CN103897221A - Chitosan/phosphorylated silicon dioxide particle hybrid film as well as preparation and application thereof - Google Patents
Chitosan/phosphorylated silicon dioxide particle hybrid film as well as preparation and application thereof Download PDFInfo
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- CN103897221A CN103897221A CN201410093433.6A CN201410093433A CN103897221A CN 103897221 A CN103897221 A CN 103897221A CN 201410093433 A CN201410093433 A CN 201410093433A CN 103897221 A CN103897221 A CN 103897221A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a phosphorylated mesoporous hollow silicon dioxide submicron spherical particle, and specifically relates to a chitosan/phosphorylated mesoporous hollow silicon dioxide submicron spherical particle hybrid film as well as a preparation method and an application thereof. The preparation method of the hybrid film comprises the steps of synthesizing the mesoporous hollow silicon dioxide particles, performing epoxidation modification on the mesoporous hollow silicon dioxide particles by using an epoxy silane coupling agent, and then performing phosphorylation modification on the epoxy mesoporous hollow silicon dioxide particles by using phosphorus oxychloride; dispersing the phosphorylated mesoporous hollow silicon dioxide particles in a film casting solution containing small molecular phosphoric acid, dissolving a chitosan high polymer, mixing thoroughly and then defoaming the film casting solution, next, casting a film on a glass plate by a tape casting method, drying at room temperature and then cross-linking in diluted sulfuric acid to obtain the hybrid film material. The preparation and phosphorylation processes of the inorganic material are efficient, controllable, and simple and convenient in conditions. The obtained hybrid film is excellent in properties if being applied to a direct-methanol fuel cell, and the proton conduction rate reaches up to 0.0934Scm<-1> under the conditions that the temperature is 110 DEG C, the relative humidity is 100%, and the filling volume of the phosphorylated mesoporous hollow silicon dioxide particles is 7.5wt.%.
Description
Technical field
The present invention relates to the mesoporous hollow silica submicron spherical of a kind of chitosan/phosphorylation particle hybridized film and its preparation method and application, belong to hybrid inorganic-organic proton exchange membrane used for direct methanol fuel cell field, especially relate to the preparation method and application of the mesoporous hollow silica submicron spherical of phosphorylation particle.
Background technology
Fuel cell is a kind of new chemical energy, and it is a kind of without burning, directly the chemical energy of fuel is changed into the device of electric energy in the mode of electrochemical reaction, have generating efficiency high, be applicable to pluralities of fuel and advantages of environment protection.Wherein, direct methanol fuel cell (direct methanol fuel cell, DMFC) be taking methanol aqueous solution as fuel, except thering is the advantage of general fuel cell, also there is the outstanding advantages such as normal temperature starts fast, energy density is high, the cheap abundant easily storage of fuel, battery structure is simple, cost is low, be described as most promising novel portable power supply of 21 century.Proton exchange membrane (proton exchange membrane, PEM) is one of DMFC most critical parts, is the key component that improves fuel cell energy transformation efficiency.At present, business-like PEM is mainly perfluoro sulfonic acid membrane, as the Nafion of DuPont company of Du Pont exploitation
?series membranes.But this type of sulfonated film is when the DMFC, under high-temperature operation condition due to film in moisture loss can cause performance degradation.In addition expensive (the 600-1200 $ m of perfluoro sulfonic acid membrane,
-2), methanol permeability is higher, has greatly limited DMFC technology popularization and application thereof.Therefore the preparation that, is applicable to high temperature low humidity DMFC operational condition, proton conductivity is high, cost is low new PE M becomes current research focus.
