles are not distributed uniformly on the fiber because nano particles are not easy to disperse, and nano particles fall off from the cellulose fibers easily by adopting a physical mixing mode in the conventional method are overcome, and the problem about environment pollution which is caused by the conventional preparation method is greatly solved.
Description
Technical field
The present invention is specifically related to the preparation method of a kind of metal nanoparticle and cellulose fibre composite, and affiliated technical field is the crossing domain of subjects such as material, chemistry.
Background technology
In recent years; Metal nanoparticle is widely used in biological owing to its excellent performance and numerous areas such as electrochemical sensor, catalyst, biomarker, magnetic material, information storage and surperficial enhancement effect, and the research of its preparation, performance characterization and application facet has received the great attention and the concern of scientific and technological circle.Yet metal nanoparticle is the same with other nano particle, although its specific area is big, active high, is prone to reunite, and is difficult to disperse, and has seriously restricted the practical application of metal nanoparticle.
Nano composition is a kind of new material that occurs along with the development of nanoscale science and technology.It is compound through nano particle and other material, not only significantly improves mechanics, electricity or the chemical property of material, and can effectively solve the problem that nano particle is difficult to disperse.Fibrous material has flexibility and good processing properties; Therefore; The nano particle fibrous composite is the emphasis of field of nanocomposite materials development, and wherein the metal nano fibrous composite receives the favor of researcher more because it has broad application prospects in every field.Cellulose fibre is a abundantest available renewable fibre resources on the earth, and environmental protection can adopt various pulping process separation and Extraction from each plant fiber raw material to obtain.Nano particle cellulose fibre composite can be processed into different shapes such as paper, is convenient to its practical application.Therefore, development metal nanoparticle and cellulose fibre composite are the research focus and emphasis of present field of nanocomposite materials.
High glycan such as cellulose, starch contains more hydroxyl, can pass through the coordination bind metal ion, further forms metal ion group bunch, thereby can reach purpose stable and the dispersing nanometer particle.Patent CN1730540A disclose a kind of on cellulose, starch, shitosan and molecule such as glycan such as height such as powdered cellulose grade the method for in-situ compounding simple-substance metal nanoparticle; Patent CN101869989A discloses a kind of stabilizing agent and the dispersant of nano-cellulose as nano particle, prepares the method for elemental metals nano particle.These two kinds of methods all are to be raw material with high glycan macromolecule or nano-cellulose, add reductant reducing metal ion, utilize the coordination in-situ preparing of hydroxyl to go out the metal simple-substance nano particle.Adopt pulping process resulting cellulose fibre from plant fiber material; Although also contain great amount of hydroxy group from molecular structure; But because its macro-size ratio nano cellulose is much bigger; Usually also contain a small amount of lignin, and the hydrogen bond content between the cellulose macromolecule is higher in the cellulose fibre, the surface demonstrates higher inertia; Therefore the lip-deep activity hydroxy content of unit mass raw material is more much lower than size nano-cellulose, compares just lower than the high glycan with unformed macromolecular structure.The difficulty that this has increased the synthetic metal nanoparticle of original position on cellulose fibre greatly adopts existing in-situ synthetic method to be difficult to prepare metal nanoparticle and cellulose fibre composite.Therefore, the main method that in the past prepared metal nanoparticle and cellulose fibre composite is a two-step method, promptly at first prepares metal nanoparticle, under certain process conditions, mixes with cellulose fibre metal nanoparticle then, obtains after the drying.This preparation method exists usually, owing to nano particle is difficult for nano particle skewness on fiber that dispersion causes, and owing to the nano particle that adopts physical admixture to cause is prone to from shortcomings such as cellulose fibre come off.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of metal nanoparticle and cellulose fibre composite; Prepared in metal nanoparticle and the cellulose fibre composite material to solve in the past; Technical problems such as metal nanoparticle is prone to reunite, is prone to from composite, come off realize metal nanoparticle and cellulose fibre greenization production.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following:
The preparation method of a kind of metal nanoparticle and cellulose fibre composite, this method comprises the steps:
(1) adopts the fiber device that dissociates, in deionized water, dissociate paper pulp and disperse the preparation fiber slurry;
(2) slaine is dissolved in the solvent, is mixed with metal salt solution;
(3) in the fiber slurry that step (1) obtains, behind the adding solvent, be stirred and heated to 40-100 ℃, keep constant temperature, drip the metal salt solution of step (2) preparation then, reacted again after dropwising 1-3 hour;
(4) after reaction finishes, carry out ageing processing and filter operation, obtain the cellulose fibre that load has metal nanoparticle;
(5) load that obtains of elution step (4) has the cellulose fibre of metal nanoparticle, obtains metal nanoparticle and fibrous composite after the drying.
