CN102352049B - Preparation method of noble metal nanoparticle-cellulose hybrid membrane - Google Patents

Preparation method of noble metal nanoparticle-cellulose hybrid membrane Download PDF

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CN102352049B
CN102352049B CN201110209029A CN201110209029A CN102352049B CN 102352049 B CN102352049 B CN 102352049B CN 201110209029 A CN201110209029 A CN 201110209029A CN 201110209029 A CN201110209029 A CN 201110209029A CN 102352049 B CN102352049 B CN 102352049B
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cellulose
noble metal
preparation
nano
film
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CN102352049A (en
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刘志明
吴文健
胡碧茹
满亚辉
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National University of Defense Technology
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Abstract

The invention relates to a preparation method of a nanometer metal-cellulose hybrid membrane, especially to a preparation method of a noble metal nanoparticle-cellulose hybrid membrane. By steps of preparing a cellulose solution, preparing a membrane by the cellulose solution, preparing noble metal nanosol, preparing the nanometer metal-cellulose hybrid membrane and the like, the noble metal nanosol is used as a noble metal source, and the self-assembly of the noble metal nanosol on the surface of the industrial regenerated cellulose membrane is realized by the irreversible diffusion process so as to prepare the high surface enriched noble metal nanoparticle-cellulose hybrid membrane. The prepared noble metal nanoparticle-cellulose hybrid membrane has excellent assembly and fixing performance for guest substances such as proteins and enzyme, and can be widely applied in the construction of nanometer dielectric conductors, bioactive molecular membranes, biochemical sensors and the like.

Description

The preparation method of a kind of nano noble metal particles-Mierocrystalline cellulose hybridized film
Technical field
The present invention relates to the preparation method of a kind of nano metal-Mierocrystalline cellulose hybridized film, the preparation method of particularly a kind of nano noble metal particles-regenerated cellulose hybridized film.
Background technology
Nano metal-polymer hybrid material not only has the excellent mechanical property of polymkeric substance, and has kept the functional performance of nano metal, and under multi-component synergistic effect, it has performances such as unique power, heat, sound, light, electricity, magnetic.Mierocrystalline cellulose is that the essential substance of plant is formed as the abundantest renewable resources of occurring in nature, has very high biocompatibility and degradability.In recent years, the nano metal of will have conduction, inhaling ripple, catalysis, biochemical detecting function hybridizes to and becomes the research of field of nanometer material technology focus in the cellulose membrane.
2004; People such as Junhui He publish an article (2003 on Chem.Mater.; 15 (23): 4401～4406); Reported that the nanoaperture of using the multiporous fiber cellulose fiber as the nanometer reaction vessel, utilizes nano metal particles and cellulosic keying action, in-situ preparing nano noble metal particles and cellulosic hybrid materials such as silver, gold, platinum, palladium.The preparation method of this kind nano noble metal particles-Mierocrystalline cellulose hybrid material depends on the structure and the character of Mierocrystalline cellulose porous material unduly, and the nano noble metal particles granularity heterogeneity of preparation, form are inhomogeneous, and are difficult to control its deployment conditions.2008; People such as Shingo Yokota once attempted using the process thiosemicarbazone grafted low polymerization degree Mierocrystalline cellulose and nanometer gold (Au) particle that are dissolved in the N-methylmorpholine oxide compound (NMMO) to carry out direct hydridization; But owing to nano Au particle takes place to reunite and can't disperse (the Angew.Chem. that fails again; 2008,120:10014～10017).The inventor once adopted the NMMO solvent method to prepare cellulose solution; Through using cheap DMSO 99.8MIN. (DMSO) as cosolvent, successfully solve nano Au particle and met NMMO solution generation aggregation phenomenon, a kind of effective ways (Chem.Mater. for preparing nano Au particle-Mierocrystalline cellulose hybridized film has been proposed; 2010; 22 (8): 2675～2680), this method uses the direct regeneration of gold sol to be dissolved in the Mierocrystalline cellulose among the NMMO, and the utilization ratio of nano Au particle and the deployment conditions in cellulose membrane thereof receive the NMMO content influence bigger; Be suitable for laboratory study, be difficult to realize suitability for industrialized production.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, solve the controlled hydridization problem of nano noble metal particles and cellulose membrane, a kind of nano noble metal particles-Mierocrystalline cellulose hybridized film preparation method who is suitable for suitability for industrialized production is provided.