As proton transfer site, phosphate radical has advantages of that both sexes (proton acceptor, protophobe), specific inductivity are high, can form higher proton density, this act under high temperature low humidity condition particularly remarkable.The water of phosphate radical in conjunction with can higher, average zero-point energy lower than sulfonate radical, can provide higher water retention capacity and lower proton jump energy barrier for mould material.The thermostability of phosphate radical is also better than sulfonate radical in addition.Just because of these advantages, phosphate radical class proton exchange membrane becomes study hotspot gradually.Because phosphorylation macromolecule member material kind is few, synthesis condition is harsh, the approach of generally introducing phosphate radical in film is by membrane matrix is soaked in the middle of phosphate aqueous solution, but this operation often causes phosphoric acid to run off in the water surrounding of DMFC work.Phosphate radical is fixed on and in inorganic materials, just becomes a kind of practicable approach.The hybrid organic-inorganic film that filling has water absorbability particle can have in the inorganic particle introducing film of leading proton ability, thus the performances such as the proton conductivity of raising film.Up to the present, the mesoporous hollow silica hybridized film of chitosan/phosphorylation has no bibliographical information for the proton exchange membrane of direct methanol fuel cell.
Summary of the invention
The object of the present invention is to provide a kind of hybrid inorganic-organic proton exchange membrane used for direct methanol fuel cell, it is prepared by the following method: first prepare mesoporous hollow silica submicron spherical particle (HMSS), then by epoxy silane coupling, its modifying surface is introduced to epoxy group(ing), re-using phosphorus oxychloride carries out phosphorylation and prepares the mesoporous hollow silica submicron spherical of phosphorylation particle (P-HMSS), finally itself and chitosan (CS) are synthesized to the mesoporous hollow silica submicron spherical of chitosan/phosphorylation particle (CS/P-HMSS) hybridized film by casting method.
The mesoporous hollow silica submicron spherical of phosphorylation provided by the invention particle is prepared as follows.
1) preparation of silicon dioxide sub-micron sphere shape particle kernel
Use silane precursor (tetraethoxy, tetraethyl orthosilicate, TEOS) and ammoniacal liquor as raw material, adopt St ber method synthetic silica, products obtained therefrom is the monodispersed spherical of diameter 130 nm, as kernel sSiO
2.
2) preparation of mesoporous hollow silica submicron spherical particle (HMSS)
First, to sSiO
2skin is coated with CTAB(cetyl trimethylammonium bromide, hexadecyl trimethyl ammonium bromide) be the mesoporous lamella of template: by sSiO
2be well-dispersed in deionized water and form dispersion liquid, in this dispersion liquid, add the CTAB, deionized water, ethanol and the ammonia soln that mix afterwards, dropwise in solution, add TEOS, sSiO in the solution of configuration
2mass/volume mark be 0.124 wt./vol.%, the mass/volume mark of CTAB is 0.186 wt./vol.%, the volume fraction of TEOS is 0.309 vol.%, keeps vigorous stirring 2-12 hour.Centrifuge washing obtains solid phase prod, and products obtained therefrom is that the coated CTAB of appearance is the solid silicon dioxide sub-micron sphere shape particle of template mesoporous lamella, is designated as CTAB@SiO
2/ sSiO
2.
By CTAB@SiO
2/ sSiO
2be scattered in 0.2 excessive mol/L aqueous sodium carbonate, solution is held in 50
oc vigorous stirring 6-38 hour, with aqueous sodium carbonate etching particle kernel.Centrifugation washing, products obtained therefrom is that CTAB is template meso-porous hollow silicon dioxide sub-micron sphere shape particle, is designated as CTAB@SiO
2.
Finally, by CTAB@SiO
2particle is scattered in excessive methanol hydrochloric acid soln, refluxes and within 48 hours, removes the CTAB template of particle.Centrifugation washing, obtains mesoporous hollow silica submicron spherical particle HMSS.
3) preparation of the mesoporous hollow silica submicron spherical of phosphorylation particle (P-HMSS):
As above the synthetic HMSS particle of method is scattered in excessive dry toluene, epoxy silane coupling (the 3-glycidyl oxygen propyl trimethoxy silicane of quality such as add, 3-glycidyloxypropyltrimethoxysilane, GPTMS), back flow reaction 24 hours, carries out epoxy group(ing) modification to HMSS.Centrifuge washing, is scattered in gained epoxy group(ing) modified particles in excessive phosphorus oxychloride, refluxes and particle is carried out to phosphorylation in 24 hours.Centrifuge washing, obtains the mesoporous hollow silica submicron spherical particle P-HMSS of phosphorylation.