Wherein,
Described metal nanoparticle is metal simple-substance nano particle or metal oxide nanoparticles.
In the step (1), described sources of paper pulp is in broadleaf wood pulp, softwood wood pulp or bamboo wood slurry.
In the step (1), described pulp quality percentage concentration is 1-5%, i.e. the paper pulp 1-5% of ionized water and paper pulp gross weight that accounts for.
In the step (2), described slaine is molysite, silver salt or mantoquita, and the form of said slaine is nitrate, hydrochloride or metal complex.
In step (2) and (3), described solvent is deionized water or absolute ethyl alcohol or is (10-90) by deionized water and absolute ethyl alcohol according to volume ratio: (90-10) mixture of preparation; The preferred volume ratio of deionized water and absolute ethyl alcohol is (50-80): (50-20).
In the step (2), described metal salt solution concentration is 1-50mmol/L, preferred 5-20mmol/L.
In the step (3), the volume ratio of fiber slurry and solvent is 1: (2-5), and preferred 1: (3-4).
In the step (3), the volume ratio of fiber slurry and metal salt solution is (1-5): 1, preferred (1-2): 1.
Ageing described in the step (4), its temperature are 40-60 ℃; Digestion time is 24-48 hour, preferred 24-30 hour.
In the step (5), described wash-out, its solvent are ethanol.
In the step (5), described drying condition is: pressure is normal pressure or decompression, and temperature is 40-180 ℃.
The inventive method, when slaine was selected molysite for use, metal nanoparticle that finally obtains and cellulose fibre composite were ferric oxide nano particles and cellulose fibre composite; When slaine was selected silver salt or mantoquita for use, metal nanoparticle that finally obtains and cellulose fibre composite were silver-colored simple substance or copper simple substance nano particle and cellulose fibre composite.
Reaction mechanism of the present invention is following: cellulose fibre mainly is made up of cellulose macromolecule.Cellulose macromolecule is to pass through 1 by β-glucose, and 4-β glycosidic bond connects formed straight chain polymer (like the cellulosic structure of Fig. 1).As shown in Figure 1, contain 3 hydroxyls (OH) that polarity is stronger on each cellulose glucose basic ring: two secondary hydroxyl group (C
2-OH and C
3-OH) with a primary hydroxyl group (C
6-OH), their hydrogen atom can attract each other with the lone pair electrons on the very big oxygen atom of electronegativity on another key and form hydrogen bond (OH ... O).Therefore, between the cellulose macromolecule, cellulose macromolecule inside can form hydrogen bond between intramolecular hydrogen bond and the molecule, give cellulosic self assembly property, crystallinity and can form the multiple architectural characteristics such as heterogeneous structure of fibril.In the mechanism of cellulose and metal salt solution; The oxygen atom at electron rich center and short of electricity interest belong to ion and carry out coordination and combine in the cellulosic hydroxyl, and be as shown in Figure 1, and as the center; Form metal ion group bunch, finally on cellulose fibre, form metal nanoparticle.
Yet, owing to the existence of a large amount of hydrogen bonds, significantly reduced the activity of hydroxyl on the cellulose fibre surface, although can increase the ratio that has the greater activity hydroxyl on the cellulose fibre surface through the method for making beating, its effect is obviously very limited.Therefore; The key of synthesis of nano metallic is to improve the coordination ability of cellulose fibre surface hydroxyl and metal ion on cellulose fibre; The metal nanoparticle of sufficient amount be could on cellulose fibre, form, metal nanoparticle and cellulose fibre composite prepared.On the one hand, because the metal ion in the aqueous solution all can aquation, promptly can combine a lot of hydrones around the metal ion; Thereby reduce the positive charge property of metal ion, reduced the coordination ability of metal ion, therefore; Can improve the coordination ability of metal ion through reducing solvent polarity; On the other hand, can be through changing the pH value of solution, can improve the electron rich center of hydroxyl and improve the coordination ability of metal ion.Thereby, finally on the cellulose fibre surface, form metal nanoparticle, through heat treated, prepare metal oxide nanoparticles and cellulose fibre composite.Simultaneously, can utilize the aldehyde radical functional group in the cellulosic molecule, reduce some metal ion (like silver ion or copper ion), prepare metal simple-substance nano particle and cellulose fibre composite synchronously with reducibility.