The present invention realizes through following technical scheme:
1, preparation cellulose solution:
Under 90 ℃, nitrogen protection, use N-methylmorpholine oxide compound monohydrate (NMMOH 2O) direct dissolving cellulos continues to stir 2～24 hours, dissolves fully until Mierocrystalline cellulose;
Described Mierocrystalline cellulose comprises alpha-cellulose, Microcrystalline Cellulose, and bleached pulp Mierocrystalline cellulose such as wood pulp cellulose, cotton pulp Mierocrystalline cellulose, straw pulp Mierocrystalline cellulose, preferably alpha-cellulose;
The mass ratio of main ingredient is Mierocrystalline cellulose: NMMOH 2O=1: 4～49;
Preferably, can add the Tenox PG (Propyl Gallate) that accounts for liquid quality fraction 5/10000ths (0.05%) uses as inhibitor;
Preferably,, can in cellulose solution, add DMSO 99.8MIN. (DMSO) and use,, can obtain amber Mierocrystalline cellulose-NMMOH at 90 ℃ of following stirring and evenly mixings as cosolvent for reducing cellulose solution viscosity, improving its film forming properties 2O-DMSO solution, the mass ratio of each component is: cellulose solution: DMSO=1: 0.1～2;
2, cellulose solution system film:
In 20～30 ℃ of envrionment temperatures, relative humidity RH≤65% time, be film forming liquid with 70～90 ℃ cellulose solutions, at bright and clean wetting ability substrate surface, with cellulose solution system film;
The system film can get rid of modes such as film, film balance membrane through glass stick knifing, whirler, or does not use substrate directly to carry out through the mode of inflation film manufacturing machine blown film, and this type of mode is that the present technique field is known;
Come out cellulose regenerated with coagulation bath submergence cellulose solution film; Use the abundant leaching regeneration cellulose membrane of deionized water; Until there not being solvent to be come out by drip washing; Regenerated cellulose film is kept under the deionized water environment, and this kind preserving type will make regenerated cellulose film keep the high reactivity hydroxyl surface;
Described wetting ability substrate comprises simple glass sheet, quartz plate, ITO conductive glass sheet, sheet mica or rock cleavage sheet;
Described coagulation bath comprises water, ethanol, propyl alcohol or their mixing solutions;
3, preparation nano-noble metal colloidal sol:
With the deionized water is solvent; The precious metal acid or the salts solution of 9 volumes, 0.5～2mmol/L concentration under agitation are heated to boiling; The Hydrocerol A or the salts solution of 1 volume, 8～80mmol/L concentration are added wherein rapidly, continue heating 25 minutes, be cooled to room temperature under continuing to stir;
Described precious metal acid or salt comprise hydrochloro-auric acid (HAuCl 4), potassium chloraurate (KAuCl 4), sodium chloraurate (NaAuCl 4), gold trichloride (AuCl 3), Silver Nitrate (AgNO 3), Platinic chloride (H 2PtCl 6), potassium platinichloride (K 2PtCl 6), sodium platinichloride (Na 2PtCl 6), inferior Platinic chloride (H 2PtCl 4), inferior potassium platinichloride (K 2PtCl 4), inferior sodium platinichloride (Na 2PtCl 4), platinum chloride (PtCl 4), Palladous chloride (PdCl 2), palladium (Pd (CH 3COO) 2), Palladous nitrate (Pd (NO 3) 2), preferably use hydrochloro-auric acid (HAuCl 4), Silver Nitrate (AgNO 3), potassium platinichloride (K 2PtCl 6), palladium (Pd (CH 3COO) 2); Said Hydrocerol A or salt comprise Hydrocerol A (H 3C 6H 5O 7), Tripotassium Citrate (K 3C 6H 5O 7), Hydrocerol A one hydrogen potassium (K 2HC 6H 5O 7), potassium citrate dihydrogen (KH 2C 6H 5O 7), Trisodium Citrate (Na 3C 6H 5O 7), Hydrocerol A one hydrogen sodium (Na 2HC 6H 5O 7), Sodium citrate (NaH 2C 6H 5O 7), preferably use Trisodium Citrate (Na 3C 6H 5O 7);
4, preparation nano-noble metal-Mierocrystalline cellulose hybridized film:
Under the normal temperature and pressure; The nano-noble metal colloidal sol that every gram Mierocrystalline cellulose use volume is 2～8L carries out immersion treatment; The control treatment time was at 12～360 hours; Use the abundant drip washing Mierocrystalline cellulose of deionized water hybridized film, then hybridized film is placed the deionized water preservation or at air drying, can obtain nano-noble metal of different nature-Mierocrystalline cellulose hybridized film.