The mesoporous hollow silica submicron spherical of chitosan/phosphorylation provided by the invention particle hybridized film (CS/P-HMSS) is prepared as follows.
Be scattered in the deionized water that contains Amino Trimethylene Phosphonic Acid (accounting for film-casting liquid total mass mark is 0.12 wt.%-0.44 wt.% for aminotrimethylene phosphonic acid, ATMP) ultrasonic a certain amount of P-HMSS.To adding in dispersion liquid, to account for film-casting liquid total mass mark be the acetic acid of 2 wt.%, and be heated to 80
oc.Under mechanical stirring condition, in solution, add chitosan, wherein to account for film-casting liquid total mass mark be 2 wt.% to chitosan, the 1.25 wt.%-10 wt.% that P-HMSS consumption is chitosan.80
ounder C, vigorous stirring is dissolved and within 2 hours, is obtained film-casting liquid.By after film-casting liquid deaeration on sheet glass curtain coating, dry, crosslinked with aqueous sulfuric acid, the dry hybridized film that obtains of then washing.The thickness of gained film is in 80 μ m left and right.
The invention has the advantages that: realize particle phosphorus acidifying by the method for introducing epoxy group(ing) at mesoporous hollow silica submicron spherical particle surface, process is gentle simple, overcome silica sphere silicon hydroxyl inertia and be difficult for the shortcoming of reacting.Using phosphate radical be successfully fixed on silicon-dioxide, the internal cavities of hollow silica is as the sour pond of fixing phosphate radical simultaneously, to the efficient phosphate radical of introducing in film as proton transfer group.After being packed into CS film, can obtain uniform phosphorylation hybrid organic-inorganic film.The mesoporous hollow silica submicron spherical particle of phosphorylation, as proton conductor, has improved hybridized film proton conduction property.The prepared phosphorylation hybridized film of the inventive method CS/P-HMSS, during for direct methanol fuel cell, 110
ounder the condition of C, relative humidity 100%, conductivity is up to 0.0934 S cm
-1, be in the methanol aqueous solution of 2 M in concentration, room temperature 25
ounder C condition, methanol permeability is minimum reaches 8.42 × 10
-7cm
2s
-1.
Brief description of the drawings
In Fig. 1 embodiment and comparative example, film is in 30
othe proton conductivity comparison diagram of C, 100% RH.
In Fig. 2 embodiment and comparative example, film is in temperature-rise period (100
oc-110
oc), the proton conductivity comparison diagram of 100% RH.
The transmission electron microscope picture (HRTEM-JEM-2100F type HRTEM, JEOL company) of the made mesoporous hollow silica submicron spherical of phosphorylation particle in Fig. 3 embodiment 2.
The transmission electron microscope picture of made mesoporous hollow silica submicron spherical particle (HRTEM-JEM-2100F type HRTEM, JEOL company) in Fig. 4 embodiment 1.
The section Electronic Speculum figure of made film CS/P-HMSS-1.25 in Fig. 5 embodiment 3 (Nanosem 430 type FESEM, FEI Co.).
The section Electronic Speculum figure of made film CS/P-HMSS-7.5 in Fig. 6 embodiment 3 (Nanosem 430 type FESEM, FEI Co.).
The section Electronic Speculum figure of made comparative film CS in Fig. 7 comparative example 1 (Nanosem 430 type FESEM, FEI Co.).
The section Electronic Speculum figure of made comparative film CS/HMSS-1.25 in Fig. 8 comparative example 2 (Nanosem 430 type FESEM, FEI Co.).
The section Electronic Speculum figure of made comparative film CS/HMSS-7.5 in Fig. 9 comparative example 2 (Nanosem 430 type FESEM, FEI Co.).