Beneficial effect: method of the present invention adopts in-situ preparation method, promptly adopts metal salt solution and cellulose fibre directly to mix, and through chemical bond, under suitable process conditions, interlock system gets metal nanoparticle and cellulose fibre composite; Utilize the reducibility of aldehyde radical in the cellulose, can under the situation of not adding other reductants, make metal simple-substance nano particle and cellulose fibre composite.Therefore; The inventive method not only can be applied to prepare elemental metals nano particle or metal oxide nanoparticles and cellulose fibre composite; And can simplify the preparation technology of metal nanoparticle and cellulose fibre composite greatly; Overcome preparation method's shortcoming in the past, reduce the problem of environmental pollution that is brought in independent preparation metal nanoparticle process.
Description of drawings
Fig. 1 is that cellulose macromolecule structure and surface hydroxyl thereof combine sketch map with slaine.
Fig. 2 is by the ferric oxide nano particles of ferric nitrate preparation and the electron micrograph of cellulose fibre composite.
Fig. 3 is by the ferric oxide nano particles of iron chloride preparation and the electron micrograph of cellulose fibre composite.
The electron micrograph of Fig. 4 Nano silver grain and cellulose fibre composite.
The electron micrograph of Fig. 5 copper nano-particle and cellulose fibre composite.
The specific embodiment
According to following embodiment, can understand the present invention better.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, process conditions and result thereof only are used to explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
Embodiment 1:
Take by weighing 10g paper pulp raw material (deriving from broad-leaved timber oar), add the 990mL deionized water, the dispersion of on fiber dissociates device, dissociating makes 1% fiber slurry.The fiber slurry of measuring 100ml 1% is in the round-bottomed flask of 500ml; And the mixed solvent 300ml of adding deionized water and absolute ethyl alcohol preparation in 50: 50 by volume, water-bath is heated to 60 ℃ on the magnetic stirring apparatus of rotating speed 1000rpm, keeps constant temperature; Dropwise drip the 100ml iron nitrate solution then; Dropwise the back and react 1h down,, filter then 40 ℃ of following ageings 24 hours at 60 ℃; Use the absolute ethyl alcohol elution samples, obtained ferric oxide nano particles and cellulose fibre composite in 24 hours in 60 ℃ of following vacuumize samples at last.The sample ultrasonic of preparation disperses the transmission electron microscope photo after 30 minutes as shown in Figure 2.Wherein the preparation condition of sample A is: iron nitrate solution concentration is 10mmol/L; The preparation condition of sample B is: iron nitrate concentration is 2.5mmol/L.
As can beappreciated from fig. 2, ferric oxide nano particles distributes comparatively intensive on fibrous matrix, and ferric oxide nano particles is granular, and its particle diameter is about 10nm.Comparison diagram A and figure B can find out that the ferric oxide nano particles of the sample that iron nitrate solution concentration is high distributes obviously more intensive, and metal oxide particle content is more.Wherein the specific area of sample A and B is respectively 27.7 and 15.7m
2/ g also contains more ferric oxide nano particles among the interpret sample A.
Embodiment 2:
Take by weighing 10g paper pulp raw material (deriving from broad-leaved timber oar), add the 990mL deionized water, on standard fibre dissociates device, disperse, obtain 1% fiber slurry.The fiber slurry of measuring 50ml 1% is in the round bottom single port flask of 500ml; And the mixed solvent 200ml of adding deionized water and absolute ethyl alcohol preparation in 10: 90 by volume; In microwave reactor, be heated with stirring to the reaction temperature in the table 1; Keep constant temperature, Dropwise 5 0ml ferric chloride solution dropwise dropwises the back and under this temperature, continues reaction 2h then.Reaction finishes the back 40 ℃ of following ageings 48 hours.Filter then, use the absolute ethyl alcohol wash-out, final sample obtained ferric oxide nano particles and cellulose fibre composite in 24 hours in 60 ℃ of following vacuumizes.The preparation condition and the specific surface area data of sample are as shown in table 1, and sample ultrasonic disperses the transmission electron microscope photo after 30 minutes as shown in Figure 3.