The inventive method is to utilize deionized water to keep the high reactivity hydroxyl surface of regenerated cellulose film; Through of the replacement of cellulolytic activity hydroxyl to the citrate of nano noble metal particles surface adsorption; Realize the self-assembly of nano noble metal particles on the cellulose membrane top layer, the controlled hydridization technical problem of solution nano noble metal particles and cellulose membrane.
Utilize the nano-noble metal-Mierocrystalline cellulose hybridized film of the inventive method preparation to have the nano noble metal particles distribution characteristics of high surface enrichment; Can need not base material support and use separately; And the preparation method is simple, is easy to realize suitability for industrialized production large area flexible nano-noble metal Mierocrystalline cellulose hybrid material.
Description of drawings
Fig. 1 is the transmission electron microscope photo (the Electronic Speculum model is JEOL JEM 1200EX, and electron energy is 120keV) in embodiment 1 film cross section, and the nano Au particle mean diameter is about 13nm;
Fig. 2 is the transmission electron microscope photo (the Electronic Speculum model is JEOL JEM 1200EX, and electron energy is 120keV) in embodiment 2 film cross sections, and nanometer platinum particles mean diameter is about 3.2nm;
Fig. 3 is the transmission electron microscope photo (the Electronic Speculum model is JEOL JEM 1200EX, and electron energy is 120keV) in embodiment 3 film cross sections, and the nano silver particles mean diameter is about 21nm;
Fig. 4 is the transmission electron microscope photo (the Electronic Speculum model is JEOL JEM 1200EX, and electron energy is 120keV) in embodiment 4 film cross sections, and nanometer palladium average particle diameter is about 6nm.
Embodiment
Below through embodiment the present invention is described further, but protection domain does not receive the restriction of these embodiment.Should be understood that in addition that after having read content of the present invention those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within appended claims of the present invention institute restricted portion equally.
Embodiment 1
Under 90 ℃, nitrogen protection, the 2g alpha-cellulose is joined among the 98g NMMOH2O, continue to stir after 2 hours, obtain cellulose solution; Under the condition of 25 ℃ of temperature, relative humidity RH=60%, be substrate with ganoid silicate glass sheet, use whirler to get rid of film on its surface at 70 ℃ of following dissolved cellulose solutions, preparation cellulose solution film, speed setting is at 1krpm; Use deionized water to soak the cellulose solution smear after 2 hours, the leaching regeneration cellulose membrane, and it is kept in the deionized water; With 1.5g hydrochloro-auric acid (HAuCl 4) be dissolved in the 4.5L deionized water, under magnetic agitation, chlorauric acid solution is heated to boiling, with 4.5g Trisodium Citrate (Na 3C 6H 5O 7) be dissolved in the 0.5L deionized water, rapidly sodium citrate soln is joined rapidly in the ebullient chlorauric acid solution after waiting to dissolve, continue heating 25 minutes; Stop heating then; Continuing to naturally cool to room temperature under the stirring, in 5L, using gold sol to soak regenerated cellulose film the gold sol constant volume; Normal temperature and pressure was handled 12 hours down, obtained nanometer gold-regenerated cellulose hybridized film that thickness is about 25 μ m.Can find out that from the transmission electron microscope photo in its cross section nano Au particle mainly is distributed in the scope of film surface 500nm, promptly nano Au particle mainly is distributed in the thickness of hybridized film 2%, has high surface enrichment characteristic.