Embodiment
The preparation of embodiment 1 HMSS
TEOS(9.5 mL), ammoniacal liquor (7 mL) is scattered in alcohol-water mixed solution (ethanol 200 mL, deionized water 20 mL), under room temperature, stir 24 hours.Centrifugal and with ethanol, water washing three times, room temperature vacuum-drying obtains sSiO to constant weight
2.
By 250 mg sSiO
2be well-dispersed in 50 mL deionized waters, keep stirring 30 minutes.Afterwards this dispersion liquid is joined to the CTAB(375 mg mixing), in deionized water (75 mL), ethanol (75 mL), ammoniacal liquor (1.375 mL) solution, keep under room temperature vigorous stirring 30 minutes.Dropwise in solution, add TEOS(0.625 mL), room temperature keeps stirring 6 hours.Centrifugation obtains solid phase prod, after deionized water wash three times, product, in room temperature vacuum-drying to constant weight, is obtained to CTAB SiO
2/ sSiO
2.
By the above-mentioned CTAB@SiO making
2/ sSiO
2with 5 mL deionized waters dispersions, then add 5 mL sodium carbonate solutions, be configured to sodium carbonate and account in the aqueous sodium carbonate that bulk solution concentration is 0.2 mol/L, solution is held in 50
oc vigorous stirring 19 hours.Centrifugation obtains solid phase prod, and after deionized water wash three times, product is in room temperature vacuum-drying to constant weight, and products obtained therefrom is CTAB SiO
2.
Finally, by 1.2 g CTAB@SiO
2particle is scattered in by the concentrated hydrochloric acid of 9 mL 37.4% and is dissolved in the methanolic hydrochloric acid solution forming in 160 mL anhydrous methanols, refluxes 48 hours.Centrifugation obtains solid phase prod, and after deionized water wash three times, product is in room temperature vacuum-drying to constant weight, and products obtained therefrom is HMSS.
The preparation of embodiment 2 P-HMSS
The HMSS making is scattered in dry toluene (60 times that quality is HMSS), the GPTMS of quality such as adds, back flow reaction 24 hours.Centrifugal and with ethanol, water washing three times, product, in room temperature vacuum-drying to constant weight, obtains epoxy group(ing) modification HMSS.Above-mentioned epoxy group(ing) modification HMSS particle is scattered in to (phosphorus oxychloride quality is 60 times of granular mass) in excessive phosphorus oxychloride, refluxes 24 hours.Centrifugal and with ethanol, water washing three times, obtain the mesoporous hollow silica submicron spherical of phosphorylation particle P-HMSS after dry.
The preparation of embodiment 3 CS/P-HMSS hybridized film
Take in a certain amount of ultrasonic 20 mL deionized waters that are scattered in the ATMP that contains 0.088 g of P-HMSS particle of preparing as embodiment 2.In dispersion liquid, add 0.3810 mL acetic acid, and be heated to 80
oc.Under mechanical stirring condition, in solution, dissolve 0.4 g chitosan.80
ounder C, vigorous stirring is dissolved 2 hours.After deaeration by film-casting liquid curtain coating on sheet glass, 25
ounder C, be dried to constant weight.In the aqueous sulfuric acid of 2 M crosslinked 24 hours subsequently, wash away residual sulfuric acid with deionized water, until washings is neutral, finally 25
ounder C, vacuum-drying film is to constant weight.The numbering of prepared film is respectively CS/P-HMSS-1.25, CS/P-HMSS-2.5, CS/P-HMSS-5, CS/P-HMSS-7.5, CS/P-HMSS-10, and wherein inorganic materials P-HMSS consumption is respectively 1.25 wt.%, 2.5 wt.%, 5 wt.%, 7.5 wt.%, 10 wt.% of chitosan dosage.