The preparation condition of table 1 sample
Can find out that by Fig. 3 the ferric oxide nano particles of sample A (water content is 20% in the solvent) is bar-shaped, and the ferric oxide nano particles of the composite under other condition is mainly graininess.Contrast B figure and D figure, when reaction temperature was increased to 80 ℃, the ferric oxide nano particles on the cellulose fibre reduced (D figure) on the contrary, and the ferric oxide nano particles distribution in 40 ℃ of following composites is comparatively intensive, the particle diameter of metal oxide nanoparticles littler (B figure).When water content in the dicyandiamide solution was 0, the prepared composite material did not have ferric oxide nano particles (F figure) on the cellulose fibre matrix.Contrast F, G and H figure, the moisture of raising dicyandiamide solution, the particle diameter of prepared Fe nanometer particles increases, serious agglomeration.And composite is handled back (sample I) through 150 ℃ of degassings, and fiber form changes, but the not significantly increase of its specific area.
Embodiment 3:
Take by weighing 30g paper pulp raw material (deriving from needle timber oar), add the 970mL deionized water, the dispersion of on fiber dissociates device, dissociating obtains 3% fiber slurry.The fiber slurry of measuring 50ml 3% is in the round bottom single port flask of 500ml; The mixed solvent 100ml that adds the preparation in 30: 70 by volume of deionized water and absolute ethyl alcohol; In microwave reactor, be heated with stirring to 60 ℃; Keep constant temperature, the 10mmol/L liquor argenti nitratis ophthalmicus of Dropwise 5 0ml dropwise then dropwises the back 60 ℃ of reactions 3 hours down.Products therefrom filters behind 60 ℃ of following ageing 24h; Use the absolute ethyl alcohol wash-out; Obtained simple substance Nano silver grain and cellulose fibre composite in 24 hours in 60 ℃ of following vacuumizes at last, the electronic fiber mirror photo of this compound material ultrasound dispersion after 30 minutes is shown in Fig. 4 (A).Can find out the Nano silver grain on the cellulose about the compound about 10nm of a large amount of particle diameters.
Embodiment 4:
Take by weighing 10g paper pulp raw material (deriving from needle timber oar), add the 990mL deionized water, the dispersion of on fiber dissociates device, dissociating obtains 1% fiber slurry.The fiber slurry of measuring 50ml 1% is in the round bottom single port flask of 500ml; And the mixed solvent 150ml of adding deionized water and absolute ethyl alcohol preparation in 50: 50 by volume; In microwave reactor, be heated with stirring to 60 ℃; Keep constant temperature, dropwise Dropwise 5 0ml concentration is the silver ammino solution of 50mmol/L then, dropwises the back and reacts 3 hours down at 60 ℃.The reaction back is taken out 40 ℃ of following ageings and was handled 24 hours.Filter then, use the absolute ethyl alcohol wash-out, obtained simple substance Nano silver grain and cellulose fibre composite in 24 hours 60 ℃ of following vacuumizes at last, the electron micrograph of this compound material ultrasound dispersion after 30 minutes is shown in Fig. 4 (B).Can find out, on the fiber load Nano silver grain of particle diameter between 10-20nm.
Embodiment 5:
Take by weighing 10g paper pulp raw material (deriving from the bamboo wood oar), add the 990mL deionized water, the dispersion of on fiber dissociates device, dissociating obtains 1% fiber slurry.The fiber slurry of measuring 50ml 1% is in the round bottom single port flask of 500ml; The mixed solvent 150ml that adds the preparation in 30: 70 by volume of deionized water and absolute ethyl alcohol again; In microwave reactor, be heated with stirring to 60 ℃; Keep constant temperature, dropwise Dropwise 5 0ml is that the concentration that acetic acid-sodium-acetate buffer of 5.4 is prepared is the copper nitrate solution of 50mmol/L by pH then, dropwises the back 60 ℃ of reactions 3 hours down.Then 40 ℃ of following ageings 30 hours.Filter successively then and the absolute ethyl alcohol wash-out, obtained elemental copper nano particle and cellulose fibre composite in 24 hours in 60 ℃ of vacuumizes at last, obtained sample ultrasonic disperses the transmission electron microscope photo after 30 minutes as shown in Figure 5.The reaction temperature of preparation sample A is 60 ℃, and the reaction temperature of sample B is by 60 ℃ of 80 ℃ of replacements.Can find out that by figure the copper nanoparticle is combined on the cellulose fibre thick and fast, show and iron, the different form of Nano silver grain.