Embodiment 2
Under 90 ℃, nitrogen protection, 8g cotton pulp Mierocrystalline cellulose, 0.05g Tenox PG are joined 92g NMMOH 2Among the O, continue to stir after 24 hours, obtain cellulose solution; Under the condition of 30 ℃ of temperature, relative humidity RH=30%, use inflation film manufacturing machine to cross tank with cellulose regenerated at 90 ℃ of following dissolved cellulose solution extruding, blown film, cross the abundant leaching regeneration cellulose membrane of steam; With 56g potassium platinichloride (K 2PtCl 6) be dissolved in the 57.6L deionized water, under magnetic agitation, potassium platinichloride solution is heated to boiling; With 98.4g Hydrocerol A (H 3C 6H 5O 7) be dissolved in the 6.4L deionized water, treat fully rapidly sodium citrate soln to be joined rapidly in the ebullient potassium platinichloride solution after the dissolving, continue heating and stop heating after 25 minutes, under continuing to stir, naturally cool to room temperature, with platinum colloidal sol constant volume in 64L; Use nanometer platinum colloidal sol to soak regenerated cellulose film, normal temperature and pressure was handled 360 hours down, obtained nanometer platinum-regenerated cellulose hybridized film that thickness is about 50 μ m.Can find out that from the transmission electron microscope photo in its cross section the nanometer platinum particles mainly is distributed in the scope of film surface 140nm, promptly the nanometer platinum particles mainly is distributed in the thickness of hybridized film 0.3%, has high surface enrichment characteristic.
Embodiment 3
Under 90 ℃, nitrogen protection, 8g straw pulp Mierocrystalline cellulose is joined 32g NMMOH 2Among the O, after continuing to stir 12h, obtain cellulose solution,, under 70 ℃, continue to stir the film forming liquid that obtains mixing 12 hours to wherein adding 80g DMSO; Under the condition of 25 ℃ of envrionment temperatures, relative humidity RH=45%, 75 ℃ film forming liquid are left standstill 20 minutes after, be substrate with the sheet mica, dipping-pulling film forming on the substrate of cleaning, pull rate 15cm/ minute; Use excessive deionized water to soak smear 2 hours, abundant then leaching regeneration cellulose membrane; Under the room temperature, with 1.2g Silver Nitrate (AgNO 3) be dissolved in the 14.4L deionized water fully dissolving under middling speed stirs; With 3.9g Tripotassium Citrate (K 3C 6H 5O 7) be dissolved in the 1.6L deionized water, treat fully to join potassium citrate solution in the silver nitrate solution rapidly rapidly after the dissolving; Continue to stir after 24 hours, with the silver sol constant volume in 16L; Use nano silver colloidal sol to soak regenerated cellulose film, normal temperature and pressure is handled 72h down, obtains nanometer silver-regenerated cellulose hybridized film that thickness is about 60 μ m.Can find out that from the transmission electron microscope photo in its cross section nano silver particles mainly is distributed in the scope of film surface 800nm, promptly nano silver particles mainly is distributed in the thickness of hybridized film 1.3%, has high surface enrichment characteristic.