The preparation of the pure CS film of comparative example 1
0.3810 mL acetate dissolution, in 20 mL deionized waters, and is heated to 80
oc dissolves 0.4 g chitosan under mechanical stirring condition in solution.80
ounder C, vigorous stirring is dissolved 2 hours.After deaeration by film-casting liquid curtain coating on sheet glass, 25
ounder C, be dried to constant weight.In the aqueous sulfuric acid of 2 M crosslinked 24 hours subsequently, wash away residual sulfuric acid with deionized water, until washings is neutral, finally 25
ounder C, vacuum-drying film, to constant weight, does not contain organic and/or inorganic materials in gained CS film.
The preparation of comparative example 2 CS/HMSS hybridized film
Take a certain amount of ultrasonic being scattered in 20 mL deionized waters of HMSS particle of preparing as embodiment 1.In dispersion liquid, add 0.3810 mL acetic acid, and be heated to 80
oc.Under mechanical stirring condition, in solution, dissolve 0.4 g chitosan.80
ounder C, vigorous stirring is dissolved 2 hours.After deaeration by film-casting liquid curtain coating on sheet glass, 25
ounder C, be dried to constant weight.In the aqueous sulfuric acid of 2 M crosslinked 24 hours subsequently, wash away residual sulfuric acid with deionized water, until washings is neutral, finally 25
ounder C, vacuum-drying film is to constant weight.The numbering of prepared film is respectively CS/HMSS-1.25, CS/HMSS-2.5, CS/HMSS-5, CS/HMSS-7.5, CS/HMSS-10, and wherein inorganic materials HMSS consumption is respectively 1.25 wt.%, 2.5 wt.%, 5 wt.%, 7.5 wt.%, 10 wt.% of chitosan dosage.
Test condition
The mould material proton conductivity test condition making in embodiment and comparative example is: the humidity of controlling diaphragm material is 100% RH, by using electrochemical workstation (electrochemical workstation in room temperature temperature-rise period, PARSTAT 2273, Princeton) level of test membrane material is to proton conductivity.In test process, temperature is elevated to certain numerical value, reach the highest tolerable temperature of mould material under 100% RH, while exceeding this temperature, the destruction of mould material recurring structure, cannot measure proton conductivity, therefore the end temp of mould material proton conduction is the highest tolerable temperature under 100% RH again, has reflected the hydrothermal stability of mould material under test condition.The methanol permeability test condition of mould material is in 2 mol/L methanol solutions, under room temperature condition, test methyl alcohol sees through the spread coefficient of film, the i.e. methanol permeability of film.
In each mould material prepared by embodiment and comparative example, inorganic materials content, the highest tolerable temperature, proton conductivity and methanol permeability are in table 1.
Table 1
ainorganic materials accounts for the massfraction of chitosan
bthe highest tolerable temperature of mould material under 100% RH proton conductivity test condition
As can be seen from Figure 1 in film, fill P-HMSS and HMSS particle, 30
ounder C condition, hybridized film proton conductivity all gets a promotion, and CS/P-HMSS hybridized film proton conductivity promotes amplitude maximum.This is because inserting in film of HMSS particle introduced more water conservations site, is conducive to transmit proton by delivery mechanism; Inserting further of P-HMSS introduced proton transfer site phosphate radical and fix proton transfer site phosphate radical in hollow acid pond at hole wall, reduced the energy barrier that transmits proton by Hopping mechanism.30
ounder C, 100% RH condition, CS/P-HMSS hybridized film proton conductivity lifting amplitude maximum can reach 98%.Fig. 2 is the proton conductivity figure of film under 100% RH intensification test condition, and the end temp of mould material test has reflected that film can tolerate top temperature under 100% RH.100
owhen C, it is identical with the pure film of CS that the filling of HMSS particle has maintained hybridized film proton conductivity substantially, and the introducing of P-HMSS particle has improved the proton conductivity of hybridized film CS/P-HMSS, higher than pure film.Exceed 100
oc, the pure film of CS is swelling excessively destroyed, 105
owhen C, CS/P-HMSS has the proton conductivity higher than CS/HMSS.Exceed 105
oc, CS/HMSS hybridized film is same swelling excessively destroyed, and CS/P-HMSS hybridized film still has hydrothermal stability and excellent proton conductivity.Explanation thus, it is 100 that the pure film of CS can tolerate top temperature under 100% RH test condition
oc, inserts the highest tolerable temperature of HMSS and can be promoted to 105
oc, the filling of P-HMSS can further be increased to 110 by tolerable temperature
oc, this explanation inorganic materials has stronger stability structure, and the structure of hybridized film has strengthened the hydrothermal stability of mould material, has improved the adaptability of film under test condition.