Claims (9)
1. the preparation method of metal nanoparticle and cellulose fibre composite is characterized in that this method comprises the steps:
(1) adopts the fiber device that dissociates, in deionized water, dissociate paper pulp and disperse the preparation fiber slurry;
(2) slaine is dissolved in the solvent, is mixed with metal salt solution;
(3) in the fiber slurry that step (1) obtains, behind the adding solvent, be stirred and heated to 40-100 ℃, keep constant temperature, drip the metal salt solution of step (2) preparation then, reacted again after dropwising 1-3 hour;
(4) after reaction finishes, carry out ageing processing and filter operation, obtain the cellulose fibre that load has metal nanoparticle;
(5) load that obtains of elution step (4) has the cellulose fibre of metal nanoparticle, obtains metal nanoparticle and fibrous composite after the drying;
Wherein,
Described metal nanoparticle is metal simple-substance nano particle or metal oxide nanoparticles;
In the step (2), described slaine is molysite, silver salt or mantoquita;
In step (2) and (3), described solvent is that deionized water and absolute ethyl alcohol are (10-90) according to volume ratio: (90-10) mixture of preparation.
2. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, in the step (1), described sources of paper pulp is in broadleaf wood pulp, softwood wood pulp or bamboo wood slurry.
3. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, in the step (1), described pulp quality percentage concentration is 1-5%.
4. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, in the step (2), described metal salt solution concentration is 1-50mmol/L.
5. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, in the step (3), the volume ratio of fiber slurry and solvent is 1: (2-5).
6. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, in the step (3), the volume ratio of fiber slurry and metal salt solution is (1-5): 1.
7. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, the ageing described in the step (4), and its temperature is 40-60 ℃, the Chen Hua time is 24-48 hour.
8. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, in the step (5), described wash-out, its solvent are ethanol.
9. the preparation method of metal nanoparticle according to claim 1 and cellulose fibre composite is characterized in that, in the step (5), described drying condition is: pressure is normal pressure or decompression, and temperature is 40-180 ℃.
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| CN102704327A (en) * | 2012-06-25 | 2012-10-03 | 湖南工业大学 | Method for preparing LDHs flame retardant paper |
| CN104305796A (en) * | 2014-09-29 | 2015-01-28 | 吉特利环保科技（厦门）有限公司 | Technology for preparing nano-silver antibacterial tableware on basis of PLC (programmable logic controller) automatic system |
| CN108142420A (en) * | 2017-12-06 | 2018-06-12 | 陕西科技大学 | A kind of anti-biotic material and preparation method thereof |
| CN109897354A (en) * | 2019-03-25 | 2019-06-18 | 杭州曦茂新材料科技有限公司 | Polylactic acid crystal is nucleated cellulose nano-fibrous preparation method and applications |
| CN110462111A (en) * | 2017-03-29 | 2019-11-15 | 古河电气工业株式会社 | Integrally formed body and the composite material, electrical contact terminal and printed wiring board that body is integrally formed with this |
| CN110698728A (en) * | 2019-09-09 | 2020-01-17 | 中国科学院金属研究所 | Cellulose/nano inorganic particle composite pigment and preparation method and application thereof |
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| CN102704327A (en) * | 2012-06-25 | 2012-10-03 | 湖南工业大学 | Method for preparing LDHs flame retardant paper |
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| CN110462111A (en) * | 2017-03-29 | 2019-11-15 | 古河电气工业株式会社 | Integrally formed body and the composite material, electrical contact terminal and printed wiring board that body is integrally formed with this |
| CN110462111B (en) * | 2017-03-29 | 2022-01-07 | 古河电气工业株式会社 | Integrated body, composite material having the same, terminal for electrical contact, and printed wiring board |
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| CN108142420A (en) * | 2017-12-06 | 2018-06-12 | 陕西科技大学 | A kind of anti-biotic material and preparation method thereof |
| CN109897354A (en) * | 2019-03-25 | 2019-06-18 | 杭州曦茂新材料科技有限公司 | Polylactic acid crystal is nucleated cellulose nano-fibrous preparation method and applications |
| CN110767883A (en) * | 2019-07-02 | 2020-02-07 | 罗宝林 | Modified fiber, preparation method and application |
| CN110698728A (en) * | 2019-09-09 | 2020-01-17 | 中国科学院金属研究所 | Cellulose/nano inorganic particle composite pigment and preparation method and application thereof |
| CN110698728B (en) * | 2019-09-09 | 2022-02-01 | 中国科学院金属研究所 | Cellulose/nano inorganic particle composite pigment and preparation method and application thereof |
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