Embodiment 4
Under 90 ℃, nitrogen protection, 5g wood pulp cellulose, 0.04g Tenox PG are joined 75g NMMOH 2Among the O, continue to stir after 24 hours, obtain cellulose solution,, under 80 ℃, continue to stir the film forming liquid that obtains mixing 12 hours to wherein adding 8g DMSO; Under the condition of 25 ℃ of temperature, relative humidity RH=65%, be substrate with the ito glass sheet of any surface finish, using diameter is the localized knifing rod of wire of 25 μ m, will be at 70 ℃ of following dissolved film forming liquid at its surperficial knifing; Use excessive deionized water to soak smear 2 hours, abundant then leaching regeneration cellulose membrane; With 10.2g palladium (Pd (CH 3COO) 2) be dissolved in the 27L deionized water, under magnetic agitation, palladium solution is heated to boiling; With 50.3g Trisodium Citrate (Na 3C 6H 5O 7) be dissolved in the 3L deionized water, treat fully rapidly sodium citrate soln to be joined rapidly in the ebullient palladium solution after the dissolving, continue heating 25 minutes, stop heating then, under continuing to stir, make solution naturally cool to room temperature, with palladium colloidal sol constant volume in 30L; Use nanometer palladium colloidal sol to soak regenerated cellulose film, normal temperature and pressure was handled 168 hours down, obtained nanometer palladium-regenerated cellulose hybridized film that thickness is about 22 μ m.Can find out that from the transmission electron microscope photo in its cross section nanometer palladium particle mainly is distributed in the scope of film surface 360nm, promptly nanometer palladium particle mainly is distributed in the thickness of hybridized film 1.6%, has high surface enrichment characteristic.

Claims (6)

1. the preparation method of nano-noble metal-Mierocrystalline cellulose hybridized film, realized by following steps:
(1) preparation cellulose solution:
Under 90 ℃, nitrogen protection, be Mierocrystalline cellulose with mass ratio: the compound of N-methylmorpholine oxide compound monohydrate=1:4～49 continues to stir 2～24 hours, dissolves fully until Mierocrystalline cellulose;
(2) cellulose solution system film:
In 20～30 ℃ of envrionment temperatures, relative humidity RH≤65% time; With the cellulose solution for preparing is raw material, at bright and clean wetting ability substrate surface, with cellulose solution system film; With coagulation bath submergence cellulose solution film; Come out cellulose regenerated, use the abundant leaching regeneration cellulose membrane of deionized water, regenerated cellulose film is kept under the deionized water environment;
(3) preparation nano-noble metal colloidal sol:
With the deionized water is solvent; The precious metal acid or the salts solution of 9 volumes, 0.5～2mmol/L concentration under agitation are heated to boiling; The Hydrocerol A or the salts solution of 1 volume, 8～80mmol/L concentration are added wherein rapidly, continue heating and continue after 25 minutes to stir to be cooled to room temperature;
(4) preparation nano metal-Mierocrystalline cellulose hybridized film:
Under the normal temperature and pressure; The nano-noble metal colloidal sol that every gram Mierocrystalline cellulose use volume is 2～8L carries out immersion treatment; The control treatment time was used the abundant drip washing Mierocrystalline cellulose of deionized water hybridized film at 12～360 hours, placed deionized water to preserve or at air drying hybridized film then.
2. the preparation method of the said a kind of nano-noble metal of claim 1-Mierocrystalline cellulose hybridized film, it is characterized in that: said Mierocrystalline cellulose is an alpha-cellulose;
3. the preparation method of claim 1 or 2 said a kind of nano-noble metal-Mierocrystalline cellulose hybridized film is characterized in that: in preparation cellulose solution process, add the Tenox PG that accounts for liquid quality fraction 5/10000ths.
4. the preparation method of claim 1 or 2 said a kind of nano-noble metal-Mierocrystalline cellulose hybridized film is characterized in that: in preparation cellulose solution process, add DMSO 99.8MIN., the mass ratio of each component is cellulose solution: DMSO 99.8MIN.=1:0.1～2.
5. the preparation method of claim 1 or 2 said a kind of nano-noble metal-Mierocrystalline cellulose hybridized film, it is characterized in that: said precious metal acid or salt are hydrochloro-auric acid, Silver Nitrate, potassium platinichloride or palladium.
6. the preparation method of claim 1 or 2 said a kind of nano-noble metal-Mierocrystalline cellulose hybridized film, it is characterized in that: said Citrate trianion is a Trisodium Citrate.
CN201110209029A 2011-07-25 2011-07-25 Preparation method of noble metal nanoparticle-cellulose hybrid membrane Expired - Fee Related CN102352049B (en)

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