Under test condition, the methanol permeability of CS/HMSS is lower than the pure film of CS, the effect that hinders methanol molecules material transfer has been played in the introducing that inorganic materials is described, improve the alcohol-rejecting ability of mould material, although the methanol permeability of CS/P-HMSS slightly increases than the pure film of CS, but substantially maintain the level of the pure film of CS, and along with the increase of inorganic materials massfraction in film, and present the trend that methanol crossover is inhibited.In sum, P-HMSS is introduced to the CS/P-HMSS hybridized film obtaining after CS membrane matrix and has the proton conductivity of enhancing, excellent hydrothermal stability, is applied to and in DMFC, has certain advantage, and its high proton conductivity can reach 0.0934 S cm
-1(CS/P-HMSS-7.5,110
oc, 100% RH), hydrothermal stability can reach 110
oc, and hinder preferably alcohol characteristic (8.42 × 10
-7cm
2s
-1).
Claims (4)
1. the mesoporous hollow silica hybridized film of chitosan/phosphorylation, it is characterized in that it is taking the mesoporous hollow silica submicron spherical of phosphorylation particle as inorganic filler, chitosan is as organic substrate, and the massfraction that the mesoporous hollow silica submicron spherical of phosphorylation particle accounts for chitosan is 1.25 wt.%-10 wt.%.
2. the preparation method of the mesoporous hollow silica hybridized film of chitosan/phosphorylation as claimed in claim 1, it is characterized in that it comprises the following steps: be scattered in the deionized water that contains certain mass Amino Trimethylene Phosphonic Acid ultrasonic mesoporous phosphorylation hollow silica particle, to adding in dispersion liquid, to account for film-casting liquid total mass mark be the acetic acid of 2 wt.%, and be heated to 80
oc, under mechanical stirring condition, in solution, add chitosan, wherein to account for film-casting liquid total mass mark be 2 wt.% to chitosan, the 1.25 wt.%-10 wt.% that the mesoporous hollow silica particle of phosphorylation consumption is chitosan, it is 0.12 wt.%-0.44 wt.% that Amino Trimethylene Phosphonic Acid accounts for film-casting liquid total mass mark, 80
ounder C, vigorous stirring is dissolved and within 2 hours, is obtained film-casting liquid, by after film-casting liquid deaeration on sheet glass curtain coating, dry, crosslinked with aqueous sulfuric acid, the dry hybridized film that obtains of then washing.
3. a preparation method for the mesoporous hollow silica hybridized film of chitosan/phosphorylation as claimed in claim 2, is characterized in that the mesoporous hollow silica particle of phosphorylation prepared as follows:
1) adopt the synthetic monodisperse silica submicron spherical particle of St ber method as kernel;
2) to step 1) to be coated with cetyl trimethylammonium bromide be template for the particle skin that makes, the mesoporous lamella that teos hydrolysis polycondensation forms;
3) kernel of use aqueous sodium carbonate etching particle;
4) the cetyl trimethylammonium bromide template of use methanolic hydrochloric acid solution removal particle, synthesising mesoporous hollow silica particle;
5) use epoxy silane coupling (3-glycidyl oxygen propyl trimethoxy silicane) in dry toluene to step 4) particle that makes carries out epoxy group(ing) modification;
6) using phosphorus oxychloride to step 5) particle that makes carries out phosphorylation.
4. the mesoporous hollow silica film of chitosan/phosphorylation as claimed in claim 1 is in the application of direct methanol fuel cell.